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Sample records for ferromagnetic transition-metal doped

  1. Ferromagnetism in Fe-doped transition metal nitrides

    Sharma, Ramesh; Sharma, Yamini

    2018-04-01

    Early transition metal mononitrides ScN and YN are refractory compounds with high hardness and melting points as well semiconducting properties. The presence of nitrogen vacancies in ScN/YN introduces asymmetric peaks in the density of states close to Fermi level, the same effects can be achieved by doping by Mn or Fe-atoms. Due to the substitution of TM atoms at Sc/Y sites, it was found that the p-d hybridization induces small magnetic moments at both Sc/Y and N sites giving rise to magnetic semiconductors (MS). From the calculated temperature dependent transport properties, the power factor and ZT is found to be lowered for doped ScN whereas it increases for doped YN. It is proposed that these materials have promising applications as spintronics and thermoelectric materials.

  2. Spectrum of ferromagnetic transition metal magnetic excitations and neutron scattering

    Kuzemskij, A.L.

    1979-01-01

    Quantum statistical models of ferromagnetic transition metals as well as methods of their solutions are reviewed. The correspondence of results on solving these models and the data on scattering thermal neutrons in ferromagnetic is discussed

  3. Magnetic excitations in transition-metal ferromagnets

    Uemura, Y.J.

    1984-01-01

    A review is given on current neutron scattering experiments at Brookhaven National Laboratory on transition-metal ferromagnets Ni, Fe, Pd 2 MnSn and MnSi. The scattering intensity in constant-energy scans, observed above T/sub c/ in all of these materials, exhibited a clear peak at finite momentum transfers. Using a simple scattering function with double-Lorentzian shape, we demonstrate that this peak is a manifestation of simple diffusive spin fluctuations. Experimental results of several parameters are compared in the context of localized-moment and itinerant-electron pictures. The ratio of spin wave stiffness constant D and transition temperature kT/sub c/ is shown to be a good yardstick for the degree of itinerancy of d-electrons

  4. Half-Metallic Ferromagnetism and Stability of Transition Metal Pnictides and Chalcogenides

    Liu, Bang-Gui

    It is highly desirable to explore robust half-metallic ferromagnetic materials compatible with important semiconductors for spintronic applications. A state-of-the-art full potential augmented plane wave method within the densityfunctional theory is reliable enough for this purpose. In this chapter we review theoretical research on half-metallic ferromagnetism and structural stability of transition metal pnictides and chalcogenides. We show that some zincblende transition metal pnictides are half-metallic and the half-metallic gap can be fairly wide, which is consistent with experiment. Systematic calculations reveal that zincblende phases of CrTe, CrSe, and VTe are excellent half-metallic ferromagnets. These three materials have wide half-metallic gaps, are low in total energy with respect to the corresponding ground-state phases, and, importantly, are structurally stable. Halfmetallic ferromagnetism is also found in wurtzite transition metal pnictides and chalcogenides and in transition-metal doped semiconductors as well as deformed structures. Some of these half-metallic materials could be grown epitaxially in the form of ultrathin .lms or layers suitable for real spintronic applications.

  5. Two-dimensional ferromagnet/semiconductor transition metal dichalcogenide contacts: p-type Schottky barrier and spin-injection control

    Gan, Liyong; Cheng, Yingchun; Schwingenschlö gl, Udo; Zhang, Qingyun

    2013-01-01

    We study the ferromagnet/semiconductor contacts formed by transition metal dichalcogenide monolayers, focusing on semiconducting MoS2 and WS2 and ferromagnetic VS2. We investigate the degree of p-type doping and demonstrate tuning of the Schottky barrier height by vertical compressive pressure. An analytical model is presented for the barrier heights that accurately describes the numerical findings and is expected to be of general validity for all transition metal dichalcogenide metal/semiconductor contacts. Furthermore, magnetic proximity effects induce a 100% spin polarization at the Fermi level in the semiconductor where the spin splitting increases up to 0.70 eV for increasing pressure.

  6. Two-dimensional ferromagnet/semiconductor transition metal dichalcogenide contacts: p-type Schottky barrier and spin-injection control

    Gan, Liyong

    2013-09-26

    We study the ferromagnet/semiconductor contacts formed by transition metal dichalcogenide monolayers, focusing on semiconducting MoS2 and WS2 and ferromagnetic VS2. We investigate the degree of p-type doping and demonstrate tuning of the Schottky barrier height by vertical compressive pressure. An analytical model is presented for the barrier heights that accurately describes the numerical findings and is expected to be of general validity for all transition metal dichalcogenide metal/semiconductor contacts. Furthermore, magnetic proximity effects induce a 100% spin polarization at the Fermi level in the semiconductor where the spin splitting increases up to 0.70 eV for increasing pressure.

  7. Properties of Transition Metal Doped Alumina

    Nykwest, Erik; Limmer, Krista; Brennan, Ray; Blair, Victoria; Ramprasad, Rampi

    Crystallographic texture can have profound effects on the properties of a material. One method of texturing is through the application of an external magnetic field during processing. While this method works with highly magnetic systems, doping is required to couple non-magnetic systems with the external field. Experiments have shown that low concentrations of rare earth (RE) dopants in alumina powders have enabled this kind of texturing. The magnetic properties of RE elements are directly related to their f orbital, which can have as many as 7 unpaired electrons. Since d-block elements can have as many as 5 unpaired electrons the effects of substitutional doping of 3d transition metals (TM) for Al in alpha (stable) and theta (metastable) alumina on the local structure and magnetic properties, in addition to the energetic cost, have been calculated by performing first-principles calculations based on density functional theory. This study has led to the development of general guidelines for the magnetic moment distribution at and around the dopant atom, and the dependence of this distribution on the dopant atom type and its coordination environment. It is anticipated that these findings can aid in the selection of suitable dopants help to guide parallel experimental efforts. This project was supported in part by an internship at the Army Research Laboratory, administered by the Oak Ridge Institute for Science and Education, along with a grant of computer time from the DoD High Performance Computing Modernization Program.

  8. Electronic structure and magnetism in transition metals doped 8-hydroxy-quinoline aluminum.

    Baik, Jeong Min; Shon, Yoon; Lee, Seung Joo; Jeong, Yoon Hee; Kang, Tae Won; Lee, Jong-Lam

    2008-10-15

    We report the room-temperature ferromagnetism in transition metals (Co, Ni)-doped 8-hydroxy-quinoline aluminum (Alq3) by thermal coevaporation of high purity metal and Alq3 powders. For 5% Co-doped Alq3, a maximum magnetization of approximately 0.33 microB/Co at 10 K was obtained and ferromagnetic behavior was observed up to 300 K. The Co atoms interact chemically with O atoms and provide electrons to Alq3, forming new states acting as electron trap sites. From this, it is suggested that ferromagnetism may be associated with the strong chemical interaction of Co atoms and Alq3 molecules.

  9. Low temperature synthesis, photoluminescence, magnetic properties of the transition metal doped wurtzite ZnS nanowires

    Cao, Jian; Han, Donglai; Wang, Bingji; Fan, Lin; Fu, Hao; Wei, Maobin; Feng, Bo; Liu, Xiaoyan; Yang, Jinghai

    2013-01-01

    In this paper, we synthesized the transition metal ions (Mn, Cu, Fe) doped and co-doped ZnS nanowires (NWs) by a one-step hydrothermal method. The results showed that the solid solubility of the Fe 2+ ions in the ZnS NWs was about two times larger than that of the Mn 2+ or Cu 2+ ions in the ZnS NWs. There was no phase transformation from hexagonal to cubic even in a large quantity transition metal ions introduced for all the samples. The Mn 2+ /Cu 2+ /Fe 2+ related emission peaks can be observed in the Mn 2+ ,Cu 2+ and Fe 2+ doped ZnS NWs. The ferromagnetic properties of the co-doped samples were investigated at room temperature. - graphical abstract: The stable wurtzite ZnS:TM 2+ (TM=Mn, Cu, Fe) nanowires with room temperature ferromagnetism properties were obtained. The different elongation of unit cell caused by the different doped ions was observed. Highlights: ► The transition metal ions doped wurtzite ZnS nanowires were synthesized at 180 °C. ► There was no phase transformation from hexagonal to cubic even in a large quantity introduced for all the samples. ► The room temperature ferromagnetism properties of the co-doped nanowires were investigated

  10. Ferromagnetism and spin glass ordering in transition metal alloys (invited)

    Crane, S.; Carnegie, D. W., Jr.; Claus, H.

    1982-03-01

    Magnetic properties of transition metal alloys near the percolation threshold are often complicated by metallurgical effects. Alloys like AuFe, VFe, CuNi, RhNi, and PdNi are in general not random solid solutions but have various degrees of atomic clustering or short-range order (SRO), depending on the heat treatment. First, it is shown how the magnetic ordering temperature of these alloys varies with the degree of clustering or SRO. Second, by systematically changing this degree of clustering or SRO, important information can be obtained about the magnetic phase diagram. In all these alloys below the percolation limit, the onset of ferromagnetic order is probably preceded by a spin glass-type ordering. However, details of the magnetic phase diagram near the critical point can be quite different alloy systems.

  11. Transition Metal Dopants Essential for Producing Ferromagnetism in Metal Oxide Nanoparticles

    Johnson, Lydia; Thurber, Aaron P.; Anghel, Josh; Sabetian, Maryam; Engelhard, Mark H.; Tenne, D.; Hanna, Charles; Punnoose, Alex

    2010-08-13

    Recent claims that ferromagnetism can be produced in nanoparticles of metal oxides without the presence of transition metal dopants has been refuted in this work by investigating 62 high quality well-characterized nanoparticle samples of both undoped and Fe doped (0-10% Fe) ZnO. The undoped ZnO nanoparticles showed zero or negligible magnetization, without any dependence on the nanoparticle size. However, chemically synthesized Zn₁₋xFexO nanoparticles showed clear ferromagnetism, varying systematically with Fe concentration. Furthermore, the magnetic properties of Zn₁₋xFexO nanoparticles showed strong dependence on the reaction media used to prepare the samples. The zeta potentials of the Zn₁₋xFexO nanoparticles prepared using different reaction media were significantly different, indicating strong differences in the surface structure. Electron paramagnetic resonance studies clearly showed that the difference in the ferromagnetic properties of Zn₁₋xFexO nanoparticles with different surface structures originate from differences in the fraction of the doped Fe³⁺ ions that are coupled ferromagnetically.

  12. Magnetism in 3d transition metal doped SnO

    Albar, Arwa

    2016-09-12

    Using first principles calculations, we investigate the structural and electronic properties of 3d transition metal doped SnO. We examine the stability of different doping sites using formation energy calculations. The magnetic behavior of the dopant atoms is found to be complex because of interplay between strong structural relaxation, spin-lattice coupling, and crystal field splitting. The interaction between dopant atoms is analyzed as a function of their separation, showing that clustering typically counteracts spin polarization. An exception is found for V doping, which thus turns out to be a promising candidate for realizing a magnetic p-type oxide.

  13. Electron-doping by hydrogen in transition-metal dichalcogenides

    Oh, Sehoon; Im, Seongil; Choi, Hyoung Joon

    Using first-principles calculations, we investigate the atomic and electronic structures of 2H-phase transition-metal dichalcogenides (TMDC), 2H-MX2, with and without defects, where M is Mo or W and X is S, Se or Te. We find that doping of atomic hydrogen on 2H-MX2 induces electron doping in the conduction band. To understand the mechanism of this electron doping, we analyze the electronic structures with and without impurities. We also calculate the diffusion energy barrier to discuss the spatial stability of the doping. Based on these results, we suggest a possible way to fabricate elaborately-patterned circuits by modulating the carrier type of 2H-MoTe2. We also discuss possible applications of this doping in designing nano-devices. This work was supported by NRF of Korea (Grant No. 2011-0018306) and KISTI supercomputing center (Project No. KSC-2016-C3-0052).

  14. The origin of magnetism in transition metal-doped ZrO2 thin films: Experiment and theory

    Hong, Nguyenhoa

    2013-10-04

    We have investigated the magnetic properties of Fe/Co/Ni-doped ZrO 2 laser ablated thin films in comparison with the known results of Mn-doped ZrO2, which is thought to be a promising material for spintronics applications. It is found that doping with a transition metal can induce room temperature ferromagnetism in \\'fake\\' diamond. Theoretical analysis based on density functional theory confirms the experimental measurements, by revealing that the magnetic moments of Mn- and Ni-doped ZrO2 thin films are much larger than that of Fe- or Co-doped ZrO2 thin films. Most importantly, our calculations confirm that Mn- and Ni-doped ZrO2 show a ferromagnetic ground state in comparison to Co- and Fe-doped ZrO 2, which favor an antiferromagnetic ground state. © 2013 IOP Publishing Ltd.

  15. Electronic and magnetic properties of SnS2 monolayer doped with 4d transition metals

    Xiao, Wen-Zhi; Xiao, Gang; Rong, Qing-Yan; Chen, Qiao; Wang, Ling-Ling

    2017-09-01

    We investigate the electronic structures and magnetic properties of SnS2 monolayers substitutionally doped with 4-d transition-metal through systematic first principles calculations. The doped complexes exhibit interesting electronic and magnetic behaviors, depending on the interplay between crystal field splitting, Hund's rule, and 4d levels. The system doped with Y is nonmagnetic metal. Both the Zr- and Pd-doped systems remain nonmagnetic semiconductors. Doping results in half-metallic states for Nb-, Ru-, Rh-, Ag, and Cd doped cases, and magnetic semiconductors for systems with Mo and Tc dopants. In particular, the Nb- and Mo-doped systems display long-ranged ferromagnetic ordering with Curie temperature above room temperature, which are primarily attributable to the double-exchange mechanism, and the p-d/p-p hybridizations, respectively. Moreover, The Mo-doped system has excellent energetic stability and flexible mechanical stability, and also possesses remarkable dynamic and thermal (500 K) stability. Our studies demonstrate that Nb- and Mo-doped SnS2 monolayers are promising candidates for preparing 2D diluted magnetic semiconductors, and hence will be a helpful clue for experimentalists.

  16. Novel doping alternatives for single-layer transition metal dichalcogenides

    Onofrio, Nicolas; Guzman, David; Strachan, Alejandro

    2017-11-01

    Successful doping of single-layer transition metal dichalcogenides (TMDs) remains a formidable barrier to their incorporation into a range of technologies. We use density functional theory to study doping of molybdenum and tungsten dichalcogenides with a large fraction of the periodic table. An automated analysis of the energetics, atomic and electronic structure of thousands of calculations results in insightful trends across the periodic table and points out promising dopants to be pursued experimentally. Beyond previously studied cases, our predictions suggest promising substitutional dopants that result in p-type transport and reveal interesting physics behind the substitution of the metal site. Doping with early transition metals (TMs) leads to tensile strain and a significant reduction in the bandgap. The bandgap increases and strain is reduced as the d-states are filled into the mid TMs; these trends reverse as we move into the late TMs. Additionally, the Fermi energy increases monotonously as the d-shell is filled from the early to mid TMs and we observe few to no gap states, indicating the possibility of both p- (early TMs) and n- (mid TMs) type doping. Quite surprisingly, the simulations indicate the possibility of interstitial doping of TMDs; the energetics reveal that a significant number of dopants, increasing in number from molybdenum disulfide to diselenide and to ditelluride, favor the interstitial sites over adsorbed ones. Furthermore, calculations of the activation energy associated with capturing the dopants into the interstitial site indicate that the process is kinetically possible. This suggests that interstitial impurities in TMDs are more common than thought to date and we propose a series of potential interstitial dopants for TMDs relevant for application in nanoelectronics based on a detailed analysis of the predicted electronic structures.

  17. Defect-mediated magnetism of transition metal doped zinc oxide thin films

    Roberts, Bradley Kirk

    Magnetism in transition metal doped wide band-gap materials is of interest to further the fundamental science of materials and future spintronics applications. Large inter-dopant separations require mediation of ferromagnetism by some method; carrier-mediated mechanisms are typically applicable to dilute magnetic semiconductors with low Curie temperatures. Dilute magnetic oxides, commonly with poor conductivity and TC above room temperature, cannot be described within this theory. Recent experiment and theory developments suggest that ferromagnetic exchange in these materials can be mediated by defects. This research includes experimental results justifying and developing this approach. Thin films of Cr doped ZnO (band gap ˜3.3 eV) were deposited with several processing variations to enhance the effects of either 0-dimensional (vacancy, hydrogen-related defect) or two-dimensional defects (surface/interface) and thereby affect magnetism and conductivity. We observe surface magnetism in dielectric thin films of oxygen-saturated ZnO:Cr with spontaneous magnetic moment and conductance dropping approximately exponentially with increasing thickness. Uniform defect concentrations would not result in such magnetic ordering behavior indicating that magnetism is mediated either by surface defects or differing concentrations of point defects near the surface. Polarized neutron reflectivity profiling confirms a magnetically active region of ˜8 nm at the film surface. Hydrogen is notoriously present as a defect and carrier dopant in ZnO, and artificial introduction of hydrogen in dielectric ZnO:Cr films results in varying electronic and magnetic behavior. Free carriers introduced with hydrogen doping are not spin-polarized requiring an alternative explanation for ferromagnetism. We find from positron annihilation spectroscopy measurements that hydrogen doping increases the concentration of an altered VZn-related defect (a preliminary interpretation) throughout the film, which

  18. Transition-metal-doped group-IV monochalcogenides: a combination of two-dimensional triferroics and diluted magnetic semiconductors

    Yang, Liu; Wu, Menghao; Yao, Kailun

    2018-05-01

    We report the first-principles evidence of a series of two-dimensional triferroics (ferromagnetic + ferroelectric + ferroelastic), which can be obtained by doping transition-metal ions in group-IV monochalcogenide (SnS, SnSe, GeS, GeSe) monolayers, noting that a ferromagnetic Fe-doped SnS2 monolayer has recently been realized (Li B et al 2017 Nat. Commun. 8 1958). The ferroelectricity, ferroelasticity and ferromagnetism can be coupled and the magnetization direction may be switched upon ferroelectric/ferroelastic switching, rendering electrical writing + magnetic reading possible. They can be also two-dimensional half-metals or diluted magnetic semiconductors, where p/n channels or even multiferroic tunneling junctions can be designed by variation in doping and incorporated into a monolayer wafer.

  19. Magnetic properties of zigzag (0,9 GaAs nanotube doped with 3d transition metals

    R Fathi

    2016-06-01

    Full Text Available of 3d transition metals (Sc, Ti, Cr, Mn , Fe, Co, Ni in both far and close situations were studied based on spin polarised density functional theory using the generalized gradient approximation (LDA with SIESTA code. The electronic structures show that zigzag (0,9 GaAs nanotubes are non-magnetic semiconductors with direct band gap. It was revealed that doping of 11.11 % Fe and Mn concentrations substituted in Ga sites in ferromagnetic phase in far situation and Cr sites in ferromagnetic phase in near situation introduces half metallic behavior with %100 spin polarization. The unique structure of spin polarised energy levels is primarily attributed to strong hybridization of 3d transition metal and its nearest-neighbor As-4p orbitals. The results of this study can be useful for empirical studies on diluted magnetic semiconductors (DMSs and systemic investigation in 3d transitional metals. We suggest that GaAs nanotubes doped by transition metals would have a potential application as a spin polarised electron source for spintronic devices in the future.

  20. Strain tunable magnetic properties of 3d transition-metal ion doped monolayer MoS2: A first-principles study

    Zhu, Yupeng; Liang, Xiao; Qin, Jun; Deng, Longjiang; Bi, Lei

    2018-05-01

    In this article, a systematic study on the magnetic properties and strain tunability of 3d transition metal ions (Mn, Fe, Co, Ni) doped MoS2 using first-principles calculations is performed. Antiferromagnetic coupling is observed between Mn, Fe ions and the nearest neighbor Mo ions; whereas ferromagnetic coupling is observed in Co and Ni systems. It is also shown that by applying biaxial tensile strain, a significant change of the magnetic moment is observed in all transition metal doped MoS2 materials with a strain threshold. The changes of total magnetic moment have different mechanisms for different doping systems including an abrupt change of the bond lengths, charge transfer and strain induced structural anisotropy. These results demonstrate applying strain as a promising method for tuning the magnetic properties in transition metal ion doped monolayer MoS2.

  1. Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses

    Das, Santanu; Choudhary, Kamal; Chernatynskiy, Aleksandr; Choi Yim, Haein; Bandyopadhyay, Asis K.; Mukherjee, Sundeep

    2016-06-01

    High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe-Co metallic glass system of composition [(Co1-x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent ‘Stoner type’ magnetization for the amorphous alloys in contrast to ‘Heisenberg type’ in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study.

  2. Prediction of Intrinsic Ferromagnetic Ferroelectricity in a Transition-Metal Halide Monolayer

    Huang, Chengxi; Du, Yongping; Wu, Haiping; Xiang, Hongjun; Deng, Kaiming; Kan, Erjun

    2018-04-01

    The realization of multiferroics in nanostructures, combined with a large electric dipole and ferromagnetic ordering, could lead to new applications, such as high-density multistate data storage. Although multiferroics have been broadly studied for decades, ferromagnetic ferroelectricity is rarely explored, especially in two-dimensional (2D) systems. Here we report the discovery of 2D ferromagnetic ferroelectricity in layered transition-metal halide systems. On the basis of first-principles calculations, we reveal that a charged CrBr3 monolayer exhibits in-plane multiferroicity, which is ensured by the combination of orbital and charge ordering as realized by the asymmetric Jahn-Teller distortions of octahedral Cr - Br6 units. As an example, we further show that (CrBr3)2Li is a ferromagnetic ferroelectric multiferroic. The explored phenomena and mechanism of multiferroics in this 2D system not only are useful for fundamental research in multiferroics but also enable a wide range of applications in nanodevices.

  3. Extended Moment Formation in Monolayer WS2 Doped with 3d Transition-Metals

    Singh, Nirpendra; Schwingenschlö gl, Udo

    2016-01-01

    First-principles calculations with onsite Coulomb interaction and spin-orbit coupling are used to investigate the electronic structure of monolayer WS2 doped substitutionally with 3d transition-metals. While neither W vacancies nor strain induce

  4. Valley polarization in magnetically doped single-layer transition-metal dichalcogenides

    Cheng, Yingchun; Zhang, Q. Y.; Schwingenschlö gl, Udo

    2014-01-01

    We demonstrate that valley polarization can be induced and controlled in semiconducting single-layer transition-metal dichalcogenides by magnetic doping, which is important for spintronics, valleytronics, and photonics devices. As an example, we

  5. Application of machine-learning methods to solid-state chemistry: ferromagnetism in transition metal alloys

    Landrum, G.A.Gregory A.; Genin, Hugh

    2003-01-01

    Machine-learning methods are a collection of techniques for building predictive models from experimental data. The algorithms are problem-independent: the chemistry and physics of the problem being studied are contained in the descriptors used to represent the known data. The application of a variety of machine-learning methods to the prediction of ferromagnetism in ordered and disordered transition metal alloys is presented. Applying a decision tree algorithm to build a predictive model for ordered phases results in a model that is 100% accurate. The same algorithm achieves 99% accuracy when trained on a data set containing both ordered and disordered phases. Details of the descriptor sets for both applications are also presented

  6. Synthesis and characterization of transition-metal-doped zinc oxide nanocrystals for spintronics

    Wang, Xuefeng

    Spintronics (spin transport electr onics), in which both spin and charge of carriers are utilized for information processing, is believed to challenge the current microelectronics and to become the next-generation electronics. Nanostructured spintronic materials and their synthetic methodologies are of paramount importance for manufacturing future nanoscale spintronic devices. This thesis aims at studying synthesis, characterization, and magnetism of transition-metal-doped zinc oxide (ZnO) nanocrystals---a diluted magnetic semiconductor (DMS)---for potential applications in future nano-spintronics. A simple bottom-up-based synthetic strategy named a solvothermal technique is introduced as the primary synthetic approach and its crystal growth mechanism is scrutinized. N-type cobalt-doped ZnO-based DMS nanocrystals are employed as a model system, and characterized by a broad spectrum of advanced microscopic and spectroscopic techniques. It is found that the self-orientation growth mechanism, imperfect oriented attachment, is intimately correlated with the high-temperature ferromagnetism via defects. The influence of processing on the magnetic properties, such as compositional variations, reaction conditions, and post-growth treatment, is also studied. In this way, an in-depth understanding of processing-structure-property interrelationships and origins of magnetism in DMS nanocrystals are obtained in light of the theoretical framework of a spin-split impurity band model. In addition, a nanoscale spinodal decomposition phase model is also briefly discussed. Following the similar synthetic route, copper- and manganese-doped ZnO nanocrystals have been synthesized and characterized. They both show high-temperature ferromagnetism in line with the aforementioned theoretical model(s). Moreover, they display interesting exchange biasing phenomena at low temperatures, revealing the complexity of magnetic phases therein. The crystal growth strategy demonstrated in this work

  7. Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

    Higgs, T. D. C.; Bonetti, S.; Ohldag, H.; Banerjee, N.; Wang, X. L.; Rosenberg, A. J.; Cai, Z.; Zhao, J. H.; Moler, K. A.; Robinson, J. W. A.

    2016-07-01

    Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. The results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

  8. A comparative study of the magnetization in transition metal ion doped CeO2, TiO2 and SnO2 nanoparticles

    Apostolov, A. T.; Apostolova, I. N.; Wesselinowa, J. M.

    2018-05-01

    Using the microscopic s-d model taking into account anharmonic spin-phonon interactions we have studied the magnetic properties of Co and Cu ion doped CeO2 and TiO2 nanoparticles and compared them with those of SnO2. By Co-doping there is a maximum in the magnetization M(x) curve for all nanoparticles observed in the most transition metal doped ones. The s-d interaction plays an important role by the decrease of M at higher dopant concentration. We have discussed the magnetization in dependence of different model parameters. By small Cu-ion doping there are some differences. In CeO2M decreases with the Cu-concentration, whereas in TiO2 and SnO2M increases. For higher Cu dopant concentrations M(X) decreases in TiO2 nanoparticles. We obtain room temperature ferromagnetism also in Zn doped CeO2, TiO2 and SnO2 nanoparticles, i.e. in non-transition metal ion doped ones. The different behavior of M in Co and Cu doped nanoparticles is due to a combination effect of multivalent metal ions, oxygen vacancies, different radius of cation dopants, connection between lattice and magnetism, as well as competition between the s-d and d-d ferromagnetic or antiferromagnetic interactions.

  9. Phase stabilisation of hexagonal barium titanate doped with transition metals: A computational study

    Dawson, J.A.; Freeman, C.L.; Harding, J.H.; Sinclair, D.C.

    2013-01-01

    Interatomic potentials recently developed for the modelling of BaTiO 3 have been used to explore the stabilisation of the hexagonal polymorph of BaTiO 3 by doping with transition metals (namely Mn, Co, Fe and Ni) at the Ti-site. Classical simulations have been completed on both the cubic and hexagonal polymorphs to investigate the energetic consequences of transition metal doping on each polymorph. Ti-site charge compensation mechanisms have been used for the multi-valent transition metal ions and cluster binding energies have been considered. Simulations show a significant energetic gain when doping occurs at Ti sites in the face sharing dimers (Ti 2 sites) of the hexagonal polymorph compared with the doping of the cubic polymorph. This energetic difference between the two polymorphs is true for all transition metals tested and all charge states and in the case of tri- and tetra-valent dopants negative solution energies are found for the hexagonal polymorph suggesting actual polymorph stabilisation occurs with the incorporation of these ions as observed experimentally. Oxidation during incorporation of Ni 2+ and Fe 3+ ions has also been considered. - Graphical abstract: The representation of the strongest binding energy clusters for tri-valent dopants—(a) Ti 2 /O 1 cluster and (b) Ti 2 /O 2 cluster. Highlights: ► Classical simulations show a significant energetic gain when doping occurs at Ti sites in the face sharing dimers (Ti2 sites) of the hexagonal polymorph compared with the doping of the cubic polymorph. ► This energetic difference between the two polymorphs is true for all transition metals tested and all charge states. ► In the case of tri- and tetra- valent dopants negative solution energies are found for the hexagonal polymorph suggesting actual polymorph stabilisation occurs with the incorporation of these ions

  10. Electronic structures and valence band splittings of transition metals doped GaNs

    Lee, Seung-Cheol; Lee, Kwang-Ryeol; Lee, Kyu-Hwan

    2007-01-01

    For a practical viewpoint, presence of spin splitting of valence band in host semiconductors by the doping of transition metal (TM) ions is an essential property when designing a diluted magnetic semiconductors (DMS) material. The first principle calculations were performed on the electronic and magnetic structure of 3d transition metal doped GaN. V, Cr, and Mn doped GaNs could not be candidates for DMS materials since most of their magnetic moments is concentrated on the TM ions and the splittings of valence band were negligible. In the cases of Fe, Co, Ni, and Cu doped GaNs, on the contrary, long-ranged spin splitting of valence band was found, which could be candidates for DMS materials

  11. Origin of exotic ferromagnetic behavior in exfoliated layered transition metal dichalcogenides MoS.sub.2./sub. and WS.sub.2./sub.

    Luxa, J.; Jankovský, O.; Sedmidubský, D.; Medlín, R.; Maryško, Miroslav; Pumera, M.; Sofer, Z.

    2016-01-01

    Roč. 8, č. 4 (2016), s. 1960-1967 ISSN 2040-3364 Institutional support: RVO:68378271 Keywords : transition metal dichalcogenides * ferromagnetism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 7.367, year: 2016

  12. Extended Moment Formation in Monolayer WS2 Doped with 3d Transition-Metals

    Singh, Nirpendra

    2016-08-30

    First-principles calculations with onsite Coulomb interaction and spin-orbit coupling are used to investigate the electronic structure of monolayer WS2 doped substitutionally with 3d transition-metals. While neither W vacancies nor strain induce spin polarization, we demonstrate an unprecedented tendency to extended moment formation under doping. The extended magnetic moments are characterized by dopant-specific spin density patterns with rich structural features involving the nearest neighbor W and S atoms.

  13. Valley polarization in magnetically doped single-layer transition-metal dichalcogenides

    Cheng, Yingchun

    2014-04-28

    We demonstrate that valley polarization can be induced and controlled in semiconducting single-layer transition-metal dichalcogenides by magnetic doping, which is important for spintronics, valleytronics, and photonics devices. As an example, we investigate Mn-doped MoS2 by first-principles calculations. We study how the valley polarization depends on the strength of the spin orbit coupling and the exchange interaction and discuss how it can be controlled by magnetic doping. Valley polarization by magnetic doping is also expected for other honeycomb materials with strong spin orbit coupling and the absence of inversion symmetry.

  14. First-principles study of hydrogen dissociation and diffusion on transition metal-doped Mg(0 0 0 1) surfaces

    Wang, Zhiwen; Guo, Xinjun; Wu, Mingyi; Sun, Qiang; Jia, Yu

    2014-01-01

    First-principles calculations within the density functional theory (DFT) have been carried out to study hydrogen molecules dissociation and diffusion on clean and transition metals (TMs) doped Mg(0 0 0 1) surfaces following Pozzo et al. work. Firstly, the stability of Mg(0 0 0 1) surface doped with transition metals atom has been studied. The results showed that transition metals on the left of the table tend to substitute Mg in the second layer, while the other transition metals prefer to substitute Mg in the first layer. Secondly, we studied hydrogen molecules dissociation and diffusion on clean and Mg(0 0 0 1) surfaces which the transition metal atoms substituted both in the first layer and second layer. When transition metal atoms substitute in the first layer, the results agree with the Pozzo et al. result; when transition metal atoms substitute in the second layer, the results showed that the transition metals on the left of the periodic table impact on the dissociation barriers is less. However, for the transition metals (Mn, Fe, Co, Ni) on the right, there is a great impact on the barriers. The transition metals doped surfaces bind the dissociated H atoms loosely, making them easily diffused. The results further reveal that the Fe dopant on the Mg surface is the best choice for H 2 dissociation and hydrogen storage.

  15. Significant enhancement of room temperature ferromagnetism in surfactant coated polycrystalline Mn doped ZnO particles

    Jayakumar, O.D. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Gopalakrishnan, I.K. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)]. E-mail: ikgopal@barc.gov.in; Sudakar, C. [Department of Physics and Astronomy, Wayne State University, Detroit, MI 48201 (United States); Kadam, R.M. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Kulshreshtha, S.K. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

    2007-07-12

    We report a surfactant assisted synthesis of Mn doped ZnO polycrystalline samples showing robust room temperature ferromagnetism as characterized by X-ray diffraction analysis, transmission electron microscopy, electron paramagnetic resonance and DC magnetization measurements. This surfactant assisted synthesis method, developed by us, is found to be highly reproducible. Further, it can also be extended to the synthesis of other transition metal doped ZnO.

  16. Understanding the Room Temperature Ferromagnetism in GaN Nanowires with Pd Doping

    Manna, S; De, S K

    2011-01-01

    We report the first synthesis and characterization of 4d transition metal palladium-doped GaN nanowires (NWs). Room temperature ferromagnetism has been observed in high quality Vapor Liquid Solid (VLS) epitaxy grown undoped n-type GaN nanowires. It was proposed that this type of magnetism is due to defects which are not observed in Bulk GaN because of large formation energy of defects in bulk GaN. Here we have successfully doped 4d transition metal Pd in GaN NWs. We find fairly strong and long-range ferromagnetic coupling between Pd substituted for Ga in GaN . The results suggest that 4d metals such as Pd may also be considered as candidates for ferromagnetic dopants in semiconductors.

  17. High energy transmission of Al2O3 doped with light transition metals

    Schuster, Cosima

    2012-01-31

    The transmission of transparent colored ceramics based on Al2O3doped with light transition metals is measured in the visible and infrared range. To clarify the role of the dopands we perform ab initiocalculations. We discuss the electronic structure and present optical spectra obtained in the independent particle approximation. We argue that the gross spectral features of Co- and Ni-doped Al2O3 samples are described by our model, while the validity of the approach is limited for Cr-doped Al2O3.

  18. High energy transmission of Al2O3 doped with light transition metals

    Schuster, Cosima; Klimke, J.; Schwingenschlö gl, Udo

    2012-01-01

    The transmission of transparent colored ceramics based on Al2O3doped with light transition metals is measured in the visible and infrared range. To clarify the role of the dopands we perform ab initiocalculations. We discuss the electronic structure and present optical spectra obtained in the independent particle approximation. We argue that the gross spectral features of Co- and Ni-doped Al2O3 samples are described by our model, while the validity of the approach is limited for Cr-doped Al2O3.

  19. Synthesis, structural and optical properties of PVP coated transition metal doped ZnS nanoparticles

    Desai, N. V.; Shaikh, I. A.; Rawal, K. G.; Shah, D. V.

    2018-05-01

    The room temperature photoluminescence (PL) of transition metal doped ZnS nanoparticles is investigated in the present study. The PVP coated ZnS nanoparticles doped with transition metals are synthesized by facile wet chemical co-precipitation method with the concentration of impurity 1%. The UV-Vis absorbance spectra have a peak at 324nm which shifts slightly to 321nm upon introduction of the impurity. The incorporation of the transition metal as dopant is confirmed by X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS). The particle size and the morphology are characterized by scanning electron microscopy (SEM), XRD and UV-Vis spectroscopy. The average size of synthesized nanoparticles is about 2.6nm. The room temperature photoluminescence (PL) of undoped and doped ZnS nanoparticles show a strong and sharp peak at 782nm and 781.6nm respectively. The intensity of the PL changes with the type of doping having maximum for manganese (Mn).

  20. Adsorption and dissociation of dinitrogen on transition metal (Ta, W and Re) doped MgO surface

    Yadav, Manoj Kumar; Vovusha, Hakkim; Sanyal, Biplab

    2016-01-01

    The adsorption and dissociation of dinitrogen on transition metal (Ta, W and Re) doped MgO(100) surface has been studied employing density functional theory. It is found that all these transition metals (TM) on MgO(100) surface are capable

  1. The electronic structure and ferromagnetism of TM (TM=V, Cr, and Mn)-doped BN(5, 5) nanotube: A first-principles study

    He, K.H.; Zheng, G.; Chen, G.; Wan, M.; Ji, G.F.

    2008-01-01

    We study the electronic structure and ferromagnetism of V-, Cr-, and Mn-doped single-wall BN(5, 5) nanotube by using polarized spin calculations within first principles. The optimized structures show that the transition-metal atoms move outwards and the calculated electronic properties demonstrate that the isolated V-, Cr-, and Mn-doped BN(5, 5) nanotubes show half-metallicity. The total ferromagnetic moments are 2μ B , 3.02μ B , and 3.98μ B for V-, Cr-, and Mn-doped BN(5, 5), respectively. The study suggests that such transition-metal (TM)-doped nanotubes may be useful in spintronics and nanomagnets

  2. Adsorption and dissociation of dinitrogen on transition metal (Ta, W and Re) doped MgO surface

    Yadav, Manoj Kumar

    2016-06-16

    The adsorption and dissociation of dinitrogen on transition metal (Ta, W and Re) doped MgO(100) surface has been studied employing density functional theory. It is found that all these transition metals (TM) on MgO(100) surface are capable of adsorbing dinitrogen (N2), however there is no dissociative adsorption of N2 on single transition metal dopant. When two TM atoms are doped on MgO(100) surface, dissociative adsorption of dinitrogen occurs in all the three cases. Whether the dissociation is spontaneous or is it associated with activation barrier depends on the orientation of N2 molecule approaching the dopant site.

  3. Chemical hole doping into large-area transition metal dichalcogenide monolayers using boron-based oxidant

    Matsuoka, Hirofumi; Kanahashi, Kaito; Tanaka, Naoki; Shoji, Yoshiaki; Li, Lain-Jong; Pu, Jiang; Ito, Hiroshi; Ohta, Hiromichi; Fukushima, Takanori; Takenobu, Taishi

    2018-01-01

    Hole carrier doping into single-crystalline transition metal dichalcogenide (TMDC) films can be achieved with various chemical reagents. However, large-area polycrystalline TMDC monolayers produced by a chemical vapor deposition (CVD) growth method have yet to be chemically doped. Here, we report that a salt of a two-coordinate boron cation, Mes2B+ (Mes: 2,4,6-trimethylphenyl group), with a chemically stable tetrakis(pentafluorophenyl)borate anion, [(C6F5)4B]−, can serve as an efficient hole-doping reagent for large-area CVD-grown tungsten diselenide (WSe2) films. Upon doping, the sheet resistance of large-area polycrystalline WSe2 monolayers decreased from 90 GΩ/sq to 3.2 kΩ/sq.

  4. Chemical hole doping into large-area transition metal dichalcogenide monolayers using boron-based oxidant

    Matsuoka, Hirofumi

    2018-01-18

    Hole carrier doping into single-crystalline transition metal dichalcogenide (TMDC) films can be achieved with various chemical reagents. However, large-area polycrystalline TMDC monolayers produced by a chemical vapor deposition (CVD) growth method have yet to be chemically doped. Here, we report that a salt of a two-coordinate boron cation, Mes2B+ (Mes: 2,4,6-trimethylphenyl group), with a chemically stable tetrakis(pentafluorophenyl)borate anion, [(C6F5)4B]−, can serve as an efficient hole-doping reagent for large-area CVD-grown tungsten diselenide (WSe2) films. Upon doping, the sheet resistance of large-area polycrystalline WSe2 monolayers decreased from 90 GΩ/sq to 3.2 kΩ/sq.

  5. Synthesis and characterization of three-dimensional transition metal ions doped zinc oxide based dilute magnetic semiconductor thin films

    Samanta, Kousik

    Dilute magnetic semiconductors (DMS), especially 3d-transition metal (TM) doped ZnO based DMS materials are the most promising candidates for optoelectronics and spintronics applications; e.g. in spin light emitting diode (SLED), spin transistors, and spin field effect transistors (SFET), etc. In the present dissertation, thin films of Zn1-xTMxO (TM = Co2+, Cu2+, and Mn2+) were grown on (0001) oriented Al2O3 substrates by pulsed laser deposition (PLD) technique. The films were highly c-axis oriented, nearly single crystalline, and defects free for a limited concentration of the dilution of transition metal ions. In particular, we have obtained single crystalline phases of Zn1-xTMxO thin films for up to 10, 3, and 5 stoichiometric percentages of Co2+, Cu2+, and Mn2+ respectively. Raman micro-probe system was used to understand the structural and lattice dynamical properties at different physical conditions. The confinement of optical phonons in the disorder lattice was explained by alloy potential fluctuation (APF) using a spatial correlation (SC) model. The detailed analysis of the optical phonon behavior in disorder lattice confirmed the substitution of the transition metal ions in Zn 2+ site of the ZnO host lattice. The secondary phases of ZnCo 2O4, CuO, and ZnMn2O4 were detected in higher Co, Cu, and Mn doped ZnO thin films respectively; where as, XRD did not detect these secondary phases in the same samples. Room temperature ferromagnetism was observed in Co2+ and Cu2+ ions doped ZnO thin films with maximum saturation magnetization (Ms) of 1.0 and 0.76 muB respectively. The origin of the observed ferromagnetism in Zn1-xCoxO thin films was tested by the controlled introduction of shallow donors (Al) in Zn0.9-x Co0.1O:Alx (x = 0.005 and 0.01) thin films. The saturation magnetization for the 10% Co-doped ZnO (1.0 muB /Co) at 300K reduced (˜0.25 muB/Co) due to Al doping. The observed ferromagnetism and the reduction due to Al doping can be explained by the Bound

  6. Recombination of charge carriers on radiation-induced defects in silicon doped by transition metals impurities

    Kazakevich, L A

    2003-01-01

    It has been studied the peculiarities of recombination of nonequilibrium charge carriers on radiation-induced defects in received according to Czochralski method p-silicon (p approx 3 - 20 Ohm centre dot cm), doped by one of the impurities of transition metals of the IV-th group of periodic table (titanium, zirconium, hafnium). Experimental results are obtained out of the analysis of temperature and injection dependence of the life time of charge carriers. The results are explained taking into consideration the influences of elastic stress fields created by the aggregates of transition metals atoms on space distribution over the crystal of oxygen and carbon background impurities as well as on the migration of movable radiation-induced defects during irradiation. (authors).

  7. Systematics of electronic and magnetic properties in the transition metal doped Sb2Te3 quantum anomalous Hall platform

    Islam, M. F.; Canali, C. M.; Pertsova, A.; Balatsky, A.; Mahatha, S. K.; Carbone, C.; Barla, A.; Kokh, K. A.; Tereshchenko, O. E.; Jiménez, E.; Brookes, N. B.; Gargiani, P.; Valvidares, M.; Schatz, S.; Peixoto, T. R. F.; Bentmann, H.; Reinert, F.; Jung, J.; Bathon, T.; Fauth, K.; Bode, M.; Sessi, P.

    2018-04-01

    The quantum anomalous Hall effect (QAHE) has recently been reported to emerge in magnetically doped topological insulators. Although its general phenomenology is well established, the microscopic origin is far from being properly understood and controlled. Here, we report on a detailed and systematic investigation of transition metal (TM) doped Sb2Te3 . By combining density functional theory calculations with complementary experimental techniques, i.e., scanning tunneling microscopy, resonant photoemission, and x-ray magnetic circular dichroism, we provide a complete spectroscopic characterization of both electronic and magnetic properties. Our results reveal that the TM dopants not only affect the magnetic state of the host material, but also significantly alter the electronic structure by generating impurity-derived energy bands. Our findings demonstrate the existence of a delicate interplay between electronic and magnetic properties in TM doped topological insulators. In particular, we find that the fate of the topological surface states critically depends on the specific character of the TM impurity: while V- and Fe-doped Sb2Te3 display resonant impurity states in the vicinity of the Dirac point, Cr and Mn impurities leave the energy gap unaffected. The single-ion magnetic anisotropy energy and easy axis, which control the magnetic gap opening and its stability, are also found to be strongly TM impurity dependent and can vary from in plane to out of plane depending on the impurity and its distance from the surface. Overall, our results provide general guidelines for the realization of a robust QAHE in TM doped Sb2Te3 in the ferromagnetic state.

  8. Density functional theory study of elemental mercury adsorption on boron doped graphene surface decorated by transition metals

    Jungsuttiwong, Siriporn, E-mail: siriporn.j@ubu.ac.th [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani 34190 (Thailand); Wongnongwa, Yutthana [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani 34190 (Thailand); Namuangruk, Supawadee [National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Klong Luang, Pathum Thani 12120 (Thailand); Kungwan, Nawee [Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Promarak, Vinich [Department of Material Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210 (Thailand); Kunaseth, Manaschai, E-mail: manaschai@nanotec.or.th [National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Klong Luang, Pathum Thani 12120 (Thailand)

    2016-01-30

    Graphical abstract: Decoration of Pd{sub 4}-A (square planar) on B-doped graphene significantly promotes Hg{sup 0} adsorption, a single site of Pd{sub 4} cluster on BDG could strongly adsorb up to six Hg atoms. - Highlights: • Transition metal atom and cluster binds strongly on B-doped graphene surface. • Decoration of transition metal on B-doped graphene significantly promotes Hg{sup 0} adsorption. • Adsorption strength of Hg{sup 0} atom on metal decorated B-doped graphene: Pd > Pt > Ru > W > Cu. • One site decorated Pd4 cluster adsorbed Hg{sup 0} strongly up to six atoms.

  9. Phase engineering of monolayer transition-metal dichalcogenide through coupled electron doping and lattice deformation

    Ouyang, Bin; Lan, Guoqiang; Song, Jun; Guo, Yinsheng; Mi, Zetian

    2015-01-01

    First-principles calculations were performed to investigate the phase stability and transition within four monolayer transition-metal dichalcogenide (TMD) systems, i.e., MX 2 (M = Mo or W and X = S or Se) under coupled electron doping and lattice deformation. With the lattice distortion and electron doping density treated as state variables, the energy surfaces of different phases were computed, and the diagrams of energetically preferred phases were constructed. These diagrams assess the competition between different phases and predict conditions of phase transitions for the TMDs considered. The interplay between lattice deformation and electron doping was identified as originating from the deformation induced band shifting and band bending. Based on our findings, a potential design strategy combining an efficient electrolytic gating and a lattice straining to achieve controllable phase engineering in TMD monolayers was demonstrated

  10. First-principles study of doping effect on the phase transition of zinc oxide with transition metal doped

    Wu, Liang; Hou, Tingjun; Wang, Yi; Zhao, Yanfei; Guo, Zhenyu; Li, Youyong; Lee, Shuit-Tong

    2012-01-01

    Highlights: ► We study the doping effect on B4, B1 structures and phase transition of ZnO. ► We calculate the phase transition barrier and phase transition path of doped ZnO. ► The transition metal doping decreases the bulk modulus and phase transition pressure. ► The magnetic properties are influenced by the phase transition process. - Abstract: Zinc oxide (ZnO) is a promising material for its wide application in solid-state devices. With the pressure raised from an ambient condition, ZnO transforms from fourfold wurtzite (B4) to sixfold coordinated rocksalt (B1) structure. Doping is an efficient approach to improve the structures and properties of materials. Here we use density-functional theory (DFT) to study doped ZnO and find that the transition pressure from B4 phase to B1 phase of ZnO always decreases with different types of transition metal (V, Cr, Mn, Fe, Co, or Ni) doped, but the phase transition path is not affected by doping. This is consistent with the available experimental results for Mn-doped ZnO and Co-doped ZnO. Doping in ZnO causes the lattice distortion, which leads to the decrease of the bulk modulus and accelerates the phase transition. Mn-doped ZnO shows the strongest magnetic moment due to its half filled d orbital. For V-doped ZnO and Cr-doped ZnO, the magnetism is enhanced by phase transition from B4 to B1. But for Mn-doped ZnO, Fe-doped ZnO, Co-doped ZnO, and Ni-doped ZnO, B1 phase shows weaker magnetic moment than B4 phase. These results can be explained by the amount of charge transferred from the doped atom to O atom. Our results provide a theoretical basis for the doping approach to change the structures and properties of ZnO.

  11. Magnetic engineering in InSe/black-phosphorus heterostructure by transition-metal-atom Sc-Zn doping in the van der Waals gap

    Ding, Yi-min; Shi, Jun-jie; Zhang, Min; Zhu, Yao-hui; Wu, Meng; Wang, Hui; Cen, Yu-lang; Guo, Wen-hui; Pan, Shu-hang

    2018-07-01

    Within the framework of the spin-polarized density-functional theory, we have studied the electronic and magnetic properties of InSe/black-phosphorus (BP) heterostructure doped with 3d transition-metal (TM) atoms from Sc to Zn. The calculated binding energies show that TM-atom doping in the van der Waals (vdW) gap of InSe/BP heterostructure is energetically favorable. Our results indicate that magnetic moments are induced in the Sc-, Ti-, V-, Cr-, Mn- and Co-doped InSe/BP heterostructures due to the existence of non-bonding 3d electrons. The Ni-, Cu- and Zn-doped InSe/BP heterostructures still show nonmagnetic semiconductor characteristics. Furthermore, in the Fe-doped InSe/BP heterostructure, the half-metal property is found and a high spin polarization of 100% at the Fermi level is achieved. The Cr-doped InSe/BP has the largest magnetic moment of 4.9 μB. The Sc-, Ti-, V-, Cr- and Mn-doped InSe/BP heterostructures exhibit antiferromagnetic ground state. Moreover, the Fe- and Co-doped systems display a weak ferromagnetic and paramagnetic coupling, respectively. Our studies demonstrate that the TM doping in the vdW gap of InSe/BP heterostructure is an effective way to modify its electronic and magnetic properties.

  12. Optical properties of 3d transition metal ion-doped sodium borosilicate glass

    Wen, Hongli; Tanner, Peter A.

    2015-01-01

    Graphical abstract: Photographs of undoped (SiO 2 ) 50 (Na 2 O) 25 (B 2 O 3 ) 25 (SiNaB) glass and transition metal ion-doped (TM) 0.5 (SiO 2 ) 49.5 (Na 2 O) 25 (B 2 O 3 ) 25 glass samples. - Highlights: • 3d transition metal ion (from Ti to Zn) doped SiO 2 -Na 2 O-B 2 O 3 glasses. • Optical properties of doped glasses investigated. • V(IV,V); Cr(III, VI); Mn(II,III); Fe(II,III); Co(II); Ni(II); Cu(II) by XANES, DRS. • Strong visible absorption but only vanadium ion gives strong emission in glass. - Abstract: SiO 2 -Na 2 O-B 2 O 3 glasses doped with 3d-transition metal species from Ti to Zn were prepared by the melting-quenching technique and their optical properties were investigated. The X-ray absorption near edge spectra of V, Cr, and Mn-doped glasses indicate that the oxidation states of V(IV, V), Cr(III, VI) and Mn(II, III) exist in the studied glasses. The oxidation states revealed from the diffuse reflectance spectra of the glasses are V(IV, V), Cr(III, VI), Mn(III), Fe(II, III), Co(II), Ni(II), and Cu(II). Most of the 3d transition element ions exhibit strong absorption in the visible spectral region in the glass. Under ultraviolet excitation, the undoped sodium borosilicate glass produces weak and broad emission, while doping of vanadium introduces strong and broad emission due to the V(V) charge transfer transition. Only weak emission is observed from Ti(IV), Mn(II), Fe(III) and Cu(II), partly resulting from the strong electron–phonon coupling of the 3d-electrons and the relatively high phonon energy of the studied glass host, with the former leading to dominant nonradiative relaxation based on multiphonon processes for most of the 3d excited states

  13. Ferromagnetism in doped or undoped spintronics nanomaterials

    Qiang, You

    2010-10-01

    Much interest has been sparked by the discovery of ferromagnetism in a range of oxide doped and undoped semiconductors. The development of ferromagnetic oxide semiconductor materials with giant magnetoresistance (GMR) offers many advantages in spintronics devices for future miniaturization of computers. Among them, TM-doped ZnO is an extensively studied n-type wide-band-gap (3.36 eV) semiconductor with a tremendous interest as future mini-computer, blue light emitting, and solar cells. In this talk, Co-doped ZnO and Co-doped Cu2O semiconductor nanoclusters are successfully synthesized by a third generation sputtering-gas-aggregation cluster technique. The Co-doped nanoclusters are ferromagnetic with Curie temperature above room temperature. Both of Co-doped nanoclusters show positive magnetoresistance (PMR) at low temperature, but the amplitude of the PMRs shows an anomalous difference. For similar Co doping concentration at 5 K, PMR is greater than 800% for Co-doped ZnO but only 5% for Co-doped Cu2O nanoclusters. Giant PMR in Co-doped ZnO which is attributed to large Zeeman splitting effect has a linear dependence on applied magnetic field with very high sensitivity, which makes it convenient for the future spintronics applications. The small PMR in Co-doped Cu2O is related to its vanishing density of states at Fermi level. Undoped Zn/ZnO core-shell nanoparticle gives high ferromagnetic properties above room temperature due to the defect induced magnetization at the interface.

  14. Adsorption of formaldehyde molecule on the pristine and transition metal doped graphene: First-principles study

    Chen, Xin; Xu, Lei; Liu, Lin-Lin; Zhao, Lu-Si; Chen, Chun-Ping; Zhang, Yong; Wang, Xiao-Chun

    2017-01-01

    Highlights: • Formaldehyde molecule (H_2CO) is a common environmental pollutant with strong toxicity. • Total 36 different initial configurations of H_2CO molecule adsorbing onto three types of substrates have been investigated. • The Ti-doped graphene has the enough binding energy, significant changes in electronic structure, and reasonable short recovery time 10"−"3 s. • The Ti-doped graphene is a promising candidate for detecting formaldehyde gas. - Abstract: The adsorption of H_2CO molecule on pristine and transition metal (Ti and V) doped graphene samples were investigated via a first-principles approach based on density functional theory. The most stable adsorption geometry, energy and charge transfer of H_2CO molecule on pristine and doped graphene are discussed respectively. We have found that Ti and V dopant atoms can significantly enhance the interaction between H_2CO molecule and graphene. The calculated net electron transfers, electronic density difference images and densities of states give the evidence that the H_2CO molecules stay on Ti (or V) – doped graphene by chemisorption. After H_2CO adsorption, there are significant changes in electronic structure near the Fermi level, for both two systems of Ti and V doped graphene. This indicates distinct changes of electron transport properties. We have also found that H_2CO molecule has a larger absorption energy on V-doped graphene (1.939 eV) compared with Ti-doped graphene (1.120 eV). It is shown that the Ti-doped graphene has enough binding energy, adequate changes in electronic structure and reasonable short recovery time 10"−"3 s, making it a promising candidate for detecting formaldehyde gas.

  15. Adsorption of formaldehyde molecule on the pristine and transition metal doped graphene: First-principles study

    Chen, Xin [Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130012 (China); Institute of Theoretical Chemistry, Jilin University, Changchun 130012 (China); Xu, Lei [Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130012 (China); College of Physics, Jilin University, Changchun, 130012 (China); Liu, Lin-Lin; Zhao, Lu-Si; Chen, Chun-Ping [Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun, 130012 (China); Zhang, Yong [Department of Electrical and Computer Engineering, The University of North Carolina at Charlotte, Charlotte, NC 28223-0001 (United States); Wang, Xiao-Chun, E-mail: wangxiaochun@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun, 130012 (China)

    2017-02-28

    Highlights: • Formaldehyde molecule (H{sub 2}CO) is a common environmental pollutant with strong toxicity. • Total 36 different initial configurations of H{sub 2}CO molecule adsorbing onto three types of substrates have been investigated. • The Ti-doped graphene has the enough binding energy, significant changes in electronic structure, and reasonable short recovery time 10{sup −3} s. • The Ti-doped graphene is a promising candidate for detecting formaldehyde gas. - Abstract: The adsorption of H{sub 2}CO molecule on pristine and transition metal (Ti and V) doped graphene samples were investigated via a first-principles approach based on density functional theory. The most stable adsorption geometry, energy and charge transfer of H{sub 2}CO molecule on pristine and doped graphene are discussed respectively. We have found that Ti and V dopant atoms can significantly enhance the interaction between H{sub 2}CO molecule and graphene. The calculated net electron transfers, electronic density difference images and densities of states give the evidence that the H{sub 2}CO molecules stay on Ti (or V) – doped graphene by chemisorption. After H{sub 2}CO adsorption, there are significant changes in electronic structure near the Fermi level, for both two systems of Ti and V doped graphene. This indicates distinct changes of electron transport properties. We have also found that H{sub 2}CO molecule has a larger absorption energy on V-doped graphene (1.939 eV) compared with Ti-doped graphene (1.120 eV). It is shown that the Ti-doped graphene has enough binding energy, adequate changes in electronic structure and reasonable short recovery time 10{sup −3} s, making it a promising candidate for detecting formaldehyde gas.

  16. Effect of transition metal-doped Ni(211) for CO dissociation: Insights from DFT calculations

    Yang, Kuiwei; Zhang, Minhua [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Yu, Yingzhe, E-mail: yzhyu@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China)

    2017-03-31

    Highlights: • Doping the step edge of Ni(211) with Fe or Ru observably enhances CO dissociation. • Rh doping is unfavorable for CO activation both kinetically and thermodynamically. • Two neat linear relations are proposed besides the Brønsted–Evans–Polanyi relation. • The differences of CO adsorption are rationalized via the Blyholder model. - Abstract: Density functional theory slab calculations were performed to investigate the adsorption and dissociation of CO over pure and M-doped Ni(211) (M = Fe, Co, Ru and Rh) with the aim to elucidate the effect of transition metal doping for CO activation. Doping the step edge of Ni(211) with Fe, Co and Ru is found to enhance the binding of CO in the initial state (IS) (in the sequence by the improvement degree: Fe > Ru > Co) as well as the co-adsorption of C and O in the final state (FS) (Ru > Fe > Co). In contrast, Rh doping is unfavorable both in the IS and in the FS. Analysis of the overall potential energy surfaces (PES) suggests CO dissociation is facilitated by Fe, Ru and Co doping both kinetically and thermodynamically, wherein Fe and Ru behave extraordinary. Interestingly, Fe substitute is slightly superior to Ru in kinetics whereas the contrary is the case in thermodynamics. Rh doping elevates the energy height from 0.97 eV on Ni(211) to 1.32 eV and releases 0.39 eV less heat relative to Ni(211), again manifesting a negative effect. Besides the classical Brønsted–Evans–Polanyi relationship, we put forward another two neat linear relations, which can well describe the feature of CO dissociation. The differences of CO adsorption and activation in the IS over pure and doped Ni(211) surfaces are rationalized via electronic structure analysis. The findings presented herein are expected to provide theoretical guidance for catalyst design and optimization in relevant processes.

  17. The Influence of Doping with Transition Metal Ions on the Structure and Magnetic Properties of Zinc Oxide Thin Films

    Jenica Neamtu

    2014-01-01

    Full Text Available Zn1−xNixO (x=0.03÷0.10 and Zn1−xFexO (x=0.03÷0.15 thin films were synthesized by sol-gel method. The structure and the surface morphology of zinc oxide thin films doped with transition metal (TM ions have been investigated by X-ray diffraction (XRD and atomic force microscopy (AFM. The magnetic studies were done using vibrating sample magnetometer (VSM at room temperature. Experimental results revealed that the substitution of Ni ions in ZnO wurtzite lattice for the contents x=0.03÷0.10 (Ni2+ leads to weak ferromagnetism of thin films. For Zn1-xFexO with x=0.03÷0.05, the Fe3+ ions are magnetic coupling by superexchange interaction via oxygen ions in wurtzite structure. For x=0.10÷0.15 (Fe3+ one can observe the increasing of secondary phase of ZnFe2O4 spinel. The Zn0.9Fe0.1O film shows a superparamagnetic behavior due to small crystallite sizes and the net spin magnetic moments arisen from the interaction between the iron ions through an oxygen ion in the spinel structure.

  18. First-Row Transition Metal Doping in Calcium Phosphate Bioceramics: A Detailed Crystallographic Study

    Guillaume Renaudin

    2017-01-01

    Full Text Available Doped calcium phosphate bioceramics are promising materials for bone repair surgery because of their chemical resemblance to the mineral constituent of bone. Among these materials, BCP samples composed of hydroxyapatite (Ca10(PO46(OH2 and β-TCP (Ca3(PO42 present a mineral analogy with the nano-multi-substituted hydroxyapatite bio-mineral part of bones. At the same time, doping can be used to tune the biological properties of these ceramics. This paper presents a general overview of the doping mechanisms of BCP samples using cations from the first-row transition metals (from manganese to zinc, with respect to the applied sintering temperature. The results enable the preparation of doped synthetic BCP that can be used to tailor biological properties, in particular by tuning the release amounts upon interaction with biological fluids. Intermediate sintering temperatures stabilize the doping elements in the more soluble β-TCP phase, which favors quick and easy release upon integration in the biological environment, whereas higher sintering temperatures locate the doping elements in the weakly soluble HAp phase, enabling a slow and continuous supply of the bio-inspired properties. An interstitial doping mechanism in the HAp hexagonal channel is observed for the six investigated cations (Mn2+, Fe3+, Co2+, Ni2+, Cu2+ and Zn2+ with specific characteristics involving a shift away from the center of the hexagonal channel (Fe3+, Co2+, cationic oxidation (Mn3+, Co3+, and also cationic reduction (Cu+. The complete crystallochemical study highlights a complex HAp doping mechanism, mainly realized by an interstitial process combined with calcium substitution for the larger cations of the series leading to potentially calcium deficient HAp.

  19. k-asymmetric spin splitting at the interface between transition metal ferromagnets and heavy metals

    Grytsiuk, Sergii

    2016-05-23

    We systematically investigate the spin-orbit coupling-induced band splitting originating from inversion symmetry breaking at the interface between a Co monolayer and 4d (Tc, Ru, Rh, Pd, and Ag) or 5d (Re, Os, Ir, Pt, and Au) transition metals. In spite of the complex band structure of these systems, the odd-in-k spin splitting of the bands displays striking similarities with the much simpler Rashba spin-orbit coupling picture. We establish a clear connection between the overall strength of the odd-in-k spin splitting of the bands and the charge transfer between the d orbitals at the interface. Furthermore, we show that the spin splitting of the Fermi surface scales with the induced orbital moment, weighted by the spin-orbit coupling.

  20. k-asymmetric spin splitting at the interface between transition metal ferromagnets and heavy metals

    Grytsyuk, Sergiy; Belabbes, Abderrezak; Haney, Paul M.; Lee, Hyun-Woo; Lee, Kyung-Jin; Stiles, M. D.; Schwingenschlö gl, Udo; Manchon, Aurelien

    2016-01-01

    We systematically investigate the spin-orbit coupling-induced band splitting originating from inversion symmetry breaking at the interface between a Co monolayer and 4d (Tc, Ru, Rh, Pd, and Ag) or 5d (Re, Os, Ir, Pt, and Au) transition metals. In spite of the complex band structure of these systems, the odd-in-k spin splitting of the bands displays striking similarities with the much simpler Rashba spin-orbit coupling picture. We establish a clear connection between the overall strength of the odd-in-k spin splitting of the bands and the charge transfer between the d orbitals at the interface. Furthermore, we show that the spin splitting of the Fermi surface scales with the induced orbital moment, weighted by the spin-orbit coupling.

  1. High-Temperature Ferromagnetism in Transition Metal Implanted Wide-Bandgap Semiconductors

    2005-07-01

    Mn)As and Its Heterostructures,” Acta Physica Polonica A, 94 (2):155–164 (August 1998). 79. Ohno, Y., D. K. Young, B. Beschoten, F. Matsukura, H. Ohno...reactive molecular-beam epitaxy,” Physical Review B , 67 (16):16205 (April 2003). 26. Dietl, T. “From Magnetic Polarons to Ferromagnetism,” Acta Physica ...samples,” Physica B , 308-310 :985–988 (December 2001). 15. Bradley, F. N. Materials for Magnetic Functions (First Edition). New York: Hayden, 1971. 16

  2. Spin-dependent electronic transport properties of transition metal atoms doped α-armchair graphyne nanoribbons

    Fotoohi, Somayeh; Haji-Nasiri, Saeed

    2018-04-01

    Spin-dependent electronic transport properties of single 3d transition metal (TM) atoms doped α-armchair graphyne nanoribbons (α-AGyNR) are investigated by non-equilibrium Green's function (NEGF) method combined with density functional theory (DFT). It is found that all of the impurity atoms considered in this study (Fe, Co, Ni) prefer to occupy the sp-hybridized C atom site in α-AGyNR, and the obtained structures remain planar. The results show that highly localized impurity states are appeared around the Fermi level which correspond to the 3d orbitals of TM atoms, as can be derived from the projected density of states (PDOS). Moreover, Fe, Co, and Ni doped α-AGyNRs exhibit magnetic properties due to the strong spin splitting property of the energy levels. Also for each case, the calculated current-voltage characteristic per super-cell shows that the spin degeneracy in the system is obviously broken and the current becomes strongly spin dependent. Furthermore, a high spin-filtering effect around 90% is found under the certain bias voltages in Ni doped α-AGyNR. Additionally, the structure with Ni impurity reveals transfer characteristic that is suitable for designing a spin current switch. Our findings provide a high possibility to design the next generation spin nanodevices with novel functionalities.

  3. Band gap tuning and fluorescence properties of lead sulfide Pb0.9A0.1S (A: Fe, Co, and Ni) nanoparticles by transition metal doping

    Parveen, Azra; Agrawal, Shraddha; Azam, Ameer

    2018-02-01

    Transition metal-doped lead sulfide nanoparticles (PbS-NPs) were synthesized by co-precipitation method. The crystallite phase and morphological studies were carried out by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Optical studies were performed by UV-Visible absorption, fluorescence emission spectroscopy and Fourier transforms infrared spectroscopy (FTIR). XRD analysis reveals that the pure and transition metal-doped PbS- NPs have a single crystalline phase with cubic structure devoided of any other secondary phase. The notable effect on optical absorbance and band gap was observed with transition metal doping in lead sulphide. The optical energy band gap values were found to increase with the doping of transition metal. UV-Visible absorption and fluorescence emission spectra display a blue shift with subsequent transition metal doping which may arise due to quantum confinement effect making it worth for having applications in optoelectronic devices.

  4. Pressure dependence of the magnetic properties of various weakly ferromagnetic transition metal alloys

    Buis, N.

    1979-01-01

    A large number of experimental results are summarized obtained in an apparatus designed for the measurement of magnetization under high pressures (up to 5k bar gas pressure), at temperatures from 4.2K to room temperature and in magnetic fields up to 5.1 T. Two alloy systems studied were Zr (Fesub(1-x)Cosub(x)) 2 and Y(Fesub(x)Cosub(1-x)) 2 and no consistent picture could be deduced from the large pressure effects on the magnetization. Apparently, one cannot apply the model for weak itinerant ferromagnetism on Zr(Fesub(1-x)Cosub(x)) 2 or a simple giant moment model on Y(Fesub(x)Cosub(1-x)) 2 with small iron content, because the magnetic behaviour of both systems is too complicated. (C.F.)

  5. Electronic structures and magnetic properties of 3d and 4d transition-metal impurities in ferromagnetic Fe

    Park, J H; Min, B I; Cho, H S

    2000-01-01

    Employing the self-consistent local approach, the tight-binding linear-muffin-tin orbital recursion method, we have investigated the electronic structures and the magnetic properties of 3d and 4d transition-metal (TM) impurities in ferromagnetic bcc Fe. In both 3d and 4d TM impurities, virtual bound states appear and are characterized by a high density of states in the energy spectrum. The characters of the states are studied by calculating the bond order between interaction orbitals. For early TM impurities, the states at the impurity sites have more antibonding characters, while the states at neighboring Fe sites have more bonding characters. For late TM impurities, the situation is reversed. late TM impurities of both the 3d and the 4d TM series have the same magnetic ordering as the host Fe atoms whereas early TM impurities have magnetic moments antiparallel to that of the host. As for the Mn impurity, an inward relaxation of neighboring Fe atoms stabilizes the antiferromagnetic ordering with respect to t...

  6. Thermoelectric material including a multiple transition metal-doped type I clathrate crystal structure

    Yang, Jihui [Lakeshore, CA; Shi, Xun [Troy, MI; Bai, Shengqiang [Shanghai, CN; Zhang, Wenqing [Shanghai, CN; Chen, Lidong [Shanghai, CN; Yang, Jiong [Shanghai, CN

    2012-01-17

    A thermoelectric material includes a multiple transition metal-doped type I clathrate crystal structure having the formula A.sub.8TM.sub.y.sub.1.sup.1TM.sub.y.sub.2.sup.2 . . . TM.sub.y.sub.n.sup.nM.sub.zX.sub.46-y.sub.1.sub.-y.sub.2.sub.- . . . -y.sub.n.sub.-z. In the formula, A is selected from the group consisting of barium, strontium, and europium; X is selected from the group consisting of silicon, germanium, and tin; M is selected from the group consisting of aluminum, gallium, and indium; TM.sup.1, TM.sup.2, and TM.sup.n are independently selected from the group consisting of 3d, 4d, and 5d transition metals; and y.sub.1, y.sub.2, y.sub.n and Z are actual compositions of TM.sup.1, TM.sup.2, TM.sup.n, and M, respectively. The actual compositions are based upon nominal compositions derived from the following equation: z=8q.sub.A-|.DELTA.q.sub.1|y.sub.1-|.DELTA.q.sub.2|y.sub.2- . . . -|.DELTA.q.sub.n|y.sub.n, wherein q.sub.A is a charge state of A, and wherein .DELTA.q.sub.1, .DELTA.q.sub.2, .DELTA.q.sub.n are, respectively, the nominal charge state of the first, second, and n-th TM.

  7. The Effect of Transition Metal Doping on the Photooxidation Process of Titania-Clay Composites

    Judit Ménesi

    2008-01-01

    Full Text Available Montmorillonite-TiO2 composites containing various transition metal ions (silver, copper, or nickel were prepared, and their photocatalytic efficiencies were tested in the degradation of ethanol vapor at 70% relative humidity. Two light sources, UV-rich ( = 254 nm and visible ( = 435 nm, were used. The kinetics of degradation was monitored by gas chromatography. It was established that, in the case of each catalyst, ethanol degradation was more efficient in UV-C ( = 254 nm than in visible light, furthermore, these samples containing silver or copper ions were in each case about twice more efficient than P25 TiO2 (Degussa AG. used as a reference. In photooxidation by visible light, TiO2/clay samples doped with silver or copper were also more efficient than the reference sample, P25 TiO2. We show that doping metal ions can also be delivered to the surface of the support by ion exchange and significantly alters the optical characteristics of the TiO2/clay composite.

  8. Electronic and magnetic properties of 1T-HfS{sub 2} by doping transition-metal atoms

    Zhao, Xu, E-mail: zhaoxu@htu.cn [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, Henan 453007 (China); Wang, Tianxing; Wang, Guangtao [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, Henan 453007 (China); Dai, Xianqi [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, Henan 453007 (China); Department of Physics, Zhengzhou Normal University, Zhengzhou, Henan 450044 (China); Xia, Congxin [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, Henan 453007 (China); Yang, Lin [School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007 (China)

    2016-10-15

    Highlights: • Pristine 1T-HfS{sub 2} is a semiconductor with indirect gaps of 1.250 eV • Magnetism can be observed for V, Cr, Mn, Fe, Co, and Cu doping. • Strong p–d hybridization was found between TM 3d orbitals and S 3p orbitals. • V-doped 1T-HfS{sub 2} is ideal for spin injection. - Abstract: We explored the electronic and magnetic properties of 1T-HfS{sub 2} doped by transition metal (TM) atom using the first-principles calculation. We doped the transition metal atoms from the IIIB to VIB groups in nonmagnetic 1T-HfS{sub 2}. Numerical results show that the pristine 1T-HfS{sub 2} is a semiconductor with indirect gaps of 1.250 eV. Magnetism can be observed for V, Cr, Mn, Fe, Co, and Cu doping. The polarized charges mainly arise from the localized 3d electrons of the TM atom. The strong p–d hybridization was found between the 3d orbitals of TM and 3p orbitals of S. The substituted 1T-HfS{sub 2} can be a metal, semiconductor or half-metal. Analysis of the band structure and magnetic properties indicates that TM-doped HfS{sub 2} (TM = V, Fe, Cu) are promising systems to explore two-dimensional diluted magnetic semiconductors. The formation energy calculations also indicate that it is energetically favorable and relatively easier to incorporate transition metal atom into the HfS{sub 2} under S-rich experimental conditions. In contrast, V-doped HfS{sub 2} has relatively wide half-metallic gap and low formation energy. So V-doped 1T-HfS{sub 2} is ideal for spin injection, which is important for application in semiconductor spintronics.

  9. Electronic and magnetic properties of 3d transition metal-doped strontium clusters: Prospective magnetic superatoms

    Chauhan, Vikas; Sen, Prasenjit

    2013-01-01

    Highlights: • Structural, electronic and magnetic properties of TM-Sr clusters are studied using DFT methods. • CrSr 9 and MnSr 10 have enhanced stability in the CrSr n and MnSrn series. • These two clusters behave as magnetic superatoms. • A qualitative understanding of the magnetic coupling between two superatom units is offered. • Reactivity of these superatoms to molecular oxygen also studied. - Abstract: Structural, electronic and magnetic properties of 3d transition metal doped strontium clusters are studied using first-principles electronic structure methods based on density functional theory. Clusters with enhanced kinetic and thermodynamic stability are identified by studying their hardness, second order energy difference and adiabatic spin excitation energy. CrSr 9 and MnSr 10 are found to have enhanced stability. They retain their structural identities in assemblies, and are classified as magnetic superatoms. A qualitative understanding of the magnetic coupling between two cluster units is arrived at. Reactivity of these superatoms with O 2 molecule is also studied. Prospects for using these magnetic superatoms in applications are discussed

  10. Spectroscopic and ultrasonic investigations on structural characterization of borate glass specimen doped with transition metal ions.

    Sathish, K; Thirumaran, S

    2015-08-05

    The present work describes the glass samples of composition (x% V₂O₅-(80-x)% B₂O₃-20% Na₂CO₃) VBS glass system and (x%MnO₂-(80-x)% B₂O₃-20% Na₂CO₃) in MBS glass system with mol% ranging from x=3, 6, 9, 12, 15 and 18 in steps of 3 mol% are prepared by melt quenching technique. For these prepared glass systems, sound velocity (longitudinal and shear velocities) and density have been measured. The sound velocity (longitudinal and shear) was measured by using pulse-echo technique at 5 MHz. The XRD study was carried to out to ascertain the amorphous nature of the glass specimen. Using these measured values, the elastic moduli, Poisson's ratio, Debye temperature, acoustic impedance and thermal expansion coefficient of the two glass systems were evaluated. The elastic and mechanical properties of the prepared glass systems are analyzed from ultrasonic study and the structural characterization from spectroscopic study. The effects due to the doping of transition metal ions with borate have been discussed. In the V₂O₅ doped glass system,(VBS glass system) the sound velocity, density and elastic moduli, steeply increases after 12 mol% comparatively with MnO₂ doped glass system (VBS glass system). The present study critically observes the doping of V₂O₅ with borate enhances the strengthening of network linkage and hardening of the glassy network structure than MnO₂. The IR spectral analysis reveals depolymerization of the borate network and conversion of BO₃ or BO4 units with the formation of non-bridging oxygen. The FTIR spectral studies confirm the presence of various functional groups of the sample. FTIR spectrum of sample exhibits broad absorption bands indicating the wide distribution of borate structural units. The effect of Na₂CO₃, V₂O₅ and MnO₂ contents on the structures of borate glass is evaluated from the FTIR spectra. The topological aspects of the prepared glass samples are exhaustively reported from SEM micrographs

  11. Time-Dependent Density Functional Theory Analysis of Triphenylamine-Functionalized Graphene Doped with Transition Metals for Photocatalytic Hydrogen Production.

    Mota, Elder A V; Neto, Abel F G; Marques, Francisco C; Mota, Gunar V S; Martins, Marcelo G; Costa, Fabio L P; Borges, Rosivaldo S; Neto, Antonio M J C

    2018-07-01

    The electronic structures and optical properties of triphenylamine-functionalized graphene (G-TPA) doped with transition metals, using water as a solvent, were theoretically investigated to verify the efficiency of photocatalytic hydrogen production with the use of transition metals. This study was performed by Density Functional Theory and Time-dependent Density Functional Theory through Gaussian 09W software, adopting the B3LYP functional for all structures. The 6-31g(d) basis set was used for H, C and N atoms, and the LANL2DZ basis set for transition metals using the Effective Core Potentials method. Two approaches were adopted: (1) using single metallic dopants (Ni, Pd, Fe, Os and Pt) and (2) using combinations of Ni with the other dopants (NiPd, NiPt, NiFe and NiOs). The DOS spectra reveal an increase of accessible states in the valence shell, in addition to a gap decrease for all dopants. This doping also increases the absorption in the visible region of solar radiation where sunlight is most intense (400 nm to 700 nm), with additional absorption peaks. The results lead us to propose the G-TPA structures doped with Ni, Pd, Pt, NiPt or NiPd to be novel catalysts for the conversion of solar energy for photocatalytic hydrogen production, since they improve the absorption of solar energy in the range of interest for solar radiation; and act as reaction centers, reducing the required overpotential for hydrogen production from water.

  12. Analysis of the electronic structures of 3d transition metals doped CuGaS2 based on DFT calculations

    Zhao Zongyan; Zhou Dacheng; Yi Juan

    2014-01-01

    3d transition metals doped CuGaS 2 are considered as possible absorbing material candidates for intermediated band thin film solar cells. The electronic structure and optical properties of 3d transition metals doped CuGaS 2 are investigated by using density functional theory calculations with the GGA + U method in the present work. The doping with 3d transition metals does not obviously change the crystal structure, band gap, and optical absorption edge of the CuGaS 2 host. However, in the case of CuGa 1−x TM x S 2 (TM = Ti, V, Cr, Fe, and Ni), there is at least one distinct isolated impurity energy level in the band gap, and the optical absorption is enhanced in the ultraviolet-light region. Therefore, these materials are ideal absorber material candidates for intermediated band thin film solar cells. The calculated results are very well consistent with experimental observations, and could better explain them. (semiconductor materials)

  13. Ferromagnetic properties of manganese doped iron silicide

    Ruiz-Reyes, Angel; Fonseca, Luis F.; Sabirianov, Renat

    We report the synthesis of high quality Iron silicide (FeSi) nanowires via Chemical Vapor Deposition (CVD). The materials exhibits excellent magnetic response at room temperature, especially when doped with manganese showing values of 2.0 X 10-04 emu for the FexMnySi nanowires. SEM and TEM characterization indicates that the synthesized nanowires have a diameter of approximately 80nm. MFM measurements present a clear description of the magnetic domains when the nanowires are doped with manganese. Electron Diffraction and XRD measurements confirms that the nanowires are single crystal forming a simple cubic structure with space group P213. First-principle calculations were performed on (111) FeSi surface using the Vienna ab initio simulation package (VASP). The exchange correlations were treated under the Ceperley-Alder (CA) local density approximation (LDA). The Brillouin Zone was sampled with 8x8x1 k-point grid. A total magnetic moment of about 10 μB was obtained for three different surface configuration in which the Iron atom nearest to the surface present the higher magnetization. To study the effect of Mn doping, Fe atom was replaced for a Mn. Stronger magnetization is presented when the Mn atom is close to the surface. The exchange coupling constant have been evaluated calculating the energy difference between the ferromagnetic and anti-ferromagnetic configurations.

  14. A DFT investigation on group 8B transition metal-doped silicon carbide nanotubes for hydrogen storage application

    Tabtimsai, Chanukorn; Ruangpornvisuti, Vithaya; Tontapha, Sarawut; Wanno, Banchob

    2018-05-01

    The binding of group 8B transition metal (TMs) on silicon carbide nanotubes (SiCNT) hydrogenated edges and the adsorption of hydrogen molecule on the pristine and TM-doped SiCNTs were investigated using the density functional theory method. The B3LYP/LanL2DZ method was employed in all calculations for the considered structural, adsorption, and electronic properties. The Os atom doping on the SiCNT is found to be the strongest binding. The hydrogen molecule displays a weak interaction with pristine SiCNT, whereas it has a strong interaction with TM-doped SiCNTs in which the Os-doped SiCNT shows the strongest interaction with the hydrogen molecule. The improvement in the adsorption abilities of hydrogen molecule onto TM-doped SiCNTs is due to the protruding structure and the induced charge transfer between TM-doped SiCNT and hydrogen molecule. These observations point out that TM-doped SiCNTs are highly sensitive toward hydrogen molecule. Moreover, the adsorptions of 2-5 hydrogen molecules on TM-doped SiCNT were also investigated. The maximum storage number of hydrogen molecules adsorbed on the first layer of TM-doped SiCNTs is 3 hydrogen molecules. Therefore, TM-doped SiCNTs are suitable to be sensing and storage materials for hydrogen gas.

  15. Room-temperature ferromagnetism in Co and Nb co-doped TiO2 nanoparticles

    Hachisu, M.; Mori, K.; Hyodo, K.; Morimoto, S.; Yamazaki, T.; Ichiyanagi, Y.

    2015-01-01

    Co- and Nb-doped TiO 2 nanoparticles encapsulated with amorphous SiO 2 were synthesized by our novel preparation method. An anatase TiO 2 single-phase structure was confirmed using X-ray diffraction. The particle size could be controlled to be about 5 nm. The composition of these nanoparticles was investigated by X-ray fluorescence analysis. X-ray absorption near-edge structure spectra showed that the Ti 4+ and Co 2+ states were dominant in our prepared samples. A reduction in the coordination number was also confirmed. The dependence of the electrical conductivity on the frequency was measured by an LCR meter, and the carrier concentration was determined. The magnetization curves for the nanoparticles indicated ferromagnetic behavior at room temperature. We concluded that the ferromagnetism originated in oxygen vacancies around the transition metal ions

  16. Research and Training of Using Neutron Scattering to Probe the Collective Phenomena in Doped Transition-Metal Oxides. Final report

    Zhang, Jiandi

    2008-01-01

    The objective of this funded research program include: explore and understand the microscopic origins of collective phenomena in doped transition-metal oxides (TMOs) using neutrons as one of the primary tools, and train new generation of neutron scatters and collaborate with Oak Ridge National Lab in both materials synthesis and characterization. The major physics issues focused on in this project consist of the microscopic correlations between lattice structure and magnetic ordering, the nature of elementary lattice and spin excitations, the origin of nanometer-scale phase separations, and the effects of dimensional confinement and broken symmetry. The main materials are doped TMOs grown as single crystals by a floating-zone technique at ORNL as well as multiplayer films grown with a laser-MBE facility at Florida International University (FIU). Our educational objective is the training of our graduate and undergraduate students, especially Hispanic and other minority students, to use neutrons as a probe for materials research by taking advantage of national neutron facilities and to grow novel materials by using the floating-zone and laser-MBE technique. The main achievements of the project include the systematic study of the spin dynamics, especially the spin wave excitations in ferromagnetic manganites; the discovery of the critical doping concentration for the magnetic phase separation of the charge-ordered state in Pr 1-x Ca x MnO 3 - ; the study of Σ 4 phonon softening associated with the lattice instability near the quantum critical point as well as the discovery of an anomalous mode in single-layered ruthenates. These results gain some important insights into the collective excitations in both spin and lattice degrees of freedom as well as their close coupling in these correlated TMO systems. Furthermore, this project also accomplished the synthesis and some characterization of the single crystals of a new material Ba 2-x Sr x CoO 4 , a compound in which

  17. Giant coercivity in ferromagnetic Co doped ZnO single crystal thin film

    Loukya, B.; Negi, D.S.; Dileep, K.; Kumar, N.; Ghatak, Jay; Datta, R.

    2013-01-01

    The origin of ferromagnetism in ZnO doped with transition metal impurities has been discussed extensively and appeared to be a highly controversial and challenging topic in today's solid state physics. Magnetism observed in this system is generally weak and soft. We have grown Co:ZnO up to 30 at% Co in single crystal thin film form on c-plane sapphire. A composition dependent coercivity is observed in this system which reaches peak value at 25 at% Co, the values are 860 Oe and 1149 Oe with applied field along parallel and perpendicular to the film substrate interface respectively. This giant coercivity might pave the way to exploit this material as a magnetic semiconductor with novel logic functionalities. The findings are explained based on defect band itinerant ferromagnetism and its partial interaction with localized d electrons of Co through charge transfer. Besides large coercivity, an increase in the band gap with Co concentration has also been observed along with blue emission peak with long tail confirming the formation of extended point defect levels in the host lattice band gap. - Highlights: • Co doped ZnO ferromagnetic single crystal thin film. • Giant coercivity in Co:ZnO thin film which may help to turn this material into application. • Cathodoluminescence (CL) data showing increase in band gap with Co concentrations. • A theoretical proposal is made to explain the observed giant coercivity

  18. Electronic Properties of a 1D Intrinsic/p-Doped Heterojunction in a 2D Transition Metal Dichalcogenide Semiconductor

    Song, Zhibo; Schultz, Thorsten; Ding, Zijing; Lei, Bo; Han, Cheng; Amsalem, Patrick; Lin, Tingting; Chi, Dongzhi; Wong, Swee Liang; Zheng, Yu Jie; Li, Ming-yang; Li, Lain-Jong; Chen, Wei; Koch, Norbert; Huang, Yu Li; Wee, Andrew Thye Shen

    2017-01-01

    Two-dimensional (2D) semiconductors offer a convenient platform to study 2D physics, for example, to understand doping in an atomically thin semiconductor. Here, we demonstrate the fabrication and unravel the electronic properties of a lateral doped/intrinsic heterojunction in a single-layer (SL) tungsten diselenide (WSe2), a prototype semiconducting transition metal dichalcogenide (TMD), partially covered with a molecular acceptor layer, on a graphite substrate. With combined experiments and theoretical modeling, we reveal the fundamental acceptor-induced p-doping mechanism for SL-WSe2. At the 1D border between the doped and undoped SL-WSe2 regions, we observe band bending and explain it by Thomas-Fermi screening. Using atomically resolved scanning tunneling microscopy and spectroscopy, the screening length is determined to be in the few nanometer range, and we assess the carrier density of intrinsic SL-WSe2. These findings are of fundamental and technological importance for understanding and employing surface doping, for example, in designing lateral organic TMD heterostructures for future devices.

  19. Electronic Properties of a 1D Intrinsic/p-Doped Heterojunction in a 2D Transition Metal Dichalcogenide Semiconductor

    Song, Zhibo

    2017-07-28

    Two-dimensional (2D) semiconductors offer a convenient platform to study 2D physics, for example, to understand doping in an atomically thin semiconductor. Here, we demonstrate the fabrication and unravel the electronic properties of a lateral doped/intrinsic heterojunction in a single-layer (SL) tungsten diselenide (WSe2), a prototype semiconducting transition metal dichalcogenide (TMD), partially covered with a molecular acceptor layer, on a graphite substrate. With combined experiments and theoretical modeling, we reveal the fundamental acceptor-induced p-doping mechanism for SL-WSe2. At the 1D border between the doped and undoped SL-WSe2 regions, we observe band bending and explain it by Thomas-Fermi screening. Using atomically resolved scanning tunneling microscopy and spectroscopy, the screening length is determined to be in the few nanometer range, and we assess the carrier density of intrinsic SL-WSe2. These findings are of fundamental and technological importance for understanding and employing surface doping, for example, in designing lateral organic TMD heterostructures for future devices.

  20. Role of electron filling in the magnetic anisotropy of monolayer WSe2 doped with 5 d transition metals

    Song, Yan; Wang, Xiaocha; Mi, Wenbo

    2017-12-01

    Exploring magnetic anisotropy (MA) in single-atom-doped two-dimensional materials provides a viable ground for realizing information storage and processing at ultimate length scales. Herein, the MA of 5 d transition-metal doped monolayer WSe2 is investigated by first-principles calculations. Large MA energy (MAE) is achieved in several doping systems. The direction of MA is determined by the dopant in-plane d states in the vicinity of the Fermi level in line with previous studies. An occupation rule that the parity of the occupation number of the in-plane d orbital of the dopant determines the preference between in-plane and out-of-plane anisotropy is found in this 5 d -doped system. Furthermore, this rule is understood by second-order perturbation theory and proved by charge-doping analysis. Considering relatively little research on two-dimensional MA and not sufficiently large MAE, suitable contact medium dopant pairs with large MAE and tunable MA pave the way to novel data storage paradigms.

  1. High-temperature ferromagnetism in heavily Fe-doped ferromagnetic semiconductor (Ga,Fe)Sb

    Tu, Nguyen Thanh; Hai, Pham Nam; Anh, Le Duc; Tanaka, Masaaki

    2016-01-01

    We show high-temperature ferromagnetism in heavily Fe-doped ferromagnetic semiconductor (Ga_1_−_x,Fe_x)Sb (x = 23% and 25%) thin films grown by low-temperature molecular beam epitaxy. Magnetic circular dichroism spectroscopy and anomalous Hall effect measurements indicate intrinsic ferromagnetism of these samples. The Curie temperature reaches 300 K and 340 K for x = 23% and 25%, respectively, which are the highest values reported so far in intrinsic III-V ferromagnetic semiconductors.

  2. High-temperature ferromagnetism in heavily Fe-doped ferromagnetic semiconductor (Ga,Fe)Sb

    Tu, Nguyen Thanh [Department of Electrical Engineering and Information Systems, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656 (Japan); Department of Physics, Ho Chi Minh City University of Pedagogy, 280, An Duong Vuong Street, District 5, Ho Chi Minh City 748242 (Viet Nam); Hai, Pham Nam [Department of Electrical Engineering and Information Systems, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656 (Japan); Department of Physical Electronics, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro, Tokyo 152-0033 (Japan); Center for Spintronics Research Network (CSRN), The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Anh, Le Duc [Department of Electrical Engineering and Information Systems, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656 (Japan); Tanaka, Masaaki [Department of Electrical Engineering and Information Systems, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656 (Japan); Center for Spintronics Research Network (CSRN), The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)

    2016-05-09

    We show high-temperature ferromagnetism in heavily Fe-doped ferromagnetic semiconductor (Ga{sub 1−x},Fe{sub x})Sb (x = 23% and 25%) thin films grown by low-temperature molecular beam epitaxy. Magnetic circular dichroism spectroscopy and anomalous Hall effect measurements indicate intrinsic ferromagnetism of these samples. The Curie temperature reaches 300 K and 340 K for x = 23% and 25%, respectively, which are the highest values reported so far in intrinsic III-V ferromagnetic semiconductors.

  3. Ferromagnetic properties of Mn-doped AlN

    Li, H.; Bao, H.Q.; Song, B.; Wang, W.J.; Chen, X.L.; He, L.J.; Yuan, W.X.

    2008-01-01

    Mn-doped AlN polycrystalline powders with a wurtzite structure were synthesized by solid-state reactions. A red-orange band at 600 nm, due to Mn 3+ incorporated into the AlN lattice, is observed in the photoluminescence (PL) spectrum at room temperature (RT). Magnetic measurements show the samples possess hysteresis loops up to 300 K, indicating that the obtained powders are ferromagnetic at around RT. The Mn concentration-induced RT ferromagnetism is less than 1 at%. Our results confirm that the RT ferromagnetism can be realized in Mn-doped AlN

  4. Room temperature ferromagnetism and absorption red-shift in nitrogen-doped TiO2 nanoparticles

    Gómez-Polo, C.; Larumbe, S.; Monge, M.

    2014-01-01

    Highlights: • N-doped TiO 2 anatase nanoparticles were obtained by sol–gel. • The nanoparticle size, controlled by the N doping, determines lattice parameters. • Correlation between room temperature ferromagnetism and absorption red-shift. • Oxygen vacancies reinforce both phenomena. • Metal transition impurities contribute to the room temperature ferromagnetism. - Abstract: In this work, room-temperature ferromagnetism and the red-shift of the optical absorption is analyzed in nitrogen doped TiO 2 semiconductor nanoparticles. The nanoparticles were synthesized by the sol–gel method using urea as the nitrogen source. Titanium Tetraisopropoxide (TTIP) was employed as the alkoxyde precursor and dissolved in ethanol. The as prepared gels were dried and calcined in air at 300 °C. Additionally, post-annealing treatments under vacuum atmosphere were performed to modify the oxygen stoichiometry of the samples. The anatase lattice parameters, analyzed by means of powder X-ray diffractometry, depend on the nanometer grain size of the nanoparticles (increase and decrease, respectively, of the tetragonal a and c lattice parameters with respect to the bulk values). The diffuse reflectance ultraviolet–visible (UV–Vis) absorbance spectra show a clear red-shift as consequence of the nitrogen and the occurrence of intragap energy levels. The samples display ferromagnetic features at room temperature that are reinforced with the nitrogen content and after the post annealings in vacuum. The results indicate a clear correlation between the room temperature ferromagnetism and the shift of the absorbance spectrum. In both phenomena, oxygen vacancies (either induced by the nitrogen doping or by the post vacuum annealings) play a dominant role. However, we conclude the existence of very low concentration of diluted transition metal impurities that determine the room ferromagnetic response (bound magnetic polaron BMP model). The contraction of the c soft axis of the

  5. Room temperature ferromagnetism and absorption red-shift in nitrogen-doped TiO{sub 2} nanoparticles

    Gómez-Polo, C., E-mail: gpolo@unavarra.es [Departamento de Física, Universidad Pública de Navarra, Campus de Arrosadia, 31006 Pamplona (Spain); Larumbe, S. [Departamento de Física, Universidad Pública de Navarra, Campus de Arrosadia, 31006 Pamplona (Spain); Monge, M. [Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26006 Logroño (Spain)

    2014-11-05

    Highlights: • N-doped TiO{sub 2} anatase nanoparticles were obtained by sol–gel. • The nanoparticle size, controlled by the N doping, determines lattice parameters. • Correlation between room temperature ferromagnetism and absorption red-shift. • Oxygen vacancies reinforce both phenomena. • Metal transition impurities contribute to the room temperature ferromagnetism. - Abstract: In this work, room-temperature ferromagnetism and the red-shift of the optical absorption is analyzed in nitrogen doped TiO{sub 2} semiconductor nanoparticles. The nanoparticles were synthesized by the sol–gel method using urea as the nitrogen source. Titanium Tetraisopropoxide (TTIP) was employed as the alkoxyde precursor and dissolved in ethanol. The as prepared gels were dried and calcined in air at 300 °C. Additionally, post-annealing treatments under vacuum atmosphere were performed to modify the oxygen stoichiometry of the samples. The anatase lattice parameters, analyzed by means of powder X-ray diffractometry, depend on the nanometer grain size of the nanoparticles (increase and decrease, respectively, of the tetragonal a and c lattice parameters with respect to the bulk values). The diffuse reflectance ultraviolet–visible (UV–Vis) absorbance spectra show a clear red-shift as consequence of the nitrogen and the occurrence of intragap energy levels. The samples display ferromagnetic features at room temperature that are reinforced with the nitrogen content and after the post annealings in vacuum. The results indicate a clear correlation between the room temperature ferromagnetism and the shift of the absorbance spectrum. In both phenomena, oxygen vacancies (either induced by the nitrogen doping or by the post vacuum annealings) play a dominant role. However, we conclude the existence of very low concentration of diluted transition metal impurities that determine the room ferromagnetic response (bound magnetic polaron BMP model). The contraction of the c soft axis

  6. Room-temperature ferromagnetism in pure and Co doped CeO2 powders

    Wen Qiye; Zhang Huaiwu; Song Yuanqiang; Yang Qinghui; Zhu Hao; Xiao, John Q

    2007-01-01

    We report the room-temperature (RT) ferromagnetism (FM) observed in pure and Co doped CeO 2 powder. An insulating nonmagnetic CeO 2 single crystal, after grinding into fine powder, shows an RT-FM with a small magnetization of 0.0045 emu g -1 . However, the CeO 2 powder became paramagnetic after oxygen annealing, which strongly suggests an oxygen vacancy meditated FM ordering. Furthermore, by doping Co into CeO 2 powder the FM can significantly enhance through a F-centre exchange (FCE) coupling mechanism, in which both oxygen vacancies and magnetic ions are involved. As the Co content increases, the FM of Co doped CeO 2 initially increases to a maximum 0.47 emu g -1 , and then degrades very quickly. The complex correlation between the Co content and saturation magnetization was well interpreted by supposing the coexistence of three subsets of Co ions in CeO 2 . Our results reveal that the large RT-FM observed in Co doped CeO 2 powder originates from a combination effect of oxygen vacancies and transition metal doping

  7. Room temperature ferromagnetism and gas sensing in ZnO nanostructures: Influence of intrinsic defects and Mn, Co, Cu doping

    Mhlongo, Gugu H., E-mail: gmhlongo@csir.co.za [DST/CSIR National Centre for Nanostructured Materials, Council for Scientific and Industrial Research, Pretoria 0001 (South Africa); Shingange, Katekani; Tshabalala, Zamaswazi P.; Dhonge, Baban P. [DST/CSIR National Centre for Nanostructured Materials, Council for Scientific and Industrial Research, Pretoria 0001 (South Africa); Mahmoud, Fawzy A. [Solid State Physics Dept., National Research Centre, P.O. 12622, Dokki, Giza (Egypt); Mwakikunga, Bonex W.; Motaung, David E. [DST/CSIR National Centre for Nanostructured Materials, Council for Scientific and Industrial Research, Pretoria 0001 (South Africa)

    2016-12-30

    Highlights: • Preparation of Mn, Co, Cu doped ZnO via microwave-assisted method. • Doping alters the morphology of ZnO nanostructures. • Concentration of zinc and oxygen related defects vary with doping. • Correlation between PL and EPR was established. • Both undoped and doped ZnO nanostructures showed selectivity towards NH{sub 3}. - Abstract: Undoped and transition metal (Cu, Co and Mn) doped ZnO nanostructures were successfully prepared via a microwave-assisted hydrothermal method followed by annealing at 500 °C. Numerous characterization facilities such as X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM) were employed to acquire the structural and morphological information of the prepared ZnO based products. Combination of defect structure analysis based on photoluminescence (PL) and electron paramagnetic resonance (EPR) indicated that co-existing oxygen vacancies (V{sub O}) and zinc interstitials (Zn{sub i}) defects are responsible for the observed ferromagnetism in undoped and transition metal (TM) doped ZnO systems. PL analysis demonstrated that undoped ZnO has more donor defects (V{sub O} and Zn{sub i}) which are beneficial for gas response enhancement. Undoped ZnO based sensor exhibited a higher sensor response to NH{sub 3} gas compared to its counterparts owing to high content of donor defects while transition metal doped sensors showed short response and recovery times compared to undoped ZnO.

  8. Magnetic properties of Mg12O12 nanocage doped with transition metal atoms (Mn, Fe, Co and Ni): DFT study

    Javan, Masoud Bezi

    2015-07-01

    Binding energy of the Mg12O12 nanocage doped with transition metals (TM=Mn, Fe, Co and Ni) in endohedrally, exohedrally and substitutionally forms were studied using density functional theory with the generalized gradient approximation exchange-correlation functional along 6 different paths inside and outside of the Mg12O12 nanocage. The most stable structures were determined with full geometry optimization near the minimum of the binding energy curves of all the examined paths inside and outside of the Mg12O12 nanocage. The results reveal that for all stable structures, the Ni atom has a larger binding energy than the other TM atoms. It is also found that for all complexes additional peaks contributed by TM-3d, 4s and 4p states appear in the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) gap of the host MgO cluster. The mid-gap states are mainly due to the hybridization between TM-3d, 4s and 4p orbitals and the cage π orbitals. The magnetic moment of the endohedrally doped TM atoms in the Mg12O12 are preserved to some extent due to the interaction between the TM and Mg12O12 nanocage, in contrast to the completely quenched magnetic moment of the Fe and Ni atoms in the Mg11(TM)O12 complexes. Furthermore, charge population analysis shows that charge transfer occurs from TM atom to the cage for endohedrally and substitutionally doping.

  9. Low-temperature synthesis of hexagonal transition metal ion doped ZnS nanoparticles by a simple colloidal method

    Wang, Liping; Huang, Shungang; Sun, Yujie

    2013-01-01

    A general route to synthesize transition metal ions doped ZnS nanoparticles with hexagonal phase by means of a conventional reverse micelle at a low temperature is developed. The synthesis involves N,N-dimethylformamide, Zn(AC) 2 solution, thiourea, ammonia, mercaptoacetic acid, as oil phase, water phase, sulfide source, pH regulator, and surfactant, respectively. Thiourea, ammonia and mercaptoacetic acid are demonstrated crucial factors, whose effects have been studied in detail. In addition, the FT-IR spectra suggest that mercaptoacetic acid may form complex chelates with Zn 2+ in the preparation. In the case of Cu 2+ as a doped ion, hexagonal ZnS:Cu 2+ nanoparticles were synthesized at 95 °C for the first time. The X-ray diffraction (XRD) and transmission electron microscope (TEM) measurements show that the ZnS:Cu 2+ nanoparticles are polycrystalline and possess uniform particle size. The possible formation mechanism of the hexagonal doped ZnS is discussed.

  10. The oxidation of carbon monoxide over transition metal doped lanthanum manganates nanoparticles

    Fal Desai, M.S.; Salker, A.V.

    2012-01-01

    Lanthanum manganates perovskites (ABO 3 ) has been widely studied and applied. Many perovskites with A and B sites doped with different metals show good catalytic activity in many oxidation reactions than the individual perovskite. In present study, an attempt has been made to show comparative account of CO oxidation by doping the B site with different cations using sol-gel method

  11. Strong Rashba-Edelstein Effect-Induced Spin–Orbit Torques in Monolayer Transition Metal Dichalcogenide/Ferromagnet Bilayers

    Shao, Qiming

    2016-11-18

    The electronic and optoelectronic properties of two-dimensional materials have been extensively explored in graphene and layered transition metal dichalcogenides (TMDs). Spintronics in these two-dimensional materials could provide novel opportunities for future electronics, for example, efficient generation of spin current, which should enable the efficient manipulation of magnetic elements. So far, the quantitative determination of charge current-induced spin current and spin-orbit torques (SOTs) on the magnetic layer adjacent to two-dimensional materials is still lacking. Here, we report a large SOT generated by current-induced spin accumulation through the Rashba-Edelstein effect in the composites of monolayer TMD (MoS or WSe)/CoFeB bilayer. The effective spin conductivity corresponding to the SOT turns out to be almost temperature-independent. Our results suggest that the charge-spin conversion in the chemical vapor deposition-grown large-scale monolayer TMDs could potentially lead to high energy efficiency for magnetization reversal and convenient device integration for future spintronics based on two-dimensional materials.

  12. Room temperature d (0) ferromagnetism in hole doped Y2O3: widening the choice of host to tailor DMS.

    Chakraborty, Brahmananda; Ramaniah, Lavanya M

    2016-08-24

    Transition metal-free-ferromagnetism in diluted magnetic semiconductors (DMS) is of much current interest in view of the search for more efficient DMS materials for spintronics applications. Our DFT results predict for the first time, that impurities from group1A (Li(+), Na(+), K(+)) doped on Y2O3 can induce a magnetic signature with a magnetic moment around 2.0 μ B per defect at hole concentrations around 1.63  ×  10(21) cm(-3), which is one order less than the critical hole density of ZnO with ferromagnetic coupling large enough to promote room temperature ferromagnetism. The induction of room temperature ferromagnetism by hole doping with an impurity atom from group 1A, which injects two holes per defect in the system, implies that the recommendation of three holes per defect given in the literature, which puts a restriction on the choice of host material and the impurity, is not a necessary criterion for hole induced room temperature ferromagnetism. DFT simulations with the generalized gradient approximation (GGA), confirmed by the more sophisticated hybrid functional, Heyd-Scuseria-Ernzerhof (HSE06), predict that the magnetic moment is mostly contributed by O atoms surrounding the impurity atom and the magnetic moment scale up with impurity concentration which is a positive indicator for practical applications. We quantitatively and extensively demonstrate through the analysis of the density of states and ferromagnetic coupling that the Stoner criterion is satisfied by pushing the Fermi level inside the valence band to activate room temperature ferromagnetism. The stability of the structure and the persistence of ferromagnetism at room temperature were demonstrated by ab initio MD simulations and computation of Curie temperature through the mean field approximation. This study widens the choice of host oxides to tailor DMS for spintronics applications.

  13. Theoretical Investigation on Single-Wall Carbon Nanotubes Doped with Nitrogen, Pyridine-Like Nitrogen Defects, and Transition Metal Atoms

    Michael Mananghaya

    2012-01-01

    Full Text Available This study addresses the inherent difficulty in synthesizing single-walled carbon nanotubes (SWCNTs with uniform chirality and well-defined electronic properties through the introduction of dopants, topological defects, and intercalation of metals. Depending on the desired application, one can modify the electronic and magnetic properties of SWCNTs through an appropriate introduction of imperfections. This scheme broadens the application areas of SWCNTs. Under this motivation, we present our ongoing investigations of the following models: (i (10, 0 and (5, 5 SWCNT doped with nitrogen (CNxNT, (ii (10, 0 and (5, 5 SWCNT with pyridine-like defects (3NV-CNxNT, (iii (10, 0 SWCNT with porphyrine-like defects (4ND-CNxNT. Models (ii and (iii were chemically functionalized with 14 transition metals (TMs: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Ag, Pt and Au. Using the spin-unrestricted density functional theory (DFT, stable configurations, deformations, formation and binding energies, the effects of the doping concentration of nitrogen, pyridine-like and porphyrine-like defects on the electronic properties were all examined. Results reveal that the electronic properties of SWCNTs show strong dependence on the concentration and configuration of nitrogen impurities, its defects, and the TMs adsorbed.

  14. Effect of 3d-transition metal doping on the shielding behavior of barium borate glasses: a spectroscopic study.

    ElBatal, H A; Abdelghany, A M; Ghoneim, N A; ElBatal, F H

    2014-12-10

    UV-visible and FT infrared spectra were measured for prepared samples before and after gamma irradiation. Base undoped barium borate glass of the basic composition (BaO 40%-B2O3 60mol.%) reveals strong charge transfer UV absorption bands which are related to unavoidable trace iron impurities (Fe(3+)) within the chemical raw materials. 3d transition metal (TM)-doped glasses exhibit extra characteristic absorption bands due to each TM in its specific valence or coordinate state. The optical spectra show that TM ions favor generally the presence in the high valence or tetrahedral coordination state in barium borate host glass. Infrared absorption bands of all prepared glasses reveal the appearance of both triangular BO3 units and tetrahedral BO4 units within their characteristic vibrational modes and the TM-ions cause minor effects because of the low doping level introduced (0.2%). Gamma irradiation of the undoped barium borate glass increases the intensity of the UV absorption together with the generation of an induced broad visible band at about 580nm. These changes are correlated with suggested photochemical reactions of trace iron impurities together with the generation of positive hole center (BHC or OHC) within the visible region through generated electrons and positive holes during the irradiation process. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Variation in band gap of lanthanum chromate by transition metals doping LaCr0.9A0.1O3 (A:Fe/Co/Ni)

    Naseem, Swaleha; Khan, Wasi; Saad, A. A.; Shoeb, M.; Ahmed, Hilal; Naqvi, A. H.; Husain, Shahid

    2014-01-01

    Transition metal (Fe, Co, Ni) doped lanthanum chromate (LaCrO 3 ) nanoparticles (NPs) were prepared by gel combustion method and calcinated at 800°C. Microstructural studies were carried by XRD and SEM/EDS techniques. The results of structural characterization show the formation of all samples in single phase without any impurity. Optical properties were studied by UV- visible and photoluminescence techniques. The energy band gap was calculated and the variation was observed with the doping of transition metal ions. Photoluminescence spectra show the emission peak maxima for the pure LaCrO 3 at about 315 nm. Influence of Fe, Co, Ni doping was studied and compared with pure lanthanum chromate nanoparticles

  16. Synthesis and structural study of the transition metal doped rhodium perovskites

    Ting, J.; Kennedy, B.; Zhang, Z.

    2009-01-01

    Full text: One of the most common structures encountered in solid state chemistry is the perovskite structure. With a general formula of AB0 3, the A-type cations are 12-coordinate within a cubo-octahedral environment, while the B-type cations are 6-coordinate, forming an interconnecting three-dimensional octahedral network with neighbouring oxygen anions. While the ideal perovskite structure is cubic in Pm 3 m, many perovskites exhibit symmetry lowering tilting of the corner-sharing B0 6o ctahedral units as a result of A- and B-type cation size disparity. This is also evident in substituted perovskites, where two cations occupy the smaller octahedral site, AB 1- xB' x0 3' Electronic effects can also lower the symmetry. The two most commonly observed effects are the polarisation of the B-cation with a d 0 electronic configuration and Jahn-Teller distortion where the B-cation has a d 4 or d 9 electronic configuration, such as Mn 3+ or Cu 2+ respectively. Manganese containing perovskites have been shown in some compounds to exhibit long-range orbital ordering, giving rise to interesting properties. Heavier transition metals such as ruthenium and iridium have been previously incorporated into these perovskites as an avenue to regulate the properties of these materials. Two orthorhombic rhodium perovskite structures are presented, LaMn 0 . 5 Rh 0 . 5 O 3 and LaCu 05 Rh 0 . 5 O 3 ' A combination of synchrotron x-ray and neutron powder diffraction has been used to elucidate their structures, and have shown both B- and B'-type cations to be disordered across the same crystallographic site for both compounds. x-ray absorption spectroscopy measurements have been used to provide an insight into the valence states of the cations, which show a valency of +3.5 for rhodium due to an extensive charge delocalisation between copper and rhodium.

  17. Room temperature ferromagnetism in Cu doped ZnO

    Ali, Nasir; Singh, Budhi; Khan, Zaheer Ahmed; Ghosh, Subhasis

    2018-05-01

    We report the room temperature ferromagnetism in 2% Cu doped ZnO films grown by RF magnetron sputtering in different argon and oxygen partial pressure. X-ray photoelectron spectroscopy was used to ascertain the oxidation states of Cu in ZnO. The presence of defects within Cu-doped ZnO films can be revealed by electron paramagnetic resonance. It has been observed that saturated magnetic moment increase as we increase the zinc vacancies during deposition.

  18. Room temperature ferromagnetism in magic-sized Cr-doped CdS diluted magnetic semiconducting quantum dots

    Srivastava, Punita; Kumar, Pushpendra; Singh, Kedar

    2011-01-01

    Manipulation of carrier spins in semiconductors for spintronics applications has received great attention driven by improved functionalities and higher speed operation. Doping of semiconductor nanocrystals by transition-metal ions pronounced as diluted magnetic semiconductors (DMS) has attracted tremendous attention. Such doping is, however, difficult to achieve in low-dimensional strongly quantum-confined nanostructures by conventional growth procedures. In the present case, magic-sized, pure, and Cr-doped CdS DM-QDs have been synthesized by solution phase chemistry (lyothermal method). Structural, optical, and magnetic investigation suggest an intrinsic nature of ferromagnetism with highly quantum-confined system. Optical and magnetic results of pure and doped QDs reveal major physical consequences of dopant localization within the capacity to engineer dopant-carrier exchange interactions introducing magnetic functionalities within the host semiconductor lattice. Unpaired Cr ions in Cd substitutional sites could create spin ordering and ferromagnetic coupling. The results presented herein illustrate some of the remarkable and unexpected complexities that can arise in doped QDs.

  19. General Synthesis of Transition-Metal Oxide Hollow Nanospheres/Nitrogen-Doped Graphene Hybrids by Metal-Ammine Complex Chemistry for High-Performance Lithium-Ion Batteries.

    Chen, Jiayuan; Wu, Xiaofeng; Gong, Yan; Wang, Pengfei; Li, Wenhui; Mo, Shengpeng; Peng, Shengpan; Tan, Qiangqiang; Chen, Yunfa

    2018-02-09

    We present a general and facile synthesis strategy, on the basis of metal-ammine complex chemistry, for synthesizing hollow transition-metal oxides (Co 3 O 4 , NiO, CuO-Cu 2 O, and ZnO)/nitrogen-doped graphene hybrids, potentially applied in high-performance lithium-ion batteries. The oxygen-containing functional groups of graphene oxide play a prerequisite role in the formation of hollow transition-metal oxides on graphene nanosheets, and a significant hollowing process occurs only when forming metal (Co 2+ , Ni 2+ , Cu 2+ , or Zn 2+ )-ammine complex ions. Moreover, the hollowing process is well correlated with the complexing capacity between metal ions and NH 3 molecules. The significant hollowing process occurs for strong metal-ammine complex ions including Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ ions, and no hollow structures formed for weak and/or noncomplex Mn 2+ and Fe 3+ ions. Simultaneously, this novel strategy can also achieve the direct doping of nitrogen atoms into the graphene framework. The electrochemical performance of two typical hollow Co 3 O 4 or NiO/nitrogen-doped graphene hybrids was evaluated by their use as anodic materials. It was demonstrated that these unique nanostructured hybrids, in contrast with the bare counterparts, solid transition-metal oxides/nitrogen-doped graphene hybrids, perform with significantly improved specific capacity, superior rate capability, and excellent capacity retention. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Notes on the photoinduced characteristics of transition metal doped and undoped titanium dioxide thin films

    Kment, Štěpán; Kmentová, Hana; Hubička, Zdeněk; Klusoň, Jan; Krýsa, J.; Církva, Vladimír; Gregora, Ivan; Šolcová, Olga; Jastrabík, Lubomír

    2010-01-01

    Roč. 348, č. 1 (2010), s. 198-205 ISSN 0021-9797 R&D Projects: GA ČR GA202/08/1009; GA AV ČR KAN301370701; GA AV ČR KAN400720701 Institutional research plan: CEZ:AV0Z10100522; CEZ:AV0Z40720504 Keywords : sol-gel * thin layers * metal doped TiO 2 * IPCE * photocurrent * photocatalysis Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.068, year: 2010

  1. Properties of transition metal-doped zinc chalcogenide crystals for tunable IR laser radiation

    DeLoach, L.D.; Page, R.H.; Wilke, G.D.

    1995-01-01

    The spectroscopic properties of Cr 2+ , Co 2+ , and Ni 2+ -doped single crystals of ZnS, ZnSe, and ZnTe have been investigated to understand their potential application as mid-IR tunable solid-state laser media. The spectroscopy indicated divalent Cr was the most favorable candidate for efficient room temperature lasing, and accordingly, a laser-pumped laser demonstration of Cr:ZnS and Cr:ZnSe has been performed. The lasers' output were peaked at ∼ 2.35 μm and the highest measured slope efficiencies were ∼ 20% in both cases

  2. Highly efficient transition metal and nitrogen co-doped carbide-derived carbon electrocatalysts for anion exchange membrane fuel cells

    Ratso, Sander; Kruusenberg, Ivar; Käärik, Maike; Kook, Mati; Puust, Laurits; Saar, Rando; Leis, Jaan; Tammeveski, Kaido

    2018-01-01

    The search for an efficient electrocatalyst for oxygen reduction reaction (ORR) to replace platinum in fuel cell cathode materials is one of the hottest topics in electrocatalysis. Among the many non-noble metal catalysts, metal/nitrogen/carbon composites made by pyrolysis of cheap materials are the most promising with control over the porosity and final structure of the catalyst a crucial point. In this work we show a method of producing a highly active ORR catalyst in alkaline media with a controllable porous structure using titanium carbide derived carbon as a base structure and dicyandiamide along with FeCl3 or CoCl2 as the dopants. The resulting transition metal-nitrogen co-doped carbide derived carbon (M/N/CDC) catalyst is highly efficient for ORR electrocatalysis with the activity in 0.1 M KOH approaching that of commercial 46.1 wt.% Pt/C. The catalyst materials are also investigated by scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy to characterise the changes in morphology and composition causing the raise in electrochemical activity. MEA performance of M/N/CDC cathode materials in H2/O2 alkaline membrane fuel cell is tested with the highest power density reached being 80 mW cm-2 compared to 90 mW cm-2 for Pt/C.

  3. Giant photocurrent enhancement by transition metal doping in quantum dot sensitized solar cells

    Rimal, Gaurab; Pimachev, Artem K.; Yost, Andrew J.; Poudyal, Uma; Maloney, Scott; Wang, Wenyong; Chien, TeYu; Dahnovsky, Yuri; Tang, Jinke

    2016-09-01

    A huge enhancement in the incident photon-to-current efficiency of PbS quantum dot (QD) sensitized solar cells by manganese doping is observed. In the presence of Mn dopants with relatively small concentration (4 at. %), the photoelectric current increases by an average of 300% (up to 700%). This effect cannot be explained by the light absorption mechanism because both the experimental and theoretical absorption spectra demonstrate several times decreases in the absorption coefficient. To explain such dramatic increase in the photocurrent we propose the electron tunneling mechanism from the LUMO of the QD excited state to the Zn2SnO4 (ZTO) semiconductor photoanode. This change is due to the presence of the Mn instead of Pb atom at the QD/ZTO interface. The ab initio calculations confirm this mechanism. This work proposes an alternative route for a significant improvement of the efficiency for quantum dot sensitized solar cells.

  4. Giant photocurrent enhancement by transition metal doping in quantum dot sensitized solar cells

    Rimal, Gaurab; Pimachev, Artem K.; Yost, Andrew J.; Poudyal, Uma; Maloney, Scott; Wang, Wenyong; Chien, TeYu; Dahnovsky, Yuri, E-mail: yurid@uwyo.edu, E-mail: jtang2@uwyo.edu; Tang, Jinke, E-mail: yurid@uwyo.edu, E-mail: jtang2@uwyo.edu [Department of Physics and Astronomy, University of Wyoming, Laramie, Wyoming 82071 (United States)

    2016-09-05

    A huge enhancement in the incident photon-to-current efficiency of PbS quantum dot (QD) sensitized solar cells by manganese doping is observed. In the presence of Mn dopants with relatively small concentration (4 at. %), the photoelectric current increases by an average of 300% (up to 700%). This effect cannot be explained by the light absorption mechanism because both the experimental and theoretical absorption spectra demonstrate several times decreases in the absorption coefficient. To explain such dramatic increase in the photocurrent we propose the electron tunneling mechanism from the LUMO of the QD excited state to the Zn{sub 2}SnO{sub 4} (ZTO) semiconductor photoanode. This change is due to the presence of the Mn instead of Pb atom at the QD/ZTO interface. The ab initio calculations confirm this mechanism. This work proposes an alternative route for a significant improvement of the efficiency for quantum dot sensitized solar cells.

  5. Stability and activity of doped transition metal zeolites in the hydrothermal processing

    Thomas François Robin

    2015-12-01

    Full Text Available This study investigates the stability and activity of HZSM-5 doped with metals such as molybdenum, nickel, copper and iron in under hydrothermal conditions used for the direct liquefaction of microalgae. Catalysts have been prepared by ion exchange techniques, and MoZSM-5 was also prepared by wet incipient impregnation for comparison. Hydrothermal liquefaction is considered as a potential route to convert microalgae into a sustainable fuel. One of the drawbacks of this process is that the bio-crude produced contains significant levels of nitrogen and oxygen compounds which have an impact on the physical and chemical propriety of the fuel. Heterogeneous catalysts have been shown to improve the quality of the bio-crude by reducing nitrogen and oxygen contents. Zeolites, such as HZSM-5, are strong candidates due to their low cost compared to noble metal catalysts but their stability and activity under hydrothermal conditions is not well understood. The stability of the catalysts has been determined under hydrothermal conditions at 350 °C. Catalysts have been characterised before and after treatment using XRD, BET physisorption and STEM microscopy. Metal leaching was determined by analysis of the water phase following hydrothermal treatment. The inserted cation following ion-exchange can influence the physical properties of HZSM-5 for example molybdenum improves the crystallinity of the zeolite. In general, metal doped zeolites were relatively stable under subcritical water. Activity of the catalysts for processing lipids, protein and microalgae has been assessed. Four feedstocks were selected: sunflower oil, soya proteins, Chlorella and P. ellipsoidea. The catalysts exhibited greater activity towards converting lipids for example MoZSM-5 enhanced the formation of aromatic compounds. NiZSM-5 and CuZSM-5 were observed to be more efficient for deoxygenation.

  6. Stability and Activity of Doped Transition Metal Zeolites in the Hydrothermal Processing

    Robin, Thomas François, E-mail: thomas.cognac@gmail.com; Ross, Andrew B.; Lea-Langton, Amanda R.; Jones, Jenny M. [School of Chemical and Process Engineering, University of Leeds, Leeds (United Kingdom)

    2015-12-14

    This study investigates the stability and activity of HZSM-5 doped with metals such as molybdenum, nickel, copper, and iron under hydrothermal conditions used for the direct liquefaction of microalgae. Catalysts have been prepared by ion-exchange techniques, and MoZSM-5 was also prepared by wet incipient impregnation for comparison. Hydrothermal liquefaction is considered a potential route to convert microalgae into a sustainable fuel. One of the drawbacks of this process is that the bio-crude produced contains significant levels of nitrogen and oxygen compounds that have an impact on the physical and chemical properties of the fuel. Heterogeneous catalysts have been shown to improve the quality of the bio-crude by reducing nitrogen and oxygen contents. Zeolites, such as HZSM-5, are strong candidates due to their low cost compared to noble metal catalysts, but their stability and activity under hydrothermal conditions are not well understood. The stability of the catalysts has been determined under hydrothermal conditions at 350°C. Catalysts have been characterized before and after treatment using X-ray diffraction, BET physisorption, and scanning transmission electronic microscopy. Metal leaching was determined by the analysis of the water phase following the hydrothermal treatment. The inserted cation following ion-exchange can influence the physical properties of HZSM-5, for example, molybdenum improves the crystallinity of the zeolite. In general, metal-doped zeolites were relatively stable in subcritical water. The activity of the catalysts for processing lipids, protein, and microalgae has been assessed. Four feedstocks were selected: sunflower oil, soya proteins, Chlorella, and Pseudochoricystis ellipsoidea. The catalysts exhibited greater activity toward converting lipids, for example, MoZSM-5 enhanced the formation of aromatic compounds. NiZSM-5 and CuZSM-5 were observed to be more efficient for deoxygenation.

  7. Stability and Activity of Doped Transition Metal Zeolites in the Hydrothermal Processing

    Robin, Thomas François; Ross, Andrew B.; Lea-Langton, Amanda R.; Jones, Jenny M.

    2015-01-01

    This study investigates the stability and activity of HZSM-5 doped with metals such as molybdenum, nickel, copper, and iron under hydrothermal conditions used for the direct liquefaction of microalgae. Catalysts have been prepared by ion-exchange techniques, and MoZSM-5 was also prepared by wet incipient impregnation for comparison. Hydrothermal liquefaction is considered a potential route to convert microalgae into a sustainable fuel. One of the drawbacks of this process is that the bio-crude produced contains significant levels of nitrogen and oxygen compounds that have an impact on the physical and chemical properties of the fuel. Heterogeneous catalysts have been shown to improve the quality of the bio-crude by reducing nitrogen and oxygen contents. Zeolites, such as HZSM-5, are strong candidates due to their low cost compared to noble metal catalysts, but their stability and activity under hydrothermal conditions are not well understood. The stability of the catalysts has been determined under hydrothermal conditions at 350°C. Catalysts have been characterized before and after treatment using X-ray diffraction, BET physisorption, and scanning transmission electronic microscopy. Metal leaching was determined by the analysis of the water phase following the hydrothermal treatment. The inserted cation following ion-exchange can influence the physical properties of HZSM-5, for example, molybdenum improves the crystallinity of the zeolite. In general, metal-doped zeolites were relatively stable in subcritical water. The activity of the catalysts for processing lipids, protein, and microalgae has been assessed. Four feedstocks were selected: sunflower oil, soya proteins, Chlorella, and Pseudochoricystis ellipsoidea. The catalysts exhibited greater activity toward converting lipids, for example, MoZSM-5 enhanced the formation of aromatic compounds. NiZSM-5 and CuZSM-5 were observed to be more efficient for deoxygenation.

  8. Defects induced ferromagnetism in Mn doped ZnO

    Chattopadhyay, S.; Neogi, S.K. [Department of Physics, University of Calcutta, 92A P C Road, Kolkata 700009 (India); Sarkar, A. [Department of Physics, Bangabasi Morning College, Kolkata 700009 (India); Mukadam, M.D.; Yusuf, S.M. [Solid State Physics Division, Bhaba Atomic Research Centre, Mumbai 400085 (India); Banerjee, A. [Department of Physics, University of Calcutta, 92A P C Road, Kolkata 700009 (India); Bandyopadhyay, S., E-mail: sbaphy@caluniv.ac.i [Department of Physics, University of Calcutta, 92A P C Road, Kolkata 700009 (India)

    2011-02-15

    Single phase Mn doped (2 at%) ZnO samples have been synthesized by the solid-state reaction technique. Before the final sintering at 500 {sup o}C, the mixed powders have been milled for different milling periods (6, 24, 48 and 96 h). The grain sizes of the samples are very close to each other ({approx}32{+-}4 nm). However, the defective state of the samples is different from each other as manifested from the variation of magnetic properties and electrical resistivity with milling time. All the samples have been found to be ferromagnetic with clear hysteresis loops at room temperature. The maximum value for saturation magnetization (0.11 {mu}{sub B}/Mn atom) was achieved for 96 h milled sample. Electrical resistivity has been found to increase with increase in milling time. The most resistive sample bears the largest saturation magnetization. Variation of average positron lifetime with milling time bears a close similarity with that of the saturation magnetization. This indicates the key role played by open volume vacancy defects, presumably zinc vacancies near grain surfaces, in inducing ferromagnetic order in Mn doped ZnO. To attain optimum defect configuration favorable for ferromagnetism in this kind of samples proper choice of milling period and annealing conditions is required. - Research highlights: 2 at% Mn doped ZnO samples are single phase. All the samples exhibit ferromagnetism at room temperature. Correlation between saturation magnetization and positron annihilation lifetime established.

  9. Defects induced ferromagnetism in Mn doped ZnO

    Chattopadhyay, S.; Neogi, S.K.; Sarkar, A.; Mukadam, M.D.; Yusuf, S.M.; Banerjee, A.; Bandyopadhyay, S.

    2011-01-01

    Single phase Mn doped (2 at%) ZnO samples have been synthesized by the solid-state reaction technique. Before the final sintering at 500 o C, the mixed powders have been milled for different milling periods (6, 24, 48 and 96 h). The grain sizes of the samples are very close to each other (∼32±4 nm). However, the defective state of the samples is different from each other as manifested from the variation of magnetic properties and electrical resistivity with milling time. All the samples have been found to be ferromagnetic with clear hysteresis loops at room temperature. The maximum value for saturation magnetization (0.11 μ B /Mn atom) was achieved for 96 h milled sample. Electrical resistivity has been found to increase with increase in milling time. The most resistive sample bears the largest saturation magnetization. Variation of average positron lifetime with milling time bears a close similarity with that of the saturation magnetization. This indicates the key role played by open volume vacancy defects, presumably zinc vacancies near grain surfaces, in inducing ferromagnetic order in Mn doped ZnO. To attain optimum defect configuration favorable for ferromagnetism in this kind of samples proper choice of milling period and annealing conditions is required. - Research highlights: → 2 at% Mn doped ZnO samples are single phase. → All the samples exhibit ferromagnetism at room temperature. → Correlation between saturation magnetization and positron annihilation lifetime established.

  10. Synthesis and characterization of TiO2 photocatalyst doped by transition metal ions (Fe3+, Cr3+ and V5+)

    Tuan Vu, Anh; Linh Bui, Thi Hai; Cuong Tran, Manh; Phuong Dang, Tuyet; Hoa Tran, Thi Kim; Tuan Nguyen, Quoc

    2010-01-01

    Nano TiO 2 was synthesized by the hydrothermal method. The sample was doped with transition metal ions (V, Cr and Fe) and non-metal (N). Doped TiO 2 samples were characterized by x-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and UV-Vis diffuse reflectance spectroscopy (UV-Vis). Photocatalytic activity in the mineralization of xylene (vapor phase), methylene blue and active dyer PR (liquid phase) was tested. In comparison with non-doped TiO 2 , V-, Cr-, Fe-doped TiO 2 and N-doped TiO 2 samples exhibited much higher photocatalytic activity using visible light instead of UV

  11. Ferromagnetism in Cr-doped passivated AlN nanowires

    Kanoun, Mohammed; Goumri-Said, Souraya; Schwingenschlö gl, Udo

    2014-01-01

    We apply first principles calculations to predict the effect of Cr doping on the electronic and magnetic properties of passivated AlN nanowires. We compare the energetics of the possible dopant sites and demonstrate the favorable configuration ferromagnetic ordering. The charge density of the pristine passivated AlN nanowires is used to elucidate the bonding character. Spin density maps demonstrate an induced spin polarization for N atoms next to dopant atoms, though most of the magnetism is carried by the Cr atoms. Cr-doped AlN nanowires turn out to be interesting for spintronic devices. © 2014 the Partner Organisations.

  12. Room temperature ferromagnetism in Co doped ZnO within an optimal doping level of 5%

    Mohapatra, J.; Mishra, D.K.; Mishra, Debabrata; Perumal, A.; Medicherla, V.R.R.; Phase, D.M.; Singh, S.K.

    2012-01-01

    Highlights: ► Zn 1−x Co x O ((0 ≤ x ≤ 0.1)) system synthesized by solid state reaction technique. ► Observation of room temperature ferromagnetism for 3 and 5% Co doped ZnO. ► XPS and EPMA studies predict the occurrence of segregated CoO clusters. ► Suppresses ferromagnetic ordering in higher doping percentage of Co (>5%). -- Abstract: We report on the structural, micro-structural and magnetic properties of Zn 1−x Co x O (0 ≤ x ≤ 0.1) system. Electron probe micro-structural analysis on 5% Co doped ZnO indicates the presence of segregated cobalt oxide which is also confirmed from the Co 2p core level X-ray photoelectron spectrum. The presence of oxygen defects in lower percentage of Co doped ZnO (≤5%) enhances the carrier mediated exchange interaction and thereby enhancing the room-temperature ferromagnetic behaviour. Higher doping percentage of cobalt (>5%) creates weak link between the grains and suppresses the carrier mediated exchange interaction. This is the reason why room temperature ferromagnetism is not observed in 7% and 10% Co doped ZnO.

  13. Chirality effect on nearly half-metallic properties in systematic endo-doping of 3d transition metals of narrow carbon nanotubes

    Malehmir, M.; Khoshnevisan, B., E-mail: b.khosh@kashanu.ac.ir

    2016-10-20

    Spin polarized density functional calculations were employed to study chirality effect on electronic and magnetic properties of 3d transition metals (TMs) endo-doped co-diameter (∼7 Å) narrow (5,5) and (9,0) single walled carbon nanotubes (CNTs). Various magnetizations up to ∼6μ{sub B} was obtained for different 3dTM-CNT systems (recall that the magnetization of fcc structure cobalt is ∼1.6μ{sub B}). In addition nearly half-metallic magnetic behavior has been observed for the most of considered systems. These results would be useful for spintronic and nano-magnetic technology.

  14. Oxygen vacancy-induced ferromagnetism in un-doped ZnO thin films

    Zhan, Peng; Wang, Weipeng; Liu, Can; Hu, Yang; Li, Zhengcao; Zhang, Zhengjun; Zhang, Peng; Wang, Baoyi; Cao, Xingzhong

    2012-02-01

    ZnO films became ferromagnetic when defects were introduced by thermal-annealing in flowing argon. This ferromagnetism, as shown by the photoluminescence measurement and positron annihilation analysis, was induced by the singly occupied oxygen vacancy with a saturated magnetization dependent positively on the amount of this vacancy. This study clarified the origin of the ferromagnetism of un-doped ZnO thin films and provides possibly an alternative way to prepare ferromagnetic ZnO films.

  15. Study of morphology effects on magnetic interactions and band gap variations for 3d late transition metal bi-doped ZnO nanostructures by hybrid DFT calculations

    Datta, Soumendu, E-mail: soumendu@bose.res.in; Baral, Sayan; Mookerjee, Abhijit [Department of Condensed Matter Physics and Material Sciences, S.N. Bose National Centre for Basic Sciences, JD Block, Sector-III, Salt Lake City, Kolkata 700 098 (India); Kaphle, Gopi Chandra [Central Department of Physics, Tribhuvan University, Kathmandu (Nepal)

    2015-08-28

    Using density functional theory (DFT) based electronic structure calculations, the effects of morphology of semiconducting nanostructures on the magnetic interaction between two magnetic dopant atoms as well as a possibility of tuning band gaps have been studied in the case of the bi-doped (ZnO){sub 24} nanostructures with the impurity dopant atoms of the 3d late transition metals—Mn, Fe, Co, Ni, and Cu. To explore the morphology effect, three different structures of the host (ZnO){sub 24} nano-system, having different degrees of spatial confinement, have been considered: a two dimensional nanosheet, a one dimensional nanotube, and a finite cage-shaped nanocluster. The present study employs hybrid density functional theory to accurately describe the electronic structure of all the systems. It is shown here that the magnetic coupling between the two dopant atoms remains mostly anti-ferromagnetic in the course of changing the morphology from the sheet geometry to the cage-shaped geometry of the host systems, except for the case of energetically most stable bi-Mn doping, which shows a transition from ferromagnetic to anti-ferromagnetic coupling with decreasing aspect ratio of the host system. The effect of the shape change, however, has a significant effect on the overall band gap variations of both the pristine as well as all the bi-doped systems, irrespective of the nature of the dopant atoms and provides a means for easy tunability of their optoelectronic properties.

  16. Room temperature ferromagnetism in Fe-doped CuO nanoparticles.

    Layek, Samar; Verma, H C

    2013-03-01

    The pure and Fe-doped CuO nanoparticles of the series Cu(1-x)Fe(x)O (x = 0.00, 0.02, 0.04, 0.06 and 0.08) were successfully prepared by a simple low temperature sol-gel method using metal nitrates and citric acid. Rietveld refinement of the X-ray diffraction data showed that all the samples were single phase crystallized in monoclinic structure of space group C2/c with average crystallite size of about 25 nm and unit cell volume decreases with increasing iron doping concentration. TEM micrograph showed nearly spherical shaped agglomerated particles of 4% Fe-doped CuO with average diameter 26 nm. Pure CuO showed weak ferromagnetic behavior at room temperature with coercive field of 67 Oe. The ferromagnetic properties were greatly enhanced with Fe-doping in the CuO matrix. All the doped samples showed ferromagnetism at room temperature with a noticeable coercive field. Saturation magnetization increases with increasing Fe-doping, becomes highest for 4% doping then decreases for further doping which confirms that the ferromagnetism in these nanoparticles are intrinsic and are not resulting from any impurity phases. The ZFC and FC branches of the temperature dependent magnetization (measured in the range of 10-350 K by SQUID magnetometer) look like typical ferromagnetic nanoparticles and indicates that the ferromagnetic Curie temperature is above 350 K.

  17. Magnetic properties of Mg{sub 12}O{sub 12} nanocage doped with transition metal atoms (Mn, Fe, Co and Ni): DFT study

    Javan, Masoud Bezi, E-mail: javan.masood@gmail.com

    2015-07-01

    Binding energy of the Mg{sub 12}O{sub 12} nanocage doped with transition metals (TM=Mn, Fe, Co and Ni) in endohedrally, exohedrally and substitutionally forms were studied using density functional theory with the generalized gradient approximation exchange-correlation functional along 6 different paths inside and outside of the Mg{sub 12}O{sub 12} nanocage. The most stable structures were determined with full geometry optimization near the minimum of the binding energy curves of all the examined paths inside and outside of the Mg{sub 12}O{sub 12} nanocage. The results reveal that for all stable structures, the Ni atom has a larger binding energy than the other TM atoms. It is also found that for all complexes additional peaks contributed by TM-3d, 4s and 4p states appear in the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) gap of the host MgO cluster. The mid-gap states are mainly due to the hybridization between TM-3d, 4s and 4p orbitals and the cage π orbitals. The magnetic moment of the endohedrally doped TM atoms in the Mg{sub 12}O{sub 12} are preserved to some extent due to the interaction between the TM and Mg{sub 12}O{sub 12} nanocage, in contrast to the completely quenched magnetic moment of the Fe and Ni atoms in the Mg{sub 11}(TM)O{sub 12} complexes. Furthermore, charge population analysis shows that charge transfer occurs from TM atom to the cage for endohedrally and substitutionally doping. - Highlights: • Binding energy of the Mg{sub 12}O{sub 12} nanocage doped with transition metals was studied. • The most stable structures were determined near the minimum of the binding energy. • The encapsulated Ni atom has a larger binding energy than the other TM atoms. • Magnetic moment of the endohedrally doped TM atoms in the Mg{sub 12}O{sub 12} are preserved.

  18. Photoluminescence and Raman studies for the confirmation of oxygen vacancies to induce ferromagnetism in Fe doped Mn:ZnO compound

    Das, J., E-mail: jayashree304@gmail.com [Department of Physics, Silicon Institute of Technology, Bhubaneswar 751024, Odisha (India); Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1710 (South Africa); Mishra, D.K. [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1710 (South Africa); Department of Physics, Institute of Technical Education and Research, Siksha ‘O’ Anusandhan University, Khandagiri Square, Bhubaneswar 751030, Odisha (India); Srinivasu, V.V. [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1710 (South Africa); Sahu, D.R. [Amity Institute of Nanotechnology, Amity University, Noida (India); Roul, B.K. [Institute of Materials Science, Planetarium Building, Acharya Vihar, Bhubaneswar, Odisha (India)

    2015-05-15

    With a motivation to compare the magnetic property, we synthesised undoped, transition metal (TM) Mn doped and (Mn:Fe) co-doped ZnO ceramics in the compositions ZnO, Zn{sub 0.98}Mn{sub 0.02}O and Zn{sub 0.96}(Mn{sub 0.02}Fe{sub 0.02})O. Systematic investigations on the structural, microstructural, defect structure and magnetic properties of the samples were performed. Low temperature as well as room temperature ferromagnetism has been observed for all our samples, however, enhanced magnetisation at room temperature has been noticed when ZnO is co-doped with Fe along with Mn. Particularly the sample with the composition Zn{sub 0.96}Mn{sub 0.02}Fe{sub 0.02}O showed a magnetisation value more than double of the sample with composition Zn{sub 0.98}Mn{sub 0.02}O, indicating long range strong interaction between the magnetic impurities leading to higher ferromagnetic ordering. Raman and PL studies reveal presence of higher defects in form of oxygen vacancy clusters created in the sample due to Fe co doping. PL study also reveals enhanced luminescence efficiency in the co doped sample. Temperature dependent magnetisation study of this sample shows the spin freezing temperature around 39 K indicating the presence of small impurity phase of Mn{sub 2−x}Zn{sub x}O{sub 3} type. Electron Spin Resonance signal obtained supports ferromagnetic state in the co doped sample. Enhancement of magnetisation is attributed to interactions mediated by magnetic impurities through large number of oxygen vacancies created by Fe{sup 3+} ions forming bound magnetic polarons (BMP) and facilitating long range ferromagnetic ordering in the co- doped system. - Highlights: • Comparison of magnetic property of ZnO, Zn{sub 0.98}Mn {sub 0.02}O and Zn{sub 0.96}(Mn{sub 0.02}Fe{sub 0.02})O. • Observation of enhanced magnetisation at room temperature in (Mn,Fe) doped ZnO. • Raman and PL studies reveal presence of higher oxygen vacancy clusters. • Electron Spin Resonance signal supports

  19. Large-Scale Synthesis of Transition-Metal-Doped TiO2 Nanowires with Controllable Overpotential

    Liu, Bin; Chen, HaoMing; Liu, Chong; Andrews, Sean; Han, Chris; Yang, Peidong

    2013-03-13

    Practical implementation of one-dimensional semiconductors into devices capable of exploiting their novel properties is often hindered by low product yields, poor material quality, high production cost, or overall lack of synthetic control. Here, we show that a molten-salt flux scheme can be used to synthesize large quantities of high-quality, single-crystalline TiO2 nanowires with controllable dimensions. Furthermore, in situ dopant incorporation of various transition metals allows for the tuning of optical, electrical, and catalytic properties. With this combination of control, robustness, and scalability, the molten-salt flux scheme can provide high-quality TiO2 nanowires to satisfy a broad range of application needs from photovoltaics to photocatalysis.

  20. Explanation of ferromagnetism origin in C-doped ZnO by first principle calculations

    El Amiri, A.; Lassri, H.; Hlil, E.K.; Abid, M.

    2015-01-01

    By ab-initio calculations, we systematically study possible source of ferromagnetism C-doped ZnO compound. The electronic structure and magnetic properties of C-doped ZnO with / without ZnO host and C defects were investigated using the Korringa–Kohn–Rostoker (KKR) method combined with coherent potential approximation (CPA). We show that Zn vacancy and presence of C defects (substitutional, interstitial or combination of both) induce the ferromagnetism in C-doped ZnO. From density of state (DOS) analysis, we show that p–p interaction between C atoms and/or C and O atoms is the mechanism of ferromagnetic coupling in C-doped ZnO. - Highlights: • We study the effect of ZnO host and C defects on ferromagnetism in C-doped ZnO. • Details of KKR method calculations performed to investigate both magnetic and electronic structures. • Magnetic moments, total and partial DOS for C-doped ZnO are well calculated and discussed. • Based on DOS calculations we interpret a origin of ferromagnetism in C-doped ZnO. • Mechanism of ferromagnetic coupling is well proposed

  1. Explanation of ferromagnetism origin in C-doped ZnO by first principle calculations

    El Amiri, A., E-mail: aelamiri@casablanca.ma [Laboratoire de Physique Fondamentale et Appliquée (LPFA), Faculté des Sciences Ain Chock, Université Hassan II, B.P. 5366 Mâarif, Casablanca, Maroc (Morocco); Lassri, H. [Laboratoire de Physique des Matériaux, Micro-électronique, Automatique et Thermique (LPMMAT). Faculté des Sciences Ain Chock, Université Hassan II, B.P. 5366 Mâarif, Casablanca, Maroc (Morocco); Hlil, E.K. [Institut Néel, CNRS et Université Joseph Fourier, BP 166, 38042 Grenoble (France); Abid, M. [Laboratoire de Physique Fondamentale et Appliquée (LPFA), Faculté des Sciences Ain Chock, Université Hassan II, B.P. 5366 Mâarif, Casablanca, Maroc (Morocco)

    2015-01-15

    By ab-initio calculations, we systematically study possible source of ferromagnetism C-doped ZnO compound. The electronic structure and magnetic properties of C-doped ZnO with / without ZnO host and C defects were investigated using the Korringa–Kohn–Rostoker (KKR) method combined with coherent potential approximation (CPA). We show that Zn vacancy and presence of C defects (substitutional, interstitial or combination of both) induce the ferromagnetism in C-doped ZnO. From density of state (DOS) analysis, we show that p–p interaction between C atoms and/or C and O atoms is the mechanism of ferromagnetic coupling in C-doped ZnO. - Highlights: • We study the effect of ZnO host and C defects on ferromagnetism in C-doped ZnO. • Details of KKR method calculations performed to investigate both magnetic and electronic structures. • Magnetic moments, total and partial DOS for C-doped ZnO are well calculated and discussed. • Based on DOS calculations we interpret a origin of ferromagnetism in C-doped ZnO. • Mechanism of ferromagnetic coupling is well proposed.

  2. Nonthermal Photocoercivity Effect in Low-Doped (Ga,Mn)As Ferromagnetic Semiconductor

    Kiessling, T.; Astakhov, G. V.; Hoffmann, H.; Korenev, V. L.; Schwittek, J.; Schott, G. M.; Gould, C.; Ossau, W.; Brunner, K.; Molenkamp, L. W.

    2011-12-01

    We report a photoinduced change of the coercive field of a low doped Ga1-xMnxAs ferromagnetic semiconductor under very low intensity illumination. This photocoercivity effect (PCE) is local and reversible, which enables the controlled formation of localized magnetization domains. The PCE arises from a light induced lowering of the domain wall pinning energy as confirmed by test experiments on high doped, fully metallic ferromagnetic Ga1-xMnxAs.

  3. Hole polaron-polaron interaction in transition metal oxides and its limit to p-type doping

    Chen, Shiyou; Wang, Lin-Wang

    2014-03-01

    Traditionally the origin of the poor p-type conductivity in some transition metal oxides (TMOs) was attributed to the limited hole concentration: the charge-compensating donor defects, such as oxygen vacancies and cation interstitials, can form spontaneously as the Fermi energy shifts down to near the valence band maximum. Besides the thermodynamic limit to the hole concentration, the limit to the hole mobility can be another possible reason, e.g., the hole carrier can form self-trapped polarons with very low carrier mobility. Although isolated hole polarons had been found in some TMOs, the polaron-polaron interaction is not well-studied. Here we show that in TMOs such as TiO2 and V2O5, the hole polarons prefer to bind with each other to form bipolarons, which are more stable than free hole carriers or separated polarons. This pushes the hole states upward into the conduction band and traps the holes. The rise of the Fermi energy suppresses the spontaneous formation of the charge-compensating donor defects, so the conventional mechanism becomes ineffective. Since it can happen in the impurity-free TMO lattices, independent of any extrinsic dopant, it acts as an intrinsic and general limit to the p-type conductivity in these TMOs. This material is based upon work performed by the JCAP, a US DOE Energy Innovation Hub, the NSFC (No. 61106087 and 91233121) and special funds for major state basic research (No. 2012CB921401).

  4. Emission channeling studies on transition-metal doped GaN and ZnO: Cation versus anion substitution

    AUTHOR|(CDS)2070176; Wahl, Ulrich; Martins Correia, Joao; Amorim, Lígia; Silva, Daniel; Decoster, Stefan; Castro Ribeiro Da Silva, Manuel; Temst, Kristiaan; Vantomme, André

    2014-01-01

    The magnetic and electric properties of impurities in semiconductors are strongly dependent on the lattice sites which they occupy. While the majority site can often be predicted based on chemical similarities with the host elements and is usually simple to confirm experimentally, minority sites are far more complicated to predict, detect and identify. We have carried out extensive beta− emission channeling studies on the lattice location of transition metal impurities in wide-gap dilute magnetic semiconductors, namely Co and Mn in GaN and ZnO, making use of radioactive 61Co and 56Mn implanted at the ISOLDE facility at CERN. In addition to the majority occupation of cation (Ga, Zn) sites, we located significant fractions (of the order of 20%) of the Co and Mn impurities in anion (N, O) sites, which are virtually unaffected by thermal annealing up to 900 °C. Here, we present the beta− emission channeling experiments on 61Co-implanted GaN. We discuss these results in the context of our recent reports of mi...

  5. Structural characterization of tellurite glasses doped with transition metal oxides using Raman spectra and ab initio calculations.

    Mohamed, Tarek A; Shaltout, I; Al Yahyaei, K M

    2006-05-01

    Systems of iron tellurite glasses were prepared by melt quenching with compositions of [85%TeO2+5%Fe2O3+10%TMO], where transition metal oxides (TMO) are TiO2, V2O5, MnO, CoO, NiO and CuO. Furthermore, the main structural units of these samples have been characterized by means of Raman spectra (150-1200 cm(-1)) as well as wavenumber predictions by means of Gaussian 98 ab initio calculations for the proposed site symmetries of TeO4(4-) triagonal bipyramid (C2v) and Te2O7(6-) bridged tetrahedra (Cs and C1). Aided by normal coordinate analysis, calculated vibrational frequencies, Raman scattering activities, force constants in internal coordinates and potential energy distributions (PEDs), revised vibrational assignments for the fundamental modes have been proposed. The main structural features are correlated to the dominant units of triagonal bipyramid (tbp) or bridged tetrahedral (TeO3+1 binds to TeO3 through TeOTe bridge; corner sharing). Moreover, the Raman spectra of the investigated tellurites reflect a structural change from tbp (coordination number is four) to triagonal pyramidal (coordination number is three).

  6. Ferromagnetic Behaviors in Fe-Doped NiO Nanofibers Synthesized by Electrospinning Method

    Yi-Dong Luo

    2013-01-01

    Full Text Available Ni1−xFexO nanofibers with different Fe doping concentration have been synthesized by electrospinning method. An analysis of the phase composition and microstructure shows that Fe doping has no influence on the crystal structure and morphology of NiO nanofibers, which reveals that the doped Fe ions have been incorporated into the NiO host lattice. Pure NiO without Fe doping is antiferromagnetic, yet all the Fe-doped NiO nanofiber samples show obvious room-temperature ferromagnetic properties. The saturation magnetization of the nanofibers can be enhanced with increasing Fe doping concentration, which can be ascribed to the double exchange mechanism through the doped Fe ions and free charge carriers. In addition, it was found that the diameter of nanofibers has significant impact on the ferromagnetic properties, which was discussed in detail.

  7. Magnetic Ground State Properties of Transition Metals

    Andersen, O. K.; Madsen, J.; Poulsen, U. K.

    1977-01-01

    We review a simple one-electron theory of the magnetic and cohesive properties of ferro- and nearly ferromagnetic transition metals at 0 K. The theory is based on the density functional formalism, it makes use of the local spin density and atomic sphere approximations and it may, with further app...

  8. Variation in band gap of lanthanum chromate by transition metals doping LaCr{sub 0.9}A{sub 0.1}O{sub 3} (A:Fe/Co/Ni)

    Naseem, Swaleha, E-mail: wasiamu@gmail.com; Khan, Wasi, E-mail: wasiamu@gmail.com; Saad, A. A., E-mail: wasiamu@gmail.com; Shoeb, M., E-mail: wasiamu@gmail.com; Ahmed, Hilal, E-mail: wasiamu@gmail.com; Naqvi, A. H. [Centre of Excellence in Materials Science (Nanomaterials), Department of Applied Physics, Z.H. College of Engg. and Technology, Aligarh Muslim University, Aligarh-202002 (India); Husain, Shahid [Department of Physics, Aligarh Muslim University, Aligarh-202002 (India)

    2014-04-24

    Transition metal (Fe, Co, Ni) doped lanthanum chromate (LaCrO{sub 3}) nanoparticles (NPs) were prepared by gel combustion method and calcinated at 800°C. Microstructural studies were carried by XRD and SEM/EDS techniques. The results of structural characterization show the formation of all samples in single phase without any impurity. Optical properties were studied by UV- visible and photoluminescence techniques. The energy band gap was calculated and the variation was observed with the doping of transition metal ions. Photoluminescence spectra show the emission peak maxima for the pure LaCrO{sub 3} at about 315 nm. Influence of Fe, Co, Ni doping was studied and compared with pure lanthanum chromate nanoparticles.

  9. Room temperature ferromagnetism and gas sensing in ZnOnanostructures: Influence of intrinsic defects and Mn, Co, Cu doping

    Mhlongo, Gugu, H

    2016-12-01

    Full Text Available analysis based on photoluminescence (PL) and electron paramagnetic resonance (EPR) indicated that co-existing oxygen vacancies (V(subO)) and zinc interstitials (Zni) defects are responsible for the observed ferromagnetism in undoped and transition metal (TM...

  10. Photo-catalytic studies of transition metal doped titanium dioxide thin films processed by metalorganic decomposition (MOD) method

    Talagala, P.; Marko, X.; Padmanabhan, K. R.; Naik, R.; Rodak, D.; Cheng, Y. T.

    2006-03-01

    We have synthesized pure and transition element (Fe, Co and V) doped Titanium oxide thin films of thickness ˜ 350 nm on sapphire, Si, and stainless steel substrates by Metalorganic Decomposition (MOD) method. The films were subsequently annealed at appropriate temperatures ( 500-750C) to obtain either anatase or the rutile phase of TiO2. Analysis of the composition of the films were performed by energy dispersive X-ray(EDAX) and Rutherford backscattering spectrometry(RBS). Ion channeling was used to identify possible epitaxial growth of the films on sapphire. Both XRD and Raman spectra of the films exhibit that the films annealed at 550C are of anatase phase, while those annealed at 700C seem to prefer a rutile structure. The water contact angle measurements of the films before and after photoactivation, demonstrate a significant reduction in the contact angle for the anatase phase. However, the variation in contact angle was observed for films exposed to UV (<10^o-30^o) and dark (25^o-50^o). Films doped with Fe show a trend towards lower contact angle than those doped with Co. Results with films doped with V will also be included.

  11. Tailoring ferromagnetism in chromium-doped zinc oxide

    Haq, Bakhtiar Ul

    2014-03-11

    The simultaneous manipulation of both charge and spin has made diluted magnetic semiconductors (DMS) a potential material for the fabrication of spintronic devices. We report DMSs based on ZnO doped with Cr in wurtzite (WZ) and zinc-blend (ZB) geometries. The injection of Cr impurities at a concentration of 6.25% has successfully tuned ferromagnetism in ZnO. To recognize the nature of magnetic interactions, two spatial configurations are investigated, where the impurity atoms are placed at minimum and maximum separation distances. The material favors the short-range magnetic coupling and has a tendency towards Cr clustering. The injection of a Cr impurity into ZnO strongly influences the electronic properties in terms of band structure, dependent on the impurity spatial distribution. It is half metallic for both structural geometries when impurity atoms have minimum separation and is metallic when they are placed far apart. Moreover, replacing Zn with Cr does not show a significant effect on the structural geometries. Our results endorse that Cr:ZnO can be efficiently used for spin-polarized transport and other spin-dependent applications in both hexagonal and cubic phases.

  12. Hole-induced d"0 ferromagnetism enhanced by Na-doping in GaN

    Zhang, Yong; Li, Feng

    2017-01-01

    The d"0 ferromagnetism in wurtzite GaN is investigated by the first-principle calculations. It is found that spontaneous magnetization occurs if sufficient holes are injected in GaN. Both Ga vacancy and Na doping can introduce holes into GaN. However, Ga vacancy has a high formation energy, and is thus unlikely to occur in a significant concentration. In contrast, Na doping has relatively low formation energy. Under N-rich growth condition, Na doping with a sufficient concentration can be achieved, which can induce half-metallic ferromagnetism in GaN. Moreover, the estimated Curie temperature of Na-doped GaN is well above the room temperature. - Highlights: • Hole-induced ferromagnetism in GaN is confirmed. • Both Ga Vacancy and Na-doping can introduce hole into GaN. • The concentration of Ga vacancy is too low to induce detectable ferromagnetism. • Na-doped GaN is a possible ferromagnet with a high curie-temperature.

  13. Room temperature ferromagnetism in Mn-doped NiO nanoparticles

    Layek, Samar, E-mail: samarlayek@gmail.com; Verma, H.C.

    2016-01-01

    Mn-doped NiO nanoparticles of the series Ni{sub 1−x}Mn{sub x}O (x=0.00, 0.02, 0.04 and 0.06) are successfully synthesized using a low temperature hydrothermal method. Samples up to 6% Mn-doping are single phase in nature as observed from powder x-ray diffraction (XRD) studies. Rietveld refinement of the XRD data shows that all the single phase samples crystallize in the NaCl like fcc structure with space group Fm-3m. Unit cell volume decreases with increasing Mn-doping. Pure NiO nanoparticles show weak ferromagnetism, may be due to nanosize nature. Introduction of Mn within NiO lattice improves the magnetic properties significantly. Room temperature ferromagnetism is found in all the doped samples whereas the magnetization is highest for 2% Mn-doping and then decreases with further doping. The ZFC and FC branches in the temperature dependent magnetization separate well above 350 K indicating transition temperature well above room temperature for 2% Mn-doped NiO Nanoparticle. The ferromagnetic Curie temperature is found to be 653 K for the same sample as measured by temperature dependent magnetization study using vibrating sample magnetometer (VSM) in high vacuum. - Highlights: • Mn-doped NiO nanoparticles are prepared by a simple hydrothermal method. • Unit cell volume decreases with increasing doping concentration. • Mn-doping leads to room temperature ferromagnetism in NiO nanoparticles. • Magnetization is highest for 2% Mn-doping. • Above 2%, magnetization decreases with increasing doping.

  14. Room temperature ferromagnetism in Mn-doped NiO nanoparticles

    Layek, Samar; Verma, H.C.

    2016-01-01

    Mn-doped NiO nanoparticles of the series Ni_1_−_xMn_xO (x=0.00, 0.02, 0.04 and 0.06) are successfully synthesized using a low temperature hydrothermal method. Samples up to 6% Mn-doping are single phase in nature as observed from powder x-ray diffraction (XRD) studies. Rietveld refinement of the XRD data shows that all the single phase samples crystallize in the NaCl like fcc structure with space group Fm-3m. Unit cell volume decreases with increasing Mn-doping. Pure NiO nanoparticles show weak ferromagnetism, may be due to nanosize nature. Introduction of Mn within NiO lattice improves the magnetic properties significantly. Room temperature ferromagnetism is found in all the doped samples whereas the magnetization is highest for 2% Mn-doping and then decreases with further doping. The ZFC and FC branches in the temperature dependent magnetization separate well above 350 K indicating transition temperature well above room temperature for 2% Mn-doped NiO Nanoparticle. The ferromagnetic Curie temperature is found to be 653 K for the same sample as measured by temperature dependent magnetization study using vibrating sample magnetometer (VSM) in high vacuum. - Highlights: • Mn-doped NiO nanoparticles are prepared by a simple hydrothermal method. • Unit cell volume decreases with increasing doping concentration. • Mn-doping leads to room temperature ferromagnetism in NiO nanoparticles. • Magnetization is highest for 2% Mn-doping. • Above 2%, magnetization decreases with increasing doping.

  15. Transition metal doped poly(aniline-co-pyrrole)/multi-walled carbon nanotubes nanocomposite for high performance supercapacitor electrode materials

    Dhibar, Saptarshi; Bhattacharya, Pallab; Hatui, Goutam; Das, C.K.

    2015-01-01

    Highlights: • The CuCl 2 doped copolymer (PANI and PPy)/MWCNTs nanocomposite was prepared. • The nanocomposite achieved highest specific capacitance of 383 F/g at a 0.5 A/g. • Nanocomposite exhibits better energy density as well as power density. • The nanocomposite also showed better electrical conductivity at room temperature. • The nanocomposite can be used as promising electrode materials for supercapacitor. - Abstract: In this present communication, copolymer of polyaniline (PANI) and polypyrrole (PPy) that is poly(aniline-co-pyrrole) [poly(An-co-Py)], copper chloride (CuCl 2 ) doped poly(aniline-co-pyrrole) [poly(An-co-Py) Cu], and CuCl 2 doped poly(aniline-co-pyrrole)/multi walled carbon nanotubes (MWCNTs) [poly(An-co-Py) Cu CNT] nanocomposite have been prepared by a simple and inexpensive in-situ chemical oxidative polymerization method, using ammonium persulfate (APS) as oxidant and hydrochloric acid (HCl) as dopant and investigated as high performance supercapacitor electrode materials. The possible interaction between CuCl 2 with copolymers and MWCNTs was investigated by Fourier transform infrared spectroscopy (FTIR) and UV–visible spectroscopy analysis. The morphological characteristic of all the electrode materials were analyzed by Field emission scanning electron microscopy (FESEM) and Transmission electron microscopy (TEM) study. The electrochemical characterizations of all the electrode materials were carried out by three electrode probe method where, standard calomel electrode and platinum were used as reference and counter electrodes, respectively. Among all the electrode materials, poly(An-co-Py) Cu CNT nanocomposite achieved highest specific capacitance value of 383 F/g at 0.5 A/g scan rate. The nanocomposite showed better electrical conductivity at room temperature and also attained nonlinear current–voltage characteristic. Based on the superior electrochemical as well as other properties the as prepared nanocomposite can be used

  16. Transition metal doped poly(aniline-co-pyrrole)/multi-walled carbon nanotubes nanocomposite for high performance supercapacitor electrode materials

    Dhibar, Saptarshi; Bhattacharya, Pallab; Hatui, Goutam; Das, C.K., E-mail: chapal12@yahoo.co.in

    2015-03-15

    Highlights: • The CuCl{sub 2} doped copolymer (PANI and PPy)/MWCNTs nanocomposite was prepared. • The nanocomposite achieved highest specific capacitance of 383 F/g at a 0.5 A/g. • Nanocomposite exhibits better energy density as well as power density. • The nanocomposite also showed better electrical conductivity at room temperature. • The nanocomposite can be used as promising electrode materials for supercapacitor. - Abstract: In this present communication, copolymer of polyaniline (PANI) and polypyrrole (PPy) that is poly(aniline-co-pyrrole) [poly(An-co-Py)], copper chloride (CuCl{sub 2}) doped poly(aniline-co-pyrrole) [poly(An-co-Py) Cu], and CuCl{sub 2} doped poly(aniline-co-pyrrole)/multi walled carbon nanotubes (MWCNTs) [poly(An-co-Py) Cu CNT] nanocomposite have been prepared by a simple and inexpensive in-situ chemical oxidative polymerization method, using ammonium persulfate (APS) as oxidant and hydrochloric acid (HCl) as dopant and investigated as high performance supercapacitor electrode materials. The possible interaction between CuCl{sub 2} with copolymers and MWCNTs was investigated by Fourier transform infrared spectroscopy (FTIR) and UV–visible spectroscopy analysis. The morphological characteristic of all the electrode materials were analyzed by Field emission scanning electron microscopy (FESEM) and Transmission electron microscopy (TEM) study. The electrochemical characterizations of all the electrode materials were carried out by three electrode probe method where, standard calomel electrode and platinum were used as reference and counter electrodes, respectively. Among all the electrode materials, poly(An-co-Py) Cu CNT nanocomposite achieved highest specific capacitance value of 383 F/g at 0.5 A/g scan rate. The nanocomposite showed better electrical conductivity at room temperature and also attained nonlinear current–voltage characteristic. Based on the superior electrochemical as well as other properties the as prepared

  17. Elucidation of structural, vibrational and dielectric properties of transition metal (Co2+) doped spinel Mg-Zn chromites

    Choudhary, Pankaj; Varshney, Dinesh

    2018-05-01

    Co2+ doped Mg-Zn spinel chromite compositions Mg0.5Zn0.5-xCoxCr2O4 (0.0 ≤ x ≤ 0.5) have been synthesized by the high-temperature solid state method. Synchrotron and X-ray diffraction (XRD) studies show single-phase crystalline nature. The structural analysis is validated by Rietveld refinement confirms the cubic structure with space group Fd3m. Crystallite size is estimated from Synchrotron XRD which was found to be 30-34 nm. Energy dispersive analysis confirms stoichiometric Mg0.5Zn0.5-xCoxCr2O4 composition. Average crystallite size distribution is estimated from imaging software (Image - J) of SEM is in the range of 100-250 nm. Raman spectroscopy reveals four active phonon modes, and a pronounced red shift is due to enhanced Co2+ concentration. Increased Co2+ concentration in Mg-Zn chromites shows a prominent narrowing of band gap from 3.46 to 2.97 eV. The dielectric response is attributed to the interfacial polarization, and the electrical modulus study supports non-Debye type of dielectric relaxation. Ohmic junctions (minimum potential drop) at electrode interface are active at lower levels of doping (x transformer applications at high frequencies.

  18. Transition Metal Ions Enable the Transition from Electrospun Prolamin Protein Fibers to Nitrogen-Doped Freestanding Carbon Films for Flexible Supercapacitors.

    Wang, Yixiang; Yang, Jingqi; Du, Rongbing; Chen, Lingyun

    2017-07-19

    Flexible carbon ultrafine fibers are highly desirable in energy storage and conversion devices. Our previous finding showed that electrospun hordein/zein fibers stabilized by Ca 2+ were successfully transferred into nitrogen-doped carbon ultrafine fibers for supercapacitors. However, their relatively brittle nature needed to be improved. Inspired by this stabilizing effect of Ca 2+ , in this work, four transition metal divalent cations were used to assist the formation of flexible hordein/zein-derived carbon ultrafine fibers. Without alteration of the electrospinnability, adequate amounts of zinc acetate and cobalt acetate supported the fibrous structure during pyrolysis. This resulted in flexible freestanding carbon films consisting of well-defined fibers with nitrogen-doped graphitic layers and hierarchical pores. These carbon films were easily cut into small square pieces and directly applied as working electrode in the three-electrode testing system without the need for polymer binders or conducting agents. Notably, the hz-Zn0.3-p electrode, synthesized with 0.3 mol/L Zn 2+ and post-acid treatment, exhibited a specific capacitance of 393 F/g (at 1 A/g), a large rate capability (72.3% remained at 20 A/g), and a capacitance retention of ∼98% after 2000 charging-discharging cycles at 10 A/g. These superior electrochemical properties were attributed to the synergistic effects of the well-developed graphitic layers induced by Zn 2+ , the nitrogen-decorated carbon structure, and the interconnected channels generated by HCl treatment. This research advances potential applications for prolamin proteins as nitrogen-containing raw materials in developing carbon structures for high-performance supercapacitors.

  19. Searching Room Temperature Ferromagnetism in Wide Gap Semiconductors Fe-doped Strontium Titanate and Zinc Oxide

    Pereira, LMC; Wahl, U

    Scientific findings in the very beginning of the millennium are taking us a step further in the new paradigm of technology: spintronics. Upgrading charge-based electronics with the additional degree of freedom of the carriers spin-state, spintronics opens a path to the birth of a new generation of devices with the potential advantages of non-volatility and higher processing speed, integration densities and power efficiency. A decisive step towards this new age lies on the attribution of magnetic properties to semiconductors, the building block of today's electronics, that is, the realization of ferromagnetic semiconductors (FS) with critical temperatures above room temperature. Unfruitful search for intrinsic RT FS lead to the concept of Dilute(d) Magnetic Semiconductors (DMS): ordinary semiconductor materials where 3 d transition metals randomly substitute a few percent of the matrix cations and, by some long-range mechanism, order ferromagnetically. The times are of intense research activity and the last fe...

  20. Substrate effect on the room-temperature ferromagnetism in un-doped ZnO films

    Zhan, Peng; Wang, Weipeng; Xie, Zheng; Li, Zhengcao; Zhang, Zhengjun; Zhang, Peng; Wang, Baoyi; Cao, Xingzhong

    2012-07-01

    Room-temperature ferromagnetism was achieved in un-doped ZnO films on silicon and quartz substrates. Photoluminescence measurement and positron annihilation analysis suggested that the ferromagnetism was originated from singly occupied oxygen vacancies (roughly estimated as ˜0.55 μB/vacancy), created in ZnO films by annealing in argon. The saturated magnetization of ZnO films was enhanced from ˜0.44 emu/g (on quartz) to ˜1.18 emu/g (on silicon) after annealing at 600 °C, as silicon acted as oxygen getter and created more oxygen vacancies in ZnO films. This study clarified the origin of ferromagnetism in un-doped ZnO and provides an idea to enhance the ferromagnetism.

  1. Doping effect on ferromagnetism, ferroelectricity and dielectric constant in sol-gel derived Bi1-xNdxFe1-yCoyO3 nanoceramics

    Das, Sananda; Sahoo, R. C.; Bera, K. P.; Nath, T. K.

    2018-04-01

    Doping at the post-transition metal site by trivalent rare-earth ions and 3d transition metal site by transition metal ions in perovskite lattice has observed a variety of magnetic and electronic orders with spatially correlated charge, spin and orbital degrees of freedom. Here, we report large ferromagnetism and enhanced dielectric constant (at ∼100 Hz) in chemically synthesized single phase multiferroic Bi1-xNdxFe1-yCoyO3 (x = 0, 0.10; y = 0, 0.10) nanoparticles (average particles size ∼45 nm). We have also examined the ferroelectric nature of our chemically synthesized samples. The Rietveld refinement of the XRD data reveals the structural symmetry breaking from distorted rhombohedral R3c structure of BiFeO3 to the triclinic P1 structure in Bi0.9Nd0.1Fe0.9Co0.1O3 (BNFCO) without having any iron rich impurity phase. The magnetization in these nanoceramics most likely originates from the coexistence of mixed valence states of Fe ion (Fe2+ and Fe3+). A high room temperature dielectric constant (∼1050) has been observed at 100 Hz of BNFCO sample. The frequency dependent anomalies near Neel temperature of antiferromagnet in temperature variation of dielectric study have been observed for all the doped and co-doped samples exhibiting typical characteristic of relaxor ferroelectrics. A spectacular enhancement of remanent magnetization MR (∼7.2 emu/gm) and noticeably large coercivity HC (∼17.4 kOe) at 5 K have been observed in this BNFCO sample. Such emergence of ferromagnetic ordering indicates the canting of the surface spins at the surface boundaries because of the reduction of particle size in nanodimension. We have also observed P-E hysteresis loops with a remanent polarization of 26 μC/cm2 and coercive field of 5.6 kV/cm of this sample at room temperature. From impedance spectroscopy study the estimated activation energy of 0.41 eV suggests the semiconducting nature of our nanoceramic BNCFO sample.

  2. Ferromagnetism in Fe-doped ZnO Nanocrystals: Experimental and Theoretical investigations

    Karmakar, Debjani; Mandal, S. K.; Kadam, R. M.; Paulose, P. L.; Rajarajan, A. K.; Nath, T. K.; Das, A. K.; Dasgupta, I.; Das, G. P.

    2007-01-01

    Fe-doped ZnO nanocrystals are successfully synthesized and structurally characterized by using x-ray diffraction and transmission electron microscopy. Magnetization measurements on the same system reveal a ferromagnetic to paramagnetic transition temperature > 450 K with a low-temperature transition from ferromagnetic to spin-glass state due to canting of the disordered surface spins in the nanoparticle system. Local magnetic probes like EPR and Mossbauer indicate the presence of Fe in both v...

  3. Origin of the defects-induced ferromagnetism in un-doped ZnO single crystals

    Zhan, Peng; Xie, Zheng; Li, Zhengcao; Wang, Weipeng; Zhang, Zhengjun; Li, Zhuoxin; Cheng, Guodong; Zhang, Peng; Wang, Baoyi; Cao, Xingzhong

    2013-02-01

    We clarified, in this Letter, that in un-doped ZnO single crystals after thermal annealing in flowing argon, the defects-induced room-temperature ferromagnetism was originated from the surface defects and specifically, from singly occupied oxygen vacancies denoted as F+, by the optical and electrical properties measurements as well as positron annihilation analysis. In addition, a positive linear relationship was observed between the ferromagnetism and the F+ concentration, which is in support with the above clarification.

  4. Density functional theory calculation of monolayer WTe2 transition metal dichalcogenides doped with H, Li and Be

    Igumbor, E.; Mapasha, R. E.; Meyer, W. E.

    2018-04-01

    Results based on density functional theory modelling of electronic and structural properties of single layer WTe2 dichalcogenides doped with X (X=H, Li and Be) were presented. The generalized gradient approximation functional of Perdew, Burke, and Ernzerhof exchange correlation was used for all calculations. Formation energies of X dopant substituted for W (XW) were obtained to be between 3.59 and 2.61 eV. The LiW defect with energy of formation of 2.14 eV was energetically the most favourable. For all dopants considered, while the HW induced no magnetic moment, the LiW and BeW induced magnetic moments of 3.44 and 0.05 μB, respectively. The band gap of the WTe2 as a result of the dopants was populated with several orbital ground states, and thus reduced within a few eV. While all XW behave as p - type dopant, the LiW defect posses half metallic character.

  5. Defect-band mediated ferromagnetism in Gd-doped ZnO thin films

    Venkatesh, S.

    2015-01-07

    Gd-doped ZnO thin films prepared by pulsed laser deposition with Gd concentrations varying from 0.02–0.45 atomic percent (at. %) showed deposition oxygen pressure controlled ferromagnetism. Thin films prepared with Gd dopant levels (ferromagnetic at room temperature. Negative magnetoresistance, electric transport properties showed that the ferromagnetic exchange is mediated by a spin-split defect band formed due to oxygen deficiency related defect complexes. Mott\\'s theory of variable range of hopping conduction confirms the formation of the impurity/defect band near the Fermi level.

  6. A close correlation between induced ferromagnetism and oxygen deficiency in Fe doped In2O3

    Singhal, R.K.; Samariya, A.; Kumar, Sudhish; Sharma, S.C.; Xing, Y.T.; Deshpande, U.P.; Shripathi, T.; Saitovitch, E.

    2010-01-01

    We report on the reversible manipulation of room temperature ferromagnetism in Fe (5%) doped In 2 O 3 polycrystalline magnetic semiconductor. The X-ray diffraction and photoemission measurements confirm that the Fe ions are well incorporated into the lattice, substituting the In 3+ ions. The magnetization measurements show that the host In 2 O 3 has a diamagnetic ground state, while it shows weak ferromagnetism at 300 K upon Fe doping. The as-prepared sample was then sequentially annealed in hydrogen, air, vacuum and finally in air. The ferromagnetic signal shoots up by hydrogenation as well as vacuum annealing and bounces back upon re-annealing the samples in air. The sequence of ferromagnetism shows a close inter-relationship with the behavior of oxygen vacancies (V o ). The Fe ions tend to a transform from 3+ to 2+ state during the giant ferromagnetic induction, as revealed by photoemission spectroscopy. A careful characterization of the structure, purity, magnetic, and transport properties confirms that the ferromagnetism is due to neither impurities nor clusters but directly related to the oxygen vacancies. The ferromagnetism can be reversibly controlled by these vacancies while a parallel variation of carrier concentration, as revealed by resistance measurements, appears to be a side effect of the oxygen vacancy variation.

  7. Lead Monoxide: Two-Dimensional Ferromagnetic Semiconductor Induced by Hole-Doping

    Wang, Yao

    2017-04-12

    We employ first-principles calculations to demonstrate ferromagnetic ground states for single- and multi-layer lead monoxide (PbO) under hole-doping, originating from a van Hove singularity at the valence band edge. Both the sample thickness and applied strain are found to have huge effects on the electronic and magnetic properties. Multi-layer PbO is an indirect band gap semiconductor, while a direct band gap is realized in the single-layer limit. In hole-doped single-layer PbO, biaxial tensile strain can enhance the stability of the ferromagnetic state.

  8. Ionized zinc vacancy mediated ferromagnetism in copper doped ZnO thin films

    Shi-Yi Zhuo

    2012-03-01

    Full Text Available This paper reports the origin of ferromagnetism in Cu-doped ZnO thin films. Room-temperature ferromagnetism is obtained in all the thin films when deposited at different oxygen partial pressure. An obviously enhanced peak corresponding to zinc vacancy is observed in the photoluminescence spectra, while the electrical spin resonance measurement implies the zinc vacancy is negative charged. After excluding the possibility of direct exchange mechanisms (via free carriers, we tentatively propose a quasi-indirect exchange model (via ionized zinc vacancy for Cu-doped ZnO system.

  9. Lead Monoxide: Two-Dimensional Ferromagnetic Semiconductor Induced by Hole-Doping

    Wang, Yao; Zhang, Qingyun; Shen, Qian; Cheng, Yingchun; Schwingenschlö gl, Udo; Huang, Wei

    2017-01-01

    We employ first-principles calculations to demonstrate ferromagnetic ground states for single- and multi-layer lead monoxide (PbO) under hole-doping, originating from a van Hove singularity at the valence band edge. Both the sample thickness and applied strain are found to have huge effects on the electronic and magnetic properties. Multi-layer PbO is an indirect band gap semiconductor, while a direct band gap is realized in the single-layer limit. In hole-doped single-layer PbO, biaxial tensile strain can enhance the stability of the ferromagnetic state.

  10. Room temperature ferromagnetism in Mn-doped NiO nanoparticles

    Layek, Samar; Verma, H. C.

    2016-01-01

    Mn-doped NiO nanoparticles of the series Ni1-xMnxO (x=0.00, 0.02, 0.04 and 0.06) are successfully synthesized using a low temperature hydrothermal method. Samples up to 6% Mn-doping are single phase in nature as observed from powder x-ray diffraction (XRD) studies. Rietveld refinement of the XRD data shows that all the single phase samples crystallize in the NaCl like fcc structure with space group Fm-3m. Unit cell volume decreases with increasing Mn-doping. Pure NiO nanoparticles show weak ferromagnetism, may be due to nanosize nature. Introduction of Mn within NiO lattice improves the magnetic properties significantly. Room temperature ferromagnetism is found in all the doped samples whereas the magnetization is highest for 2% Mn-doping and then decreases with further doping. The ZFC and FC branches in the temperature dependent magnetization separate well above 350 K indicating transition temperature well above room temperature for 2% Mn-doped NiO Nanoparticle. The ferromagnetic Curie temperature is found to be 653 K for the same sample as measured by temperature dependent magnetization study using vibrating sample magnetometer (VSM) in high vacuum.

  11. Oligocyclopentadienyl transition metal complexes

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.

    2002-01-18

    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  12. Structure and magnetism of transition-metal implanted dilute magnetic semiconductors

    Pereira, Lino; Temst, K; Araújo, JP; Wahl, U

    The discovery of a dilute magnetic semiconductor (DMS) in which ferromagnetism is carrier-mediated and persists above room temperature is a critical step towards the development of semiconductor-based spintronics. Among the many types of DMS materials which have been investigated, the current research interest can be narrowed down to two main classes of materials: (1) narrow-gap III-V semiconductors, mostly GaAs and InAs, doped with Mn; (2) wide-gap oxides and nitrides doped with 3d transition metals, mostly Mn- and Co-doped ZnO and Mn-doped GaN. With a number of interesting functionalities deriving from the carrier-mediated ferromagnetism and demonstrated in various proof-of-concept devices, Mn-doped GaAs has become, among DMS materials, one of the best candidates for technological application. However, despite major developments over the last 15 years, the maximum Curie temperature (185 K) remains well below room temperature. On the other hand, wide-gap DMS materials appear to exhibit ferromagnetic behavior...

  13. Room temperature ferromagnetism in Fe-doped semiconductor ZrS2 single crystals

    Muhammad, Zahir; Lv, Haifeng; Wu, Chuanqiang; Habib, Muhammad; Rehman, Zia ur; Khan, Rashid; Chen, Shuangming; Wu, Xiaojun; Song, Li

    2018-04-01

    Two dimensional (2D) layered magnetic materials have obtained much attention due to their intriguing properties with a potential application in the field of spintronics. Herein, room-temperature ferromagnetism with 0.2 emu g‑1 magnetic moment is realized in Fe-doped ZrS2 single crystals of millimeter size, in comparison with diamagnetic behaviour in ZrS2. The electron paramagnetic resonance spectroscopy reveals that 5.2wt% Fe-doping ZrS2 crystal exhibit high spin value of g-factor about 3.57 at room temperature also confirmed this evidence, due to the unpaired electrons created by doped Fe atoms. First principle static electronic and magnetic calculations further confirm the increased stability of long range ferromagnetic ordering and enhanced magnetic moment in Fe-doped ZrS2, originating from the Fe spin polarized electron near the Fermi level.

  14. Ferromagnetism in Gd doped ZnO nanowires: A first principles study

    Aravindh, S. Assa; Schwingenschloegl, Udo, E-mail: udo.schwingenschloegl@kaust.edu.sa, E-mail: iman.roqan@kaust.edu.sa; Roqan, Iman S., E-mail: udo.schwingenschloegl@kaust.edu.sa, E-mail: iman.roqan@kaust.edu.sa [Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900 (Saudi Arabia)

    2014-12-21

    In several experimental studies, room temperature ferromagnetism in Gd-doped ZnO nanostructures has been achieved. However, the mechanism and the origin of the ferromagnetism remain controversial. We investigate the structural, magnetic, and electronic properties of Zn{sub 48}O{sub 48} nanowires doped with Gd, using density functional theory. Our findings indicate that substitutionally incorporated Gd atoms prefer occupying the surface Zn sites. Moreover, the formation energy increases with the distance between Gd atoms, signifying that no Gd-Gd segregation occurs in the nanowires within the concentration limit of ≤2%. Gd induces ferromagnetism in ZnO nanowires with magnetic coupling energy up to 21 meV in the neutral state, which increases with additional electron and O vacancy, revealing the role of carriers in magnetic exchange. The potential for achieving room temperature ferromagnetism and high T{sub C} in ZnO:Gd nanowires is evident from the large ferromagnetic coupling energy (200 meV) obtained with the O vacancy. Density of states shows that Fermi level overlaps with Gd f states with the introduction of O vacancy, indicating the possibility of s-f coupling. These results will assist in understanding experimental findings in Gd-doped ZnO nanowires.

  15. Ferromagnetism in Gd doped ZnO nanowires: A first principles study

    Aravindh, S. Assa

    2014-12-19

    In several experimental studies, room temperature ferromagnetism in Gd-doped ZnO nanostructures has been achieved. However, the mechanism and the origin of the ferromagnetism remain controversial. We investigate the structural, magnetic, and electronic properties of Zn 48O48 nanowires doped with Gd, using density functional theory. Our findings indicate that substitutionally incorporated Gd atoms prefer occupying the surface Zn sites. Moreover, the formation energy increases with the distance between Gd atoms, signifying that no Gd-Gd segregation occurs in the nanowires within the concentration limit of ≤2%. Gd induces ferromagnetism in ZnO nanowires with magnetic coupling energy up to 21 meV in the neutral state, which increases with additional electron and O vacancy, revealing the role of carriers in magnetic exchange. The potential for achieving room temperature ferromagnetism and high TC in ZnO:Gd nanowires is evident from the large ferromagnetic coupling energy (200 meV) obtained with the O vacancy. Density of states shows that Fermi level overlaps with Gd f states with the introduction of O vacancy, indicating the possibility of s-f coupling. These results will assist in understanding experimental findings in Gd-doped ZnO nanowires.

  16. Ferromagnetism in Gd doped ZnO nanowires: A first principles study

    Aravindh, S. Assa; Schwingenschlö gl, Udo; Roqan, Iman S.

    2014-01-01

    In several experimental studies, room temperature ferromagnetism in Gd-doped ZnO nanostructures has been achieved. However, the mechanism and the origin of the ferromagnetism remain controversial. We investigate the structural, magnetic, and electronic properties of Zn 48O48 nanowires doped with Gd, using density functional theory. Our findings indicate that substitutionally incorporated Gd atoms prefer occupying the surface Zn sites. Moreover, the formation energy increases with the distance between Gd atoms, signifying that no Gd-Gd segregation occurs in the nanowires within the concentration limit of ≤2%. Gd induces ferromagnetism in ZnO nanowires with magnetic coupling energy up to 21 meV in the neutral state, which increases with additional electron and O vacancy, revealing the role of carriers in magnetic exchange. The potential for achieving room temperature ferromagnetism and high TC in ZnO:Gd nanowires is evident from the large ferromagnetic coupling energy (200 meV) obtained with the O vacancy. Density of states shows that Fermi level overlaps with Gd f states with the introduction of O vacancy, indicating the possibility of s-f coupling. These results will assist in understanding experimental findings in Gd-doped ZnO nanowires.

  17. Defect mediated magnetic interaction and high Tc ferromagnetism in Co doped ZnO nanoparticles.

    Pal, Bappaditya; Giri, P K

    2011-10-01

    Structural, optical and magnetic studies have been carried out for the Co-doped ZnO nanoparticles (NPs). ZnO NPs are doped with 3% and 5% Co using ball milling and ferromagnetism (FM) is studied at room temperature and above. A high Curie temperature (Tc) has been observed from the Co doped ZnO NPs. X-ray diffraction and high resolution transmission electron microscopy analysis confirm the absence of metallic Co clusters or any other phase different from würtzite-type ZnO. UV-visible absorption and photoluminescence studies on the doped samples show change in band structure and oxygen vacancy defects, respectively. Micro-Raman studies of doped samples shows defect related additional strong bands at 547 and 574 cm(-1) confirming the presence of oxygen vacancy defects in ZnO lattice. The field dependence of magnetization (M-H curve) measured at room temperature exhibits the clear M-H loop with saturation magnetization and coercive field of the order of 4-6 emu/g and 260 G, respectively. Temperature dependence of magnetization measurement shows sharp ferromagnetic to paramagnetic transition with a high Tc = 791 K for 3% Co doped ZnO NPs. Ferromagnetic ordering is interpreted in terms of overlapping of polarons mediated through oxygen vacancy defects based on the bound magnetic polaron (BMP) model. We show that the observed FM data fits well with the BMP model involving localised carriers and magnetic cations.

  18. Defect controlled room temperature ferromagnetism in Co-doped barium titanate nanocrystals

    Ray, Sugata; Kolen'ko, Yury V; Watanabe, Tomoaki; Yoshimura, Masahiro; Itoh, Mitsuru; Kovnir, Kirill A; Lebedev, Oleg I; Turner, Stuart; Erni, Rolf; Tendeloo, Gustaaf Van; Chakraborty, Tanushree

    2012-01-01

    Defect mediated high temperature ferromagnetism in oxide nanocrystallites is the central feature of this work. Here, we report the development of room temperature ferromagnetism in nanosized Co-doped barium titanate particles with a size of around 14 nm, synthesized by a solvothermal drying method. A combination of x-ray diffraction with state-of-the-art electron microscopy techniques confirms the intrinsic doping of Co into BaTiO 3 . The development of the room temperature ferromagnetism was tracked down to the different donor defects, namely hydroxyl groups at the oxygen site and oxygen vacancies and their relative concentrations at the surface and the core of the nanocrystal, which could be controlled by post-synthesis drying and thermal treatments.

  19. Ferromagnetism carried by highly delocalized hybrid states in Sc-doped ZnO thin films

    Benali Kanoun, Mohammed; Goumri-Said, Souraya; Manchon, Aurelien; Schwingenschlö gl, Udo

    2012-01-01

    We present first-principles results for Sc-doped ZnOthin films. Neighboring Sc atoms in the surface and/or subsurface layers are found to be coupled ferromagnetically, where only two of the possible configurations induce spin polarization

  20. Transition from diamagnetic to ferromagnetic state in laser ablated nitrogen doped ZnO thin films

    Kajal Jindal

    2015-02-01

    Full Text Available Transition from room temperature diamagnetic to ferromagnetic state in N doped ZnO (ZnO:N films grown by pulsed laser deposition with tunable energy density has been identified. ZnO:N films deposited with moderate laser energy density of 2.5 J/cm2 are single phase and nearly defect free having N dopant substitution at O sites in ZnO lattice, exhibiting intrinsic ferromagnetism. When energy density reduces (<2.5 J/cm2, defects in ZnO:N film degrades ferromagnetism and exhibit diamagnetic phase when grown at energy density of 1.0 J/cm2. Growth kinetics, which in turn depends on laser energy density is playing important role in making transition from ferromagnetic to diamagnetic in ZnO:N films.

  1. Intrinsic and spatially nonuniform ferromagnetism in Co-doped ZnO films

    Tseng, L. T.; Suter, A.; Wang, Y. R.; Xiang, F. X.; Bian, P.; Ding, X.; Tseng, A.; Hu, H. L.; Fan, H. M.; Zheng, R. K.; Wang, X. L.; Salman, Z.; Prokscha, T.; Suzuki, K.; Liu, R.; Li, S.; Morenzoni, E.; Yi, J. B.

    2017-09-01

    Co doped ZnO films have been deposited by a laser-molecular beam epitaxy system. X-ray diffraction and UV spectra analysis show that Co effectively substitutes the Zn site. Transmission electron microscopy (TEM) and secondary ion mass spectroscopy analysis indicate that there are no clusters. Co dopants are uniformly distributed in ZnO film. Ferromagnetic ordering is observed in all samples deposited under an oxygen partial pressure, PO2=10-3 , 10-5, and 10-7 torr, respectively. However, the magnetization of PO2=10-3 and 10-5 is very small at room temperature. At low temperature, the ferromagnetic ordering is enhanced. Muon spin relaxation (μ SR ) measurements confirm the ferromagnetism in all samples, and the results are consistent with magnetization measurements. From μ SR and TEM analysis, the film deposited under PO2=10-7 torr shows intrinsic ferromagnetism. However, the volume fraction of the ferromagnetism phase is approximately 70%, suggesting that the ferromagnetism is not carrier mediated. Resistivity versus temperature measurements indicate Efros variable range hopping dominates the conductivity. From the above results, we can confirm that a bound magnetic polaron is the origin of the ferromagnetism.

  2. Preparation of Mn doped CeO_2 nanoparticles with enhanced ferromagnetism

    Ravi, S.; Winfred Shashikanth, F.

    2017-01-01

    Spherical-like CeO_2 and Mn-doped CeO_2 using 6-aminohexanoic acid as surfactant exhibit enhanced ferromagnetism. The optical absorption spectra reveal a red shift with a band gap of 2.51 eV. The mechanics of ferromagnetism and the red shift were analyzed. These results provide a promising platform for developing a dilute magnetic semiconductor in spintronics. - Highlights: • Pure and Mn-doped CeO_2 is prepared with aminohexanoic acid as capping. • They exhibit wide optical absorption with red-shift in their band gap. • Mn-doped CeO_2 nanoparticle exhibit hysteresis at room temperature. • Results were promising to use in spintronics and opto-electronics field.

  3. Preparation of Mn doped CeO{sub 2} nanoparticles with enhanced ferromagnetism

    Ravi, S., E-mail: sravi@mepcoeng.ac.in; Winfred Shashikanth, F.

    2017-06-15

    Spherical-like CeO{sub 2} and Mn-doped CeO{sub 2} using 6-aminohexanoic acid as surfactant exhibit enhanced ferromagnetism. The optical absorption spectra reveal a red shift with a band gap of 2.51 eV. The mechanics of ferromagnetism and the red shift were analyzed. These results provide a promising platform for developing a dilute magnetic semiconductor in spintronics. - Highlights: • Pure and Mn-doped CeO{sub 2} is prepared with aminohexanoic acid as capping. • They exhibit wide optical absorption with red-shift in their band gap. • Mn-doped CeO{sub 2} nanoparticle exhibit hysteresis at room temperature. • Results were promising to use in spintronics and opto-electronics field.

  4. Rare earth doped M-type hexaferrites; ferromagnetic resonance and magnetization dynamics

    Vipul Sharma

    2018-05-01

    Full Text Available M-type hexagonal barium ferrites come in the category of magnetic material that plays a key role in electromagnetic wave propagation in various microwave devices. Due to their large magnetic anisotropy and large magnetization, their operating frequency exceeds above 50 GHz. Doping is a way to vary its magnetic properties to such an extent that its ferromagnetic resonance (FMR response can be tuned over a broad frequency band. We have done a complete FMR study of rare earth elements neodymium (Nd and samarium (Sm, with cobalt (Co as base, doped hexaferrite nanoparticles (NPs. X-ray diffractometry, vibrating sample magnetometer (VSM, and ferromagnetic resonance (FMR techniques were used to characterize the microstructure and magnetic properties of doped hexaferrite nanoparticles. Using proper theoretical electromagnetic models, various parameters are extracted from FMR data which play important role in designing and fabricating high-frequency microwave devices.

  5. Structural, optical and ferromagnetic properties of Cr doped TiO2 nanoparticles

    Choudhury, Biswajit; Choudhury, Amarjyoti

    2013-01-01

    Graphical abstract: Doping of Cr 3+ distorts the lattice of TiO 2 , generate oxygen vacancies and create d-band states in the mid band gap of TiO 2 . Incorporation of Cr 3+ also imparts magnetism in non-magnetic TiO 2 by undergoing coupling with the neighboring oxygen vacancies. -- Highlights: • Incorporation of Cr 3+ increases the concentration of oxygen vacancies in TiO 2 nanoparticles. • Doped TiO 2 nanoparticles contain absorption peaks corresponding to d–d transition of Cr 3+ into TiO 2 . • Pure and doped TiO 2 nanoparticles contain emission peaks related to oxygen vacancies. • Pure TiO 2 shows diamagnetism while Cr doped TiO 2 shows ferromagnetism. • The ferromagnetism is due to the interaction of Cr 3+ ions via oxygen vacancies. -- Abstract: Cr doped TiO 2 nanoparticles are prepared with three different concentrations of chromium, 1.5%, 3.0% and 4.5 mol% respectively. Doping decreases the crystallinity and increases the width of the X-ray diffraction peak. The Raman active E g peak of TiO 2 nanoparticles become asymmetric and shifted to higher energy on doping of 4.5% chromium. Electron paramagnetic resonance spectra reveal the presence of Cr 3+ in the host TiO 2 matrix. The absorption spectra of Cr doped TiO 2 nanoparticles contain absorption peaks corresponding to d–d transition of Cr 3+ in octahedral coordination. Most of the visible emission peaks are due to the electrons trapped in the oxygen vacancy centers. Undoped TiO 2 nanoparticles show diamagnetism at room temperature while all chromium doped samples show ferromagnetism. The magnetization of the doped samples increases at 1.5% and 3.0% and decreases at 4.5%. The ferromagnetism arises owing to the interaction of the neighboring Cr 3+ ions via oxygen vacancies. The decrease of magnetization at the highest doping is possibly due to the antiferromagnetic interactions of Cr 3+ pairs or due to Cr 3+ -O 2− -Cr 3+ superexchange interaction in the lattice

  6. Room temperature ferromagnetism and phonon properties of pure and doped TiO{sub 2} nanoparticles

    Apostolova, I.N. [University of Forestry, Faculty of Forest Industry, 10, Kl. Ohridsky Blvd., 1756 Sofia (Bulgaria); Apostolov, A.T. [University of Architecture, Civil Engineering and Geodesy, Faculty of Hydrotechnics, Department of Physics, 1, Hristo Smirnenski Blvd., 1046 Sofia (Bulgaria); Bahoosh, S.G. [Max Planck Institute of Microstructure Physics, Weinberg 2, 06120 Halle (Germany); Wesselinowa, J.M., E-mail: julia@phys.uni-sofia.bg [University of Sofia, Department of Physics, 5, J. Bouchier Blvd., 1164 Sofia (Bulgaria)

    2014-03-15

    We have considered the origin of RTFM in TiO{sub 2} nanoparticles (NPs). Further we have studied the properties of the E{sub g1} phonon mode. The phonon frequency of anatase TiO{sub 2} NPs increases whereas in the case of rutile TiO{sub 2} NPs it decreases as the particle size decreases. The phonon damping is always enhanced in the nanosized materials. The hardening of the E{sub g1} mode and the softening of the E{sub g3} mode in anatase TiO{sub 2} NPs could be explained with the different anharmonic spin–phonon interaction constants of these modes. The doping effects with different transition metal ions on the E{sub g1} phonon mode are also discussed. - Highlights: • The origin of RTFM in TiO{sub 2} nanoparticles is investigated. • With decreasing of particle size the phonon frequency of anatase and rutile TiO{sub 2} NPs increases and decreases, respectively. • This could be explained with the different anharmonic spin–phonon interaction constants of these modes. • The phonon damping is always enhanced in the nanosized materials. • The doping effects with different transition metal ions on the E{sub g1} phonon mode are also discussed.

  7. Ferromagnetic domain structures and spin configurations measured in doped manganite

    He, J.Q.; Volkov, V.V.; Beleggia, Marco

    2010-01-01

    We report on measurements of the spin configuration across ferromagnetic domains in La0.325Pr0.3Ca0.375MnO3 films obtained by means of low-temperature Lorentz electron microscopy with in situ magnetizing capabilities. Due to the particular crystal symmetry of the material, we observe two sets of ...... and the crystal symmetry might affect the magnetoresistivity under an applied magnetic field in a strongly correlated electron system....

  8. Exchange coupling in transition-metal ferromagnets

    Frota-Pessoa, S.; Muniz, R. B.; Kudrnovský, Josef

    2000-01-01

    Roč. 62, č. 9 (2000), s. 5293-5296 ISSN 0163-1829 R&D Projects: GA AV ČR IAA1010829 Institutional research plan: CEZ:AV0Z1010914 Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.065, year: 2000

  9. Room temperature ferromagnetism and half metallicity in nickel doped ZnS: Experimental and DFT studies

    Akhtar, Muhammad Saeed [School of Materials, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Centre of Excellence in Solid State Physics, University of the Punjab, Lahore 54590 (Pakistan); Malik, Mohammad Azad, E-mail: Azad.malik@manchester.ac.uk [School of Materials, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Riaz, Saira; Naseem, Shahzad [Centre of Excellence in Solid State Physics, University of the Punjab, Lahore 54590 (Pakistan)

    2015-06-15

    The nickel doped nanocrystalline ZnS thin films were deposited onto glass substrates by chemical bath deposition (CBD). Also ZnS:Ni nanoparticles were synthesized by CBD/co-precipitation method. Powder X-ray diffraction (p-XRD) studies demonstrate that both thin films and nanoparticles correspond to sphalerite (cubic) phase of ZnS with slight shift towards higher 2θ values due to incorporation of nickel in the ZnS lattice. The crystallite sizes estimated by Scherrer equation were 4 and 2.6 nm for ZnNiS thin films and nanoparticles, respectively. Scanning Electron Microscopy (SEM) images reveal that the morphology of thin films is based on quasi-spherical particles with nano scale dimensions. Energy Dispersive X-ray (EDX) spectroscopy confirms that the as-deposited thin films have a stoichiometry consistent with the nickel doped ZnS. Full-potential linearized augmented plane wave (FP-L/APW) method based on spin-polarized density functional theory (DFT) was employed to investigate the electronic and magnetic properties of ZnNiS for the doping concentration. Exchange-correlation functional was studied using generalized gradient approximation (GGA + U) method. Electronic band structures and density of states (DOS) demonstrate 100% spin polarization (half metallicity) with ferromagnetic exchange interactions. Superconducting quantum interference device (SQUID) analysis confirms the theoretical observation of ferromagnetism in nickel doped ZnS. These ZnS based half metallic ferromagnets seem to have virtuous applications in future spintronic devices. - Highlights: • ZnS.Ni thin films and nanoparticles were deposited onto glass substrates by CBD. • p-XRD correspond to sphalerite (cubic) phase of ZnS with slight shift in peaks. • DFT was employed to investigate the properties of ZnS.Ni. • DOS demonstrate 100% spin polarization with ferromagnetic exchange interactions. • SQUID analysis confirms the theoretical observations of nickel doped ZnS.

  10. Nature of ferromagnetic coupling in Cobalt-doped ZnO; Ursache der magnetischen Kopplung in Kobalt-dotiertem ZnO

    Nielsen, K W

    2007-12-12

    Aim of this thesis was on the one hand to produce Co doped ZnO films, which exhibit a ferromagnetic signal and on the other hand to study the cause of the magnetic coupling. For this purpose Zn{sub 0.95}Co{sub 0.05} films wer fabricated by pulsed laser deposition. Three different substrate materials ((0001)ZnO, (0001)Al{sub 2}O{sub 3}, and (0001)ScAlMgO{sub 4}) were applied anf the growth temperature T{sub g} varied between 300 C and 600 C. Furthermore non-transition-metal doped films were grown at T{sub g}=320 C. By means of X-ray diffractometry the samples were studied concerning their structure, phase purity, and mosaicism. In the films on ZnO a foreign phase was detected, which can be explained by metallic Co inclusions. An estimation of the particle sizes yielded diameters between 2.2 nm and 5.4 nm. With SQID magnetometry measurements of the magnetization M were performed in dependence on the magnetic field H and the temperature T. At 300 K in all Co doped samples on ZnO and in samples on Al{sub 2}O{sub 3} and ScAlMgO{sub 4} with T{sub g}<400 C in the M(H) curves a distinct magnetic moment was observed, which cannot be explained by paramagnetic CO{sup 2+}. The magnetization measurements prove the existence of superparamegnetic nanoparticles. By means of high-resolution transmission electron microscopy it was possible to detect the Co inclusions in the Co doped film on ZnO with T{sub g}=500 C. For the Co and the non-transition-metal-doped samples on Al{sub 2}O{sub 3} and ScAlMgO{sub 4} with T{sub g}=320 C the electric trasnport properties were determined in dependence on H and T.

  11. Ga vacancy induced ferromagnetism enhancement and electronic structures of RE-doped GaN

    Zhong Guohua; Zhang Kang; He Fan; Ma Xuhang; Lu Lanlan; Liu Zhuang; Yang Chunlei

    2012-01-01

    Because of their possible applications in spintronic and optoelectronic devices, GaN dilute magnetic semiconductors (DMSs) doped by rare-earth (RE) elements have attracted much attention since the high Curie temperature was obtained in RE-doped GaN DMSs and a colossal magnetic moment was observed in the Gd-doped GaN thin film. We have systemically studied the GaN DMSs doped by RE elements (La, Ce-Yb) using the full-potential linearized augmented plane wave method within the framework of density functional theory and adding the considerations of the electronic correlation and the spin-orbital coupling effects. We have studied the electronic structures of DMSs, especially for the contribution from f electrons. The origin of magnetism, magnetic interaction and the possible mechanism of the colossal magnetic moment were explored. We found that, for materials containing f electrons, electronic correlation was usually strong and the spin-orbital coupling was sometimes crucial in determining the magnetic ground state. It was found that GaN doped by La was non-magnetic. GaN doped by Ce, Nd, Pm, Eu, Gd, Tb and Tm are stabilized at antiferromagnetic phase, while GaN doped by other RE elements show strong ferromagnetism which is suitable materials for spintronic devices. Moreover, we have identified that the observed large enhancement of magnetic moment in GaN is mainly caused by Ga vacancies (3.0μB per Ga vacancy), instead of the spin polarization by magnetic ions or originating from N vacancies. Various defects, such as substitutional Mg for Ga, O for N under the RE doping were found to bring a reduction of ferromagnetism. In addition, intermediate bands were observed in some systems of GaN:RE and GaN with intrinsic defects, which possibly opens the potential application of RE-doped semiconductors in the third generation high efficiency photovoltaic devices.

  12. Defect mediated ferromagnetism in Ni-doped ZnO nanocrystals evidenced by positron annihilation spectroscopy

    Chen, Zhi-Yuan; Chen, Z. Q.; Zou, B.; Zhao, X. G.; Tang, Z.; Wang, S. J.

    2012-10-01

    NiO/ZnO nanocomposites with NiO content of 4 at. % and 20 at. % were annealed up to 1200 °C to get Ni doped ZnO nanocrystals. Raman scattering spectra illustrate a broad and strong band at 500-600cm-1 in all nanocomposites after annealing above 700 °C, which suggests incorporation of Ni in the ZnO lattice. However, x-ray diffraction measurements show that NiO phase can be still observed in all nanocomposites after annealing, which indicates that Ni is partially doped into the ZnO structure. Positron annihilation measurements reveal large number of vacancy defects in the interface region of all nanocomposites, and they are gradually recovered with increasing annealing temperature up to 1000 °C. Room temperature ferromagnetism can be observed in the NiO/ZnO nanocomposites, which is stronger in the 20 at. % NiO/ZnO nanocomposites, and the magnetization decreases continuously with increasing annealing temperature. This indicates that the ferromagnetism at low annealing temperatures originates from the NiO nanograins, and they become antiferromanetic after subsequent higher temperature annealing which leads to the weakening of ferromagnetism. After annealing up to 1000 °C, the ferromagnetism in both the two samples becomes nearly invisible. The disappearance of ferromagnetism shows good coincidence with the recovery of vacancy defects in NiO/ZnO nanocomposites. It can be inferred that the ferromagnetism is mediated by vacancy defects which are distributed in the interface region.

  13. Half-metallic ferromagnetism in nitrogen - doped ionic insulator (Li2O): a DFT study

    Eithiraj, R.D.; Kalpana, G.

    2010-01-01

    The tight binding linear muffin-tin orbital (TB-LMTO) method, is used to study the electronic structure and magnetism in nitrogen - doped Li 2 O (antifluorite - CaF 2 structure). Total energy calculations show that the antifluorite ferromagnetic state is more stable than the antifluorite non-magnetic state at equilibrium volume. Ground state properties such as equilibrium lattice constant and bulk modulus were calculated. The calculations reveal that non-magnetic impurities can induce stable half-metallic ferromagnetic ground state in Li 2 O. The magnetic moment of nitrogen doped Li 2 O can be tuned over a range between 1.00 μ B and 3.00 μ B by changing the concentration of nitrogen from 25% to 75%. (author)

  14. Ferromagnetism carried by highly delocalized hybrid states in Sc-doped ZnO thin films

    Benali Kanoun, Mohammed

    2012-05-29

    We present first-principles results for Sc-doped ZnOthin films. Neighboring Sc atoms in the surface and/or subsurface layers are found to be coupled ferromagnetically, where only two of the possible configurations induce spin polarization. In the first configuration, the polarization is carried by the Sc d states as expected for transition metaldoping. However, there is a second configuration which is energetically favorable. It is governed by polarized hybrid states of the Zns, O p, and Sc d orbitals. Such highly delocalized states can be an important ingredient for understanding the magnetism of dopedZnOthin films.

  15. Superconductivity in transition metals.

    Slocombe, Daniel R; Kuznetsov, Vladimir L; Grochala, Wojciech; Williams, Robert J P; Edwards, Peter P

    2015-03-13

    A qualitative account of the occurrence and magnitude of superconductivity in the transition metals is presented, with a primary emphasis on elements of the first row. Correlations of the important parameters of the Bardeen-Cooper-Schrieffer theory of superconductivity are highlighted with respect to the number of d-shell electrons per atom of the transition elements. The relation between the systematics of superconductivity in the transition metals and the periodic table high-lights the importance of short-range or chemical bonding on the remarkable natural phenomenon of superconductivity in the chemical elements. A relationship between superconductivity and lattice instability appears naturally as a balance and competition between localized covalent bonding and so-called broken covalency, which favours d-electron delocalization and superconductivity. In this manner, the systematics of superconductivity and various other physical properties of the transition elements are related and unified. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

  16. Ferromagnetism in CVT grown tungsten diselenide single crystals with nickel doping

    Habib, Muhammad; Muhammad, Zahir; Khan, Rashid; Wu, Chuanqiang; Rehman, Zia ur; Zhou, Yu; Liu, Hengjie; Song, Li

    2018-03-01

    Two dimensional (2D) single crystal layered transition materials have had extensive consideration owing to their interesting magnetic properties, originating from their lattices and strong spin-orbit coupling, which make them of vital importance for spintronic applications. Herein, we present synthesis of a highly crystalline tungsten diselenide layered single crystal grown by chemical vapor transport technique and doped with nickel (Ni) to tailor its magnetic properties. The pristine WSe2 single crystal and Ni-doped crystal were characterized and analyzed for magnetic properties using both experimental and computational aspects. It was found that the magnetic behavior of the 2D layered WSe2 crystal changed from diamagnetic to ferromagnetic after Ni-doping at all tested temperatures. Moreover, first principle density functional theory (DFT) calculations further confirmed the origin of room temperature ferromagnetism of Ni-doped WSe2, where the d-orbitals of the doped Ni atom promoted the spin moment and thus largely contributed to the magnetism change in the 2D layered material.

  17. Indium vacancy induced d0 ferromagnetism in Li-doped In2O3 nanoparticles

    Cao, Haiming; Xing, Pengfei; Zhou, Wei; Yao, Dongsheng; Wu, Ping

    2018-04-01

    Li-doped In2O3 nanoparticles with room temperature d0 ferromagnetism were prepared by a sol-gel method. X-ray diffraction, X-ray photoelectron spectroscopy and photoluminescence were carried out to investigate the effects of Li incorporation on the lattice defects. As the content of Li increases, non-monotonic changes in shifts of XRD peak (2 2 2) and the intensity ratios of indium vacancies related photoluminescence peak (PII) with respect to oxygen vacancies related peak (PI) are observed. Results show that at low doping level (≤2 at.%) Li prefers to occupy In sites, while with further doping the interstitial sites are more favorable for Li. Combined with the consistent non-monotonic change in saturation magnetization, we think that indium vacancies resulting from Li-doping play an important role in inducing d0 ferromagnetism in our Li-doped In2O3 nanoparticles, and the FM coupling is mainly mediated by the LiIn-ONN-VIn-ONN-LiIn chains.

  18. Room temperature ferromagnetism in Fe-doped CeO2 nanoparticles.

    Maensiri, Santi; Phokha, Sumalin; Laokul, Paveena; Seraphin, Supapan

    2009-11-01

    RT ferromagnetism was observed in nanoparticles of Fe-doped CeO2 (i.e., Ce(0.97)Fe(0.03)O2) synthesized by a sol-gel method. The undoped and Fe-doped CeO2 were characterized by XRD, Raman spectroscopy, TEM, and VSM. The undoped samples and Ce(0.97)Fe(0.03)O2 precursor exhibit a diamagnetic behavior. The 673 K-calcined Ce(0.97)Fe(0.03)O2 sample is paramagnetic whereas 773 and 873 K-calcined Ce(0.97)Fe(0.03)O2 samples are ferromagnetism having the magnetizations of 4.65 x 10(-3) emu/g and 6.20 x 10(-3) emu/g at 10 kOe, respectively. Our results indicate that the ferromagnetic property is intrinsic to the Fe-doped CeO2 system and is not a result of any secondary magnetic phase or cluster formation.

  19. Doping dependent room-temperature ferromagnetism and structural properties of dilute magnetic semiconductor ZnO:Cu2+ nanorods

    Sharma, Prashant K.; Dutta, Ranu K.; Pandey, Avinash C.

    2009-01-01

    Copper doped ZnO nanoparticles were synthesized by the chemical technique based on the hydrothermal method. The crystallite structure, morphology and size were determined by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) for different doping percentages of Cu 2+ (1-10%). TEM/SEM images showed formation of uniform nanorods, the aspect ratio of which varied with doping percentage of Cu 2+ . The wurtzite structure of ZnO gradually degrades with the increasing Cu 2+ doping concentration and an additional CuO associated diffraction peak was observed above 8% of Cu 2+ doping. The change in magnetic behavior of the nanoparticles of ZnO with varying Cu 2+ doping concentrations was investigated using a vibrating sample magnetometer (VSM). Initially these nanoparticles showed strong room-temperature ferromagnetic behavior, however at higher doping percentage of copper the ferromagnetic behavior was suppressed and paramagnetic nature was enhanced.

  20. Room temperature p-type conductivity and coexistence of ferroelectric order in ferromagnetic Li doped ZnO nanoparticles

    Awan, Saif Ullah; Hasanain, S. K.; Anjum, Dalaver H.; Awan, M. S.; Shah, Saqlain A.

    2014-01-01

    for long range order ferromagnetic coupling in Li doped samples. Room temperature ferroelectric hysteresis loops were observed in 8% and 10% Li doped samples. We demonstrated ferroelectric coercivity (remnant polarization) 2.5kV/cm (0.11 μC/cm2) and 2.8k

  1. Half-metallic ferromagnetism in Fe-doped Zn3P2 from first-principles calculations

    Jaiganesh, G.; Jaya, S. Mathi

    2014-01-01

    Using the first-principles calculations based on the density functional theory, we have studied the magnetism and electronic structure of Fe-doped Zinc Phosphide (Zn 3 P 2 ). Our results show that the half-metallic ground state and ferromagnetic stability for the small Fe concentrations considered in our study. The stability of the doped material has been studied by calculating the heat of formation and analyzing the minimum total energies in nonmagnetic and ferromagnetic phases. A large value of the magnetic moment is obtained from our calculations and our calculation suggests that the Fe-doped Zn 3 P 2 may be a useful material in semiconductor spintronics

  2. Interplay of dopants and defects in making Cu doped TiO{sub 2} nanoparticle a ferromagnetic semiconductor

    Choudhury, Biswajit, E-mail: biswa.tezu@gmail.com [Department of Physics, Tezpur University, Napaam 784028, Assam (India); Choudhury, Amarjyoti [Department of Physics, Tezpur University, Napaam 784028, Assam (India); Borah, Debajit [Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, Assam (India)

    2015-10-15

    Here we have studied the role of oxygen defects and Cu dopants on ferromagnetism in Cu doped TiO{sub 2} nanoparticles with nominal Cu concentration of 2%, 4% and 6 mol%. Electron paramagnetic resonance (EPR) spectra analysis reveals the presence of Cu{sup 2+} in the distorted octahedral coordination of TiO{sub 2}. Cu d-states undergo strong p-d coupling with the valence band O 2p state of TiO{sub 2} resulting the extended absorption hump in the visible region. Photoluminescence results reveal the presence of oxygen defect related emission peaks in Cu doped TiO{sub 2}. Room temperature ferromagnetism is observed in all the Cu doped TiO{sub 2} nanoparticles. Saturation magnetization is the highest at 4 mol% and then there is a decrease in magnetization at 6 mol%. Ferromagnetism completely disappears on calcinations of 4% Cu doped TiO{sub 2} in air at 450 °C for 8 h. It is speculated that both oxygen vacancies and Cu d-states are involved in the room temperature ferromagnetism. Spin polarization occurs by the formation of bound magnetic polaron between electrons in Cu{sup 2+}d-states and the unpaired spins in oxygen vacancies. Presence of Cu{sup 2+}-Cu{sup 2+}d-d exchange interaction and Cu{sup 2+}-O{sup 2−}-Cu{sup 2+} antiferromagnetic superexchange interactions might have resulted in the reduction in magnetization at 6 mol% Cu. - Graphical abstract: Ferromagnetism in Cu doped TiO{sub 2} requires presence of both Cu dopant and oxygen vacancies. - Highlights: • Cu doped TiO{sub 2} nanoparticle displays room temperature ferromagnetism. • Ferromagnetism requires presence of both Cu and oxygen vacancies. • Antiferromagnetic interaction persists at high Cu dopant concentration. • Paramagnetism appears on air annealing of the doped system for longer period.

  3. Above room-temperature ferromagnetism of Mn delta-doped GaN nanorods

    Lin, Y. T.; Wadekar, P. V.; Kao, H. S.; Chen, T. H.; Chen, Q. Y.; Tu, L. W.; Huang, H. C.; Ho, N. J.

    2014-01-01

    One-dimensional nitride based diluted magnetic semiconductors were grown by plasma-assisted molecular beam epitaxy. Delta-doping technique was adopted to dope GaN nanorods with Mn. The structural and magnetic properties were investigated. The GaMnN nanorods with a single crystalline structure and with Ga sites substituted by Mn atoms were verified by high-resolution x-ray diffraction and Raman scattering, respectively. Secondary phases were not observed by high-resolution x-ray diffraction and high-resolution transmission electron microscopy. In addition, the magnetic hysteresis curves show that the Mn delta-doped GaN nanorods are ferromagnetic above room temperature. The magnetization with magnetic field perpendicular to GaN c-axis saturates easier than the one with field parallel to GaN c-axis

  4. Room temperature ferromagnetism in Mg-doped ZnO nanoparticles

    Singh, Jaspal; Vashihth, A.; Gill, Pritampal Singh; Verma, N. K.

    2015-01-01

    Zn 1-x Mg x O (x = 0, 0,10) nanoparticles were successfully synthesized using sol-gel method. X-ray diffraction (XRD) confirms that the synthesized nanoparticles possess wurtzite phase having hexagonal structure. Morphological analysis was carried out using transmission electron microscopy (TEM) which depicts the spherical morphology of ZnO nanoparticles. Energy dispersive spectroscopy (EDS) showed the presence of Mg in ZnO nanoparticles. Electron spin resonance (ESR) signal was found to be decreasing with increasing of Mg-doping concentration. The room temperature ferromagnetism was observed in undoped and Mg-doped ZnO nanoparticles. The increase of Mg-doping concentration resulted in decrease of saturation magnetization value which could be attributed to decrease of oxygen vacancies present in host nanoparticles

  5. Peculiar ferromagnetic insulator state in the low-hole-doped manganites

    Algarabel, P.A.; Teresa, J.M. de; Blasco, J.; Ibarra, M.R.; Kapusta, Cz.; Sikora, M.; Zajac, D.; Riedi, P.C.; Ritter, C.

    2003-01-01

    In this work we show the very different nature of the ferromagnetic state of the low-hole-doped manganites with respect to other manganites showing colossal magnetoresistance. High-field measurements definitively prove the coexistence of ferromagnetic-metallic and ferromagnetic-insulating regions even when the sample is magnetically saturated, with the ground state being inhomogeneous. We have investigated La 0.9 Ca 0.1 MnO 3 as a prototype compound. A wide characterization by means of magnetic and magnetotransport measurements, neutron diffraction, small-angle neutron scattering, and nuclear magnetic resonance has allowed us to establish that the ground state is based on the existence of disordered nanometric double-exchange metallic clusters that coexist with long-range superexchange-based ferromagnetic insulating regions. Under high magnetic field the system reaches magnetization saturation by aligning the magnetic clusters and the insulating matrix, but even if they grow in size, they do not reach the percolation limit

  6. Half-metallic ferromagnetism in Cu-doped zinc-blende ZnO from first principles study

    Li, X.F.; Zhang, J.; Xu, B.; Yao, K.L.

    2012-01-01

    Electronic structures and magnetism of Cu-doped zinc-blende ZnO have been investigated by the first-principle method based on density functional theory (DFT). The results show that Cu can induce stable ferromagnetic ground state. The magnetic moment of supercell including single Cu atom is 1.0 μ B . Electronic structure shows that Cu-doped zinc-blende ZnO is a p-type half-metallic ferromagnet. The half-metal property is mainly attribute to the crystal field splitting of Cu 3d orbital, and the ferromagnetism is dominated by the hole-mediated double exchange mechanism. Therefore, Cu-doped zinc-blende ZnO should be useful in semiconductor spintronics and other applications. - Highlights: → Magnetism of Cu-doped zinc-blende ZnO. → Cu-doped zinc-blende ZnO shows interesting half-metal character. → Total energies calculations reveal that Cu can induce ferromagnetic ground state. → Ferromagnetism dominated by the hole-mediated double exchange mechanism.

  7. Experimental and first-principles study of ferromagnetism in Mn-doped zinc stannate nanowires

    Deng, Rui; Zhou, Hang; Li, Yong-Feng; Wu, Tao; Yao, Bin; Qin, Jie-Ming; Wan, Yu-Chun; Jiang, Da-Yong; Liang, Qing-Cheng; Liu, Lei

    2013-01-01

    Room temperature ferromagnetism was observed in Mn-doped zinc stannate (ZTO:Mn) nanowires, which were prepared by chemical vapor transport. Structural and magnetic properties and Mn chemical states of ZTO:Mn nanowires were investigated by X-ray diffraction, superconducting quantum interference device (SQUID) magnetometry and X-ray photoelectron spectroscopy. Manganese predominantly existed as Mn2+ and substituted for Zn (Mn Zn) in ZTO:Mn. This conclusion was supported by first-principles calculations. MnZn in ZTO:Mn had a lower formation energy than that of Mn substituted for Sn (MnSn). The nearest neighbor MnZn in ZTO stabilized ferromagnetic coupling. This observation supported the experimental results. © 2013 AIP Publishing LLC.

  8. Experimental and first-principles study of ferromagnetism in Mn-doped zinc stannate nanowires

    Deng, Rui

    2013-07-17

    Room temperature ferromagnetism was observed in Mn-doped zinc stannate (ZTO:Mn) nanowires, which were prepared by chemical vapor transport. Structural and magnetic properties and Mn chemical states of ZTO:Mn nanowires were investigated by X-ray diffraction, superconducting quantum interference device (SQUID) magnetometry and X-ray photoelectron spectroscopy. Manganese predominantly existed as Mn2+ and substituted for Zn (Mn Zn) in ZTO:Mn. This conclusion was supported by first-principles calculations. MnZn in ZTO:Mn had a lower formation energy than that of Mn substituted for Sn (MnSn). The nearest neighbor MnZn in ZTO stabilized ferromagnetic coupling. This observation supported the experimental results. © 2013 AIP Publishing LLC.

  9. Dielectric response and room temperature ferromagnetism in Cr doped anatase TiO2 nanoparticles

    Naseem, Swaleha; Khan, Wasi; Khan, Shakeel; Husain, Shahid; Ahmad, Abid

    2018-02-01

    In the present work, nanocrystalline samples of Ti1-xCrxO2 (x = 0, 0.02, 0.04, 0.06 and 0.08) were synthesized in anatase phase through simple and cost effective acid modified sol gel method. The influence of Cr doping on thermal, microstructural, electrical and magnetic properties was investigated in TiO2 host matrix. The surface morphology has revealed less agglomeration and considerable reduction in particle size in case of Cr doped TiO2 as compared to undoped TiO2 nanoparticles (NPs). Energy dispersive x-ray spectroscopy (EDS), Raman and X-ray photoelectron spectroscopy (XPS) established high purity, appropriate stoichiometry and oxidation states of the compositions. The dielectric properties of the nanoparticles were altered by the doping concentration, applied frequency as well as temperature variation. The variation in dielectric constant (ε‧), dielectric loss (δ) and ac conductivity as a function of frequency and temperature at different doping concentration of Cr were interpreted in the light of Maxwell Wagner theory, space charge polarization mechanism and drift mobility of charge carriers. Both undoped and Cr doped TiO2 samples exhibit room temperature ferromagnetism (RTFM) that remarkably influenced by means of the Cr content. The significant enhancement in the magnetization was observed at 4% Cr doping. However, decrease in magnetization for higher doping signify antiferromagnetic interactions between Cr ions or superexchange mechanism. These results reveal that the oxygen vacancies play a crucial role to initiate the RTFM. Therefore, the present investigation suggests the potential applications of Cr doped TiO2 nanoparticles for spintronics application.

  10. Density functional calculations on the geometric structure and properties of the 3d transition metal atom doped endohedral fullerene M@C20F20 (M = Sc–Ni)

    Chun-Mei, Tang; Wei-Hua, Zhu; Kai-Ming, Deng

    2010-01-01

    This paper uses the generalised gradient approximation based on density functional theory to analyse the geometric structure and properties of the 3d transition metal atom doped endohedral fullerene M@C 20 F 20 (M = Sc–Ni). The geometric optimization shows that the cage centre is the most stable position for M, forming the structure named as M@C 20 F 20 -4. The inclusion energy, zero-point energy, and energy gap calculations tell us that N@C 20 F 20 -4 should be thermodynamically and kinetically stablest. M@C 20 F 20 -4 (M = Sc–Co) possesses high magnetic moments varied from 1 to 6 μ B , while Ni@C 20 F 20 -4 is nonmagnetic. The Ni–C bond in Ni@C 20 F 20 -4 contains both the covalent and ionic characters

  11. Vacancies in transition metals

    Allan, G.; Lannoo, M.

    1976-01-01

    A calculation of the formation energy and volume for a vacancy in transition metals is described. A tight-binding scheme is used for the d band and a Born-Mayer type potential to account for the repulsive part of the energy at small distances. The results show that the relaxation energy is small in all cases, less than 0.1 eV. This seems to be coherent with the good agreement obtained for the theoretical and experimental values of the formation energy Esub(F)sup(V) of the vacancy, without including relaxation. The center of the transitional series is found to give a contraction (Formation volume of order -0.4 at.vol.) whereas the edges are found to produce dilations. (author)

  12. Ferromagnetic semiconductor-metal transition in heterostructures of electron doped europium monoxide

    Stollenwerk, Tobias

    2013-09-01

    In the present work, we develop and solve a self-consistent theory for the description of the simultaneous ferromagnetic semiconductor-metal transition in electron doped Europium monoxide. We investigate two different types of electron doping, Gadolinium impurities and Oxygen vacancies. Besides the conduction band occupation, we can identify low lying spin fluctuations on magnetic impurities as the driving force behind the doping induced enhancement of the Curie temperature. Moreover, we predict the signatures of these magnetic impurities in the spectra of scanning tunneling microscope experiments. By extending the theory to allow for inhomogeneities in one spatial direction, we are able to investigate thin films and heterostructures of Gadolinium doped Europium monoxide. Here, we are able to reproduce the experimentally observed decrease of the Curie temperature with the film thickness. This behavior is attributed to missing coupling partners of the localized 4f moments as well as to an electron depletion at the surface which leads to a reduction of the number of itinerant electrons. By investigating the influence of a metallic substrate onto the phase transition in Gadolinium doped Europium monoxide, we find that the Curie temperature can be increased up to 20%. However, as we show, the underlying mechanism of metal-interface induced charge carrier accumulation is inextricably connected to a suppression of the semiconductor-metal transition.

  13. Ferromagnetic semiconductor-metal transition in heterostructures of electron doped europium monoxide

    Stollenwerk, Tobias

    2013-09-15

    In the present work, we develop and solve a self-consistent theory for the description of the simultaneous ferromagnetic semiconductor-metal transition in electron doped Europium monoxide. We investigate two different types of electron doping, Gadolinium impurities and Oxygen vacancies. Besides the conduction band occupation, we can identify low lying spin fluctuations on magnetic impurities as the driving force behind the doping induced enhancement of the Curie temperature. Moreover, we predict the signatures of these magnetic impurities in the spectra of scanning tunneling microscope experiments. By extending the theory to allow for inhomogeneities in one spatial direction, we are able to investigate thin films and heterostructures of Gadolinium doped Europium monoxide. Here, we are able to reproduce the experimentally observed decrease of the Curie temperature with the film thickness. This behavior is attributed to missing coupling partners of the localized 4f moments as well as to an electron depletion at the surface which leads to a reduction of the number of itinerant electrons. By investigating the influence of a metallic substrate onto the phase transition in Gadolinium doped Europium monoxide, we find that the Curie temperature can be increased up to 20%. However, as we show, the underlying mechanism of metal-interface induced charge carrier accumulation is inextricably connected to a suppression of the semiconductor-metal transition.

  14. Nonthermal Photocoercivity Effect in a Low-Doped (Ga,Mn)As Ferromagnetic Semiconductor

    Astakhov, G. V.; Hoffmann, H.; Korenev, V. L.; Kiessling, T.; Schwittek, J.; Schott, G. M.; Gould, C.; Ossau, W.; Brunner, K.; Molenkamp, L. W.

    2009-05-01

    We report a photoinduced change of the coercive field, i.e., a photocoercivity effect (PCE), under very low intensity illumination of a low-doped (Ga,Mn)As ferromagnetic semiconductor. We find a strong correlation between the PCE and the sample resistivity. Spatially resolved dynamics of the magnetization reversal rule out any role of thermal heating in the origin of this PCE, and we propose a mechanism based on the light-induced lowering of the domain wall pinning energy. The PCE is local and reversible, allowing writing and erasing of magnetic images using light.

  15. Nitrogen induced ferromagnetism in Cobalt doped BaTiO3

    Chandrima Mitra

    2012-09-01

    Full Text Available The electronic structure and magnetism of Cobalt doped BaTiO3 (BaTi1−xCoxO3 is investigated. Substitutional Nitrogen on an Oxygen site is found to play an important role in inducing net magnetic moments in the system. The presence of a Nitrogen atom as nearest neighbour to a Cobalt atom is crucial in producing spin splitting of both the Nitrogen and Cobalt states thereby introducing a net local magnetic moment. The introduction of Nitrogen is further found to enhance ferromagnetic interactions between Cobalt atoms.

  16. Dependences on RE of superconducting properties of transition metal co-doped (Ca, RE)FeAs_2 with RE = La–Gd

    Yakita, H.; Ogino, H.; Sala, A.; Okada, T.; Yamamoto, A.; Kishio, K.; Iyo, A.; Eisaki, H.; Shimoyama, J.

    2015-01-01

    Highlights: • We synthesized Co or Ni co-doped (Ca, RE)FeAs_2 with RE = La–Gd. • Co or Ni co-doping improved superconducting properties of all (Ca, RE)FeAs_2 samples. • T_c of (Ca, RE)FeAs_2 decreased with decreasing ionic radii of RE"3"+. • Eu doped samples showed exceptionally low T_c and long interlayer distance. • Long interlayer distance of Eu doped samples suggested co-existence of Eu"2"+ and Eu"3"+. - Abstract: Dependence of superconducting properties of (Ca, RE)(Fe, TM)As_2 [(Ca, RE)112, TM: Co, Ni)] on RE elements (RE = La–Gd) was systematically investigated. Improvement of superconducting properties by Co or Ni co-doping was observed for all (Ca, RE)112, which is similar to Co-co-doped (Ca, La)112 or (Ca, Pr)112. T_c of Co-co-doped samples decreased from 38 K for RE = La to 29 K for RE = Gd with decreasing ionic radii of RE"3"+. However, Co-co-doped (Ca, Eu)112 showed exceptionally low T_c = 21 K probably due to the co-existence of Eu"3"+ and Eu"2"+ suggested by longer interlayer distance d_F_e_–_F_e of (Ca, Eu)112 than other (Ca, RE)112.

  17. Facile synthesis of ferromagnetic Ni doped CeO{sub 2} nanoparticles with enhanced anticancer activity

    Abbas, Fazal; Jan, Tariq [Laboratory of Nanoscience and Technology, Department of Physics, International Islamic University Islamabad (Pakistan); Iqbal, Javed, E-mail: javed.saggu@iiu.edu.pk [Laboratory of Nanoscience and Technology, Department of Physics, International Islamic University Islamabad (Pakistan); Ahmad, Ishaq [Experimental Physics Labs, National Center for Physics, Islamabad (Pakistan); Naqvi, M. Sajjad H. [Department of Biochemistry, University of Karachi, Karachi (Pakistan); Malik, Maaza [UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk Ridge, PO Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, PO Box 722, Somerset West, Western Cape Province (South Africa)

    2015-12-01

    Highlights: • The synthesized undoped and Ni doped CeO{sub 2} nanoparticles exhibited RTFM. • Oxygen vacancies and magnetic ions both were believed to be responsible for RTFM. • The prepared nanoparticles exhibited selective cytotoxicity. • Ni doping enhanced the anticancer activity of CeO{sub 2} nanoparticles. • Differential ROS generation was observed to control their cytotoxicity. - Abstract: Ni{sub x}Ce{sub 1−x}O{sub 2} (where x = 0, 0.01, 0.03, 0.05 and 0.07) nanoparticles were synthesized by soft chemical method and were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman, UV–vis absorption spectroscopy and vibrating sample magnetometer (VSM). XRD and Raman results indicated the formation of single phase cubic fluorite structure for the synthesized nanoparticles. Ni dopant induced excessive structural changes such as decrease in crystallite size as well as lattice constants and enhancement in oxygen vacancies in CeO{sub 2} crystal structure. These structural variations significantly influenced the optical and magnetic properties of CeO{sub 2} nanoparticles. The synthesized Ni{sub x}Ce{sub 1−x}O{sub 2} nanoparticles exhibited room temperature ferromagnetic behavior. Ni doping induced effects on the cytotoxicity of CeO{sub 2} nanoparticles were examined against HEK-293 healthy cell line and SH-SY5Y neuroblastoma cancer cell line. The prepared Ni{sub x}Ce{sub 1−x}O{sub 2} nanoparticles demonstrated differential cytotoxicity. Furthermore, anticancer activity of CeO{sub 2} nanoparticles observed to be significantly enhanced with Ni doping which was found to be strongly correlated with the level of reactive oxygen species (ROS) production. The prepared ferromagnetic Ni{sub x}Ce{sub 1−x}O{sub 2} nanoparticles with differential cytotoxic nature may be potential for future targeted cancer therapy.

  18. Electronic structure and magnetic properties of substitutional transition-metal atoms in GaN nanotubes

    Zhang Min; Shi Jun-Jie

    2014-01-01

    The electronic structure and magnetic properties of the transition-metal (TM) atoms (Sc—Zn, Pt and Au) doped zigzag GaN single-walled nanotubes (NTs) are investigated using first-principles spin-polarized density functional calculations. Our results show that the bindings of all TM atoms are stable with the binding energy in the range of 6–16 eV. The Sc- and V-doped GaN NTs exhibit a nonmagnetic behavior. The GaN NTs doped with Ti, Mn, Ni, Cu and Pt are antiferromagnetic. On the contrary, the Cr-, Fe-, Co-, Zn- and Au-doped GaN NTs show the ferromagnetic characteristics. The Mn- and Co-doped GaN NTs induce the largest local moment of 4μ B among these TM atoms. The local magnetic moment is dominated by the contribution from the substitutional TM atom and the N atoms bonded with it. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  19. Room-temperature ferromagnetic Cr-doped Ge/GeOx core–shell nanowires

    Katkar, Amar S.; Gupta, Shobhnath P.; Motin Seikh, Md; Chen, Lih-Juann; Walke, Pravin S.

    2018-06-01

    The Cr-doped tunable thickness core–shell Ge/GeOx nanowires (NWs) were synthesized and characterized using x-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy and magnetization studies. The shell thickness increases with the increase in synthesis temperature. The presence of metallic Cr and Cr3+ in core–shell structure was confirmed from XPS study. The magnetic property is highly sensitive to the core–shell thickness and intriguing room temperature ferromagnetism is realized only in core–shell NWs. The magnetization decreases with an increase in shell thickness and practically ceases to exist when there is no core. These NWs show remarkably high Curie temperature (TC > 300 K) with the dominating values of its magnetic remanence (MR) and coercivity (HC) compared to germanium dilute magnetic semiconductor nanomaterials. We believe that our finding on these Cr-doped Ge/GeOX core–shell NWs has the potential to be used as a hard magnet for future spintronic devices, owing to their higher characteristic values of ferromagnetic ordering.

  20. Microstructure, ferromagnetic and photoluminescence properties of ITO and Cr doped ITO nanoparticles using solid state reaction

    Babu, S. Harinath [Thin Films Laboratory, Centre for Crystal Growth, VIT University, Vellore-632014, Tamilnadu, India. (India); Kaleemulla, S., E-mail: skaleemulla@gmail.com [Thin Films Laboratory, Centre for Crystal Growth, VIT University, Vellore-632014, Tamilnadu, India. (India); Rao, N. Madhusudhana [Thin Films Laboratory, Centre for Crystal Growth, VIT University, Vellore-632014, Tamilnadu, India. (India); Rao, G. Venugopal [Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102, Tamilnadu (India); Krishnamoorthi, C. [Thin Films Laboratory, Centre for Crystal Growth, VIT University, Vellore-632014, Tamilnadu, India. (India)

    2016-11-01

    Indium-tin-oxide (ITO) (In{sub 0.95}Sn{sub 0.05}){sub 2}O{sub 3} and Cr doped indium-tin-oxide (In{sub 0.90}Sn{sub 0.05}Cr{sub 0.05}){sub 2}O{sub 3} nanoparticles were prepared using simple low cost solid state reaction method and characterized by different techniques to study their structural, optical and magnetic properties. Microstructures, surface morphology, crystallite size of the nanoparticles were studied using X-ray diffractometer (XRD), field emission scanning electron microscope (FE-SEM). From these methods it was found that the particles were about 45 nm. Chemical composition and valence states of the nanoparticles were studied using energy dispersive analysis of X-rays (EDAX) and X-ray photoelectron spectroscopy (XPS). From these techniques it was observed that the elements of indium, tin, chromium and oxygen were present in the system in appropriate ratios and they were in +3, +4, +3 and −2 oxidation states. Raman studies confirmed that the nanoparticle were free from unintentional impurities. Two broad emission peaks were observed at 330 nm and 460 nm when excited wavelength of 300 nm. Magnetic studies were carried out at 300 K and 100 K using vibrating sample magnetometer (VSM) and found that the ITO nanoparticles were ferromagnetic at 100 K and 300 K. Where-as the room temperature ferromagnetism completely disappeared in Cr doped ITO nanoparticles at 100 K and 300 K.

  1. Microstructure, ferromagnetic and photoluminescence properties of ITO and Cr doped ITO nanoparticles using solid state reaction

    Babu, S. Harinath; Kaleemulla, S.; Rao, N. Madhusudhana; Rao, G. Venugopal; Krishnamoorthi, C.

    2016-11-01

    Indium-tin-oxide (ITO) (In0.95Sn0.05)2O3 and Cr doped indium-tin-oxide (In0.90Sn0.05Cr0.05)2O3 nanoparticles were prepared using simple low cost solid state reaction method and characterized by different techniques to study their structural, optical and magnetic properties. Microstructures, surface morphology, crystallite size of the nanoparticles were studied using X-ray diffractometer (XRD), field emission scanning electron microscope (FE-SEM). From these methods it was found that the particles were about 45 nm. Chemical composition and valence states of the nanoparticles were studied using energy dispersive analysis of X-rays (EDAX) and X-ray photoelectron spectroscopy (XPS). From these techniques it was observed that the elements of indium, tin, chromium and oxygen were present in the system in appropriate ratios and they were in +3, +4, +3 and -2 oxidation states. Raman studies confirmed that the nanoparticle were free from unintentional impurities. Two broad emission peaks were observed at 330 nm and 460 nm when excited wavelength of 300 nm. Magnetic studies were carried out at 300 K and 100 K using vibrating sample magnetometer (VSM) and found that the ITO nanoparticles were ferromagnetic at 100 K and 300 K. Where-as the room temperature ferromagnetism completely disappeared in Cr doped ITO nanoparticles at 100 K and 300 K.

  2. The electronic structures and ferromagnetism of Fe-doped GaSb: The first-principle calculation study

    Lin, Xue-ling; Niu, Cao-ping; Pan, Feng-chun; Chen, Huan-ming; Wang, Xu-ming

    2017-09-01

    The electronic structures and the magnetic properties of Fe doped GaSb have been investigated by the first-principles calculation based on the framework of the generalized gradient approximation (GGA) and GGA+U schemes. The calculated results indicated that Fe atoms tend to form the anti-ferromagnetic (AFM) coupling with the nearest-neighbor positions preferentially. Compared with the anti-ferromagnetic coupling, the ferromagnetic interactions occurred at the second nearest-neighbor and third nearest-neighbor sites have a bigger superiority energetically. The effect of strong electron correlation at Fe-d orbit taking on the magnetic properties predicted by GGA+U approach demonstrated that the ferromagnetic (FM) coupling between the Fe ions is even stronger in consideration of the strong electron correlation effect. The ferromagnetism in Fe doped GaSb system predicted by our investigation implied that the doping of Fe into GaSb can be as a vital routine for manufacturing the FM semiconductors with higher Curie temperature.

  3. Defect mediated reversible ferromagnetism in Co and Mn doped zinc oxide epitaxial films

    Mal, Siddhartha; Nori, Sudhakar; Narayan, J. [Department of Material Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695 (United States); Mula, Suhrit [Department of Material Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695 (United States); Department of Metallurgical and Materials Engineering, National Institute of Technology, Rourkela 769008 (India); Prater, J. T. [Materials Science Division, Army Research Office, Research Triangle Park, North Carolina 27709 (United States)

    2012-12-01

    We have introduced defects in ZnO (undoped and doped with Co and Mn) epitaxial thin films using laser irradiation from nanosecond laser pulses and thermal annealing in oxygen ambient. In contrast to the as grown samples, the laser irradiated films show a significant increase in conductivity, enhancement in UV emission, while maintaining the same wurtzite crystal structure. Room-temperature ferromagnetism (RTFM) is observed in laser-irradiated samples, which increased with the number of laser pulses up to a certain value where magnetic moment saturates. The induced ferromagnetism as well as the enhanced electrical conductivity can be reversed with thermal annealing in oxygen ambient. The magnetization in Co and Mn doped films was found to be strong function of growth conditions and defect concentration. X-ray diffraction and optical absorption experiments suggested a 2+ valance state and tetrahedral coordination for both Co and Mn ions. There is a simultaneous increase in n-type electrical conductivity with the number of laser pulses and continue to exhibit semiconducting behavior in both undoped and doped films. The saturation magnetization was found to be 0.08 {mu}{sub B}/Co and 0.05 {mu}{sub B}/Mn, much lower than 3.0 {mu}{sub B}/Co and 5.0 {mu}{sub B}/Mn, indicating the prominent role of intrinsic defects in RTFM with some contribution from Co{sup 2+}-oxygen vacancy complexes. We propose a unified mechanism based upon introduction of intrinsic defects to explain RTFM and n-type conductivity enhancements during pulsed laser and thermal annealing.

  4. Doping of alkali, alkaline-earth, and transition metals in covalent-organic frameworks for enhancing CO2 capture by first-principles calculations and molecular simulations.

    Lan, Jianhui; Cao, Dapeng; Wang, Wenchuan; Smit, Berend

    2010-07-27

    We use the multiscale simulation approach, which combines the first-principles calculations and grand canonical Monte Carlo simulations, to comprehensively study the doping of a series of alkali (Li, Na, and K), alkaline-earth (Be, Mg, and Ca), and transition (Sc and Ti) metals in nanoporous covalent organic frameworks (COFs), and the effects of the doped metals on CO2 capture. The results indicate that, among all the metals studied, Li, Sc, and Ti can bind with COFs stably, while Be, Mg, and Ca cannot, because the binding of Be, Mg, and Ca with COFs is very weak. Furthermore, Li, Sc, and Ti can improve the uptakes of CO2 in COFs significantly. However, the binding energy of a CO2 molecule with Sc and Ti exceeds the lower limit of chemisorptions and, thus, suffers from the difficulty of desorption. By the comparative studies above, it is found that Li is the best surface modifier of COFs for CO2 capture among all the metals studied. Therefore, we further investigate the uptakes of CO2 in the Li-doped COFs. Our simulation results show that at 298 K and 1 bar, the excess CO2 uptakes of the Li-doped COF-102 and COF-105 reach 409 and 344 mg/g, which are about eight and four times those in the nondoped ones, respectively. As the pressure increases to 40 bar, the CO2 uptakes of the Li-doped COF-102 and COF-105 reach 1349 and 2266 mg/g at 298 K, respectively, which are among the reported highest scores to date. In summary, doping of metals in porous COFs provides an efficient approach for enhancing CO2 capture.

  5. Selenophene transition metal complexes

    White, Carter James [Iowa State Univ., Ames, IA (United States)

    1994-07-27

    This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the η5- and the η1(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The 77Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of η1(S)-bound thiophenes, η1(S)-benzothiophene and η1(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the η1(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh3)Re(2-benzothioenylcarbene)]O3SCF3 was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the η1(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

  6. Defect types and room temperature ferromagnetism in N-doped rutile TiO2 single crystals

    Qin, Xiu-Bo; Li, Dong-Xiang; Li, Rui-Qin; Zhang, Peng; Li, Yu-Xiao; Wang, Bao-Yi

    2014-06-01

    The magnetic properties and defect types of virgin and N-doped TiO2 single crystals are probed by superconducting quantum interference device (SQUID), X-ray photoelectron spectroscopy (XPS), and positron annihilation analysis (PAS). Upon N doping, a twofold enhancement of the saturation magnetization is observed. Apparently, this enhancement is not related to an increase in oxygen vacancy, rather to unpaired 3d electrons in Ti3+, arising from titanium vacancies and the replacement of O with N atoms in the rutile structure. The production of titanium vacancies can enhance the room temperature ferromagnetism (RTFM), and substitution of O with N is the onset of ferromagnetism by inducing relatively strong ferromagnetic ordering.

  7. Positive magnetoresistance in ferromagnetic Nd-doped In2O3 thin films grown by pulse laser deposition

    Xing, G. Z.; Yi, J. B.; Yan, F.; Wu, Tao; Li, S.

    2014-01-01

    temperature ferromagnetism in the as-prepared films. The strong sp-f exchange interaction as a result of the rare earth doping is discussed as the origin of the magnetotransport behaviours. A positive magnetoresistance (∼29.2%) was observed at 5 K and ascribed

  8. Gd doping induced weak ferromagnetic ordering in ZnS nanoparticles synthesized by low temperature co-precipitation technique

    Kaur, Palvinder [Department of Physics, Punjabi University, Patiala, Punjab, 147002 (India); Kumar, Sanjeev, E-mail: sanjeev04101977@gmail.com [Applied Science Department, PEC University of Technology, Chandigarh, 160012 (India); Chen, Chi-Liang, E-mail: chen.cl@nsrrc.org.tw [National Synchrotron Radiation Research Center (NSRRC), Hsinchu, 30076, Taiwan (China); Yang, Kai-Siang [National Synchrotron Radiation Research Center (NSRRC), Hsinchu, 30076, Taiwan (China); Department of Mechanical Engineering, National Taipei University of Technology, Taipei, Taiwan (China); Wei, Da-Hua [Department of Mechanical Engineering, National Taipei University of Technology, Taipei, Taiwan (China); Dong, Chung-Li [Department of Physics, Tamkang University, Tamsui, Taiwan (China); Srivastava, C. [Materials Engineering Department, Indian Institute of Science, Bangalore, 560012 (India); Rao, S.M. [Department of Physics, Punjabi University, Patiala, Punjab, 147002 (India); Institute of Physics, Academia Sinica, Taipei, 11529, Taiwan (China)

    2017-01-15

    Zn{sub 1−x}Gd{sub x}S nanoparticles with Gd concentration x = 0.00, 0.02 and 0.04 were synthesized by the chemical co-precipitation technique using thioglycerol as capping agent. X-ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy, X-ray absorption near-edge structure (XANES) and vibrating sample magnetometer (VSM) were employed to characterize the as synthesized Gd doped ZnS nanoparticles. XRD and TEM studies show the formation of cubic ZnS nanoparticles with an average size in the range 5–10 nm. The doping did not alter the phase of the ZnS. The PL spectra of doped ZnS nanoparticles showed the presence of sulphur vacancies in the lattice. XANES of Gd doped ZnS nanoparticles depicts spectral changes may arise from charge transfer between host Zn and dopant Gd ions. A VSM study shows that the weak ferromagnetic behaviour increases with increase in Gd doping ZnS nanoparticles. - Highlights: • Gd doped ZnS nanoparticles synthesized using co-precipitation technique. • PL studies depict sulphur and zinc vacancies in Gd doped ZnS nanoparticles. • XANES studies depict the charge transfer between host Zn and dopant Gd ions. • Room temperature weak ferromagnetism is observed in Gd doped ZnS nanoparticles.

  9. Gd doping induced weak ferromagnetic ordering in ZnS nanoparticles synthesized by low temperature co-precipitation technique

    Kaur, Palvinder; Kumar, Sanjeev; Chen, Chi-Liang; Yang, Kai-Siang; Wei, Da-Hua; Dong, Chung-Li; Srivastava, C.; Rao, S.M.

    2017-01-01

    Zn_1_−_xGd_xS nanoparticles with Gd concentration x = 0.00, 0.02 and 0.04 were synthesized by the chemical co-precipitation technique using thioglycerol as capping agent. X-ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy, X-ray absorption near-edge structure (XANES) and vibrating sample magnetometer (VSM) were employed to characterize the as synthesized Gd doped ZnS nanoparticles. XRD and TEM studies show the formation of cubic ZnS nanoparticles with an average size in the range 5–10 nm. The doping did not alter the phase of the ZnS. The PL spectra of doped ZnS nanoparticles showed the presence of sulphur vacancies in the lattice. XANES of Gd doped ZnS nanoparticles depicts spectral changes may arise from charge transfer between host Zn and dopant Gd ions. A VSM study shows that the weak ferromagnetic behaviour increases with increase in Gd doping ZnS nanoparticles. - Highlights: • Gd doped ZnS nanoparticles synthesized using co-precipitation technique. • PL studies depict sulphur and zinc vacancies in Gd doped ZnS nanoparticles. • XANES studies depict the charge transfer between host Zn and dopant Gd ions. • Room temperature weak ferromagnetism is observed in Gd doped ZnS nanoparticles.

  10. Stability and magnetic properties of SnSe monolayer doped by transition metal atom (Mn, Fe, and Co): a first-principles study

    Tang, Chao; Li, Qinwen; Zhang, Chunxiao; He, Chaoyu; Li, Jin; Ouyang, Tao; Li, Hongxing; Zhong, Jianxin

    2018-06-01

    Two dimensional (2D) tin selenium (SnSe) is an intriguing material with desired thermal and electric properties in nanoelectronics. In this paper, we carry on a density functional theory study on the stability and dilute magnetism of the 3d TM (Mn, Fe, and Co) doped 2D SnSe. Both the adsorption and substitution are in consideration here. We find that all the defects are electrically active and the cation substitutional doping (TM@Sn) is energetically favorable. The TM@Sn prefers to act as accepters and exhibits high-spin state with nonzero magnetic moment. The magnetic moment is mainly contributed by the spin-polarized charge density of the TM impurities. The magnetism is determined by the arrangement of the TM-3d orbitals, which is the result of the crystal field splitting and spin exchange splitting under specific symmetry. The magnetic and electronic properties of the TM@Sn are effectively modulated by external electric field (Eext) and charge doping. The Eext shifts the TM impurities relative to the SnSe host and then modifies the crystal field splitting. In particular, the magnetic moment is sensitive to the Eext in the Fe@Sn because the Eext induces distinct structure transformation. Based on the formation energy, doping electrons is a viable way to modulate the magnetic moment of TM@Sn. Doping electrons shift the 3d states towards low energy level, which induces the occupation of more 3d states and then the reduction of magnetism. These results render SnSe monolayer a promising 2D material for applications in future spintronics.

  11. Transition metals in carbohydrate chemistry

    Madsen, Robert

    1997-01-01

    This review describes the application of transition metal mediated reactions in carbohydrate synthesis. The different metal mediated transformations are divided into reaction types and illustrated by various examples on monosaccharide derivatives. Carbon-carbon bond forming reactions are further ...

  12. Microwave-assisted aqueous synthesis of transition metal ions doped ZnSe/ZnS core/shell quantum dots with tunable white-light emission

    Zhang, Jie [Laboratory of Advanced Materials, Fudan University, Shanghai 200438 (China); Chen, Qiuhang; Zhang, Wanlu; Mei, Shiliang; He, Liangjie; Zhu, Jiatao [Engineering Research Center of Advanced Lighting Technology, Ministry of Education, Institute for Electric Light Sources, Fudan University, Shanghai 200433 (China); Chen, Guoping [School of Information Science and Technology, Fudan University, Shanghai 200433 (China); Guo, Ruiqian, E-mail: rqguo@fudan.edu.cn [Engineering Research Center of Advanced Lighting Technology, Ministry of Education, Institute for Electric Light Sources, Fudan University, Shanghai 200433 (China)

    2015-10-01

    Highlights: • ZnSe-based QDs were formed via a microwave-assisted aqueous approach. • The stabilizer, ZnS coats and UV irradiation played a role in the PL enhancement. • Tunable white-light-emitting Mn:ZnSe QDs and Cu,Mn:ZnSe/ZnS QDs were synthesized. • The formation mechanism of Cu,Mn:ZnSe QDs was clarified. • The corresponding CIE color coordinates of different PL spectra were obtained. - Abstract: Synthesis of bright white-light emitting Mn and Cu co-doped ZnSe/ZnS core/shell quantum dots (QDs) (Cu,Mn:ZnSe/ZnS) was reported. Water-soluble ZnSe-based QDs with Mn and Cu doping were prepared using a versatile hot-injection method in aqueous solution with a microwave-assisted approach. Influence of the Se/S ratio, stabilizer, refluxing time and the concentration of Cu/Mn dopant ions on the particle size and photoluminescence (PL) were investigated. The as-prepared QDs in the different stages of growth were characterized by X-ray powder diffractometer (XRD), high-resolution transmission electron microscopy (HRTEM), UV–visible (UV–vis) spectrophotometer, and fluorescence spectrophotometer. It is found that these ZnSe-based QDs synthesized under mild conditions exhibit emission in the range of 390–585 nm. The PL quantum yield (QY) of the as-prepared water-soluble ZnSe QDs can be up to 24.3% after the UV-irradiation treatment. The band-gap emission of ZnSe is effectively restrained through Mn and Cu doping. The refluxing time influences the doping of not only Mn, but also Cu, which leads to the best refluxing time of Mn:ZnSe and the red-shift of the emission of Cu:ZnSe d-dots. Co-doping induced white-light emission (WLE) from Cu,Mn:ZnSe/ZnS core/shell QDs were obtained, which can offer the opportunity for future-generation white-light emitting diodes (LEDs)

  13. Density-functional study on the robust ferromagnetism in rare-earth element Yb-doped SnO{sub 2}

    Zhang, Kai-Cheng, E-mail: kczhang@yeah.net [College of Mathematics and Physics, Bohai University, Jinzhou 121013 (China); Li, Yong-Feng [Key Laboratory of Integrated Exploitation of Bayan Obo Multi-Metal ResourcesInner Mongolia University of Science and Technology, Baotou 014010 (China); School of Mathematics, Physics and Biological Engineering, Inner Mongolia University of Science and Technology, Baotou 014010 (China); Liu, Yong [State Key Laboratory of Metastable Materials Science and Technology and College of Science, Yanshan University, Qinhuangdao, Hebei 066004 (China); Chi, Feng [College of Engineering, Bohai University, Jinzhou 121013 (China)

    2014-06-01

    So far, little has been known about the ferromagnetism induced by p–f hybridization. We investigate the magnetic properties of Yb-doped SnO{sub 2} by first-principles calculations. We find that the doped system favors the ferromagnetic state and a room-temperature ferromagnetism can be expected in it. The origin of ferromagnetism can be attributed to the p–f hybridization between Yb impurity and its surrounding oxygen atoms. The formation energy of defect complex is calculated and the magnetic mediation of intrinsic vacancies is studied. Our results reveal that the formation energy of the defect complex with Sn vacancy is about 7.3 eV lower in energy than that with oxygen vacancy. This means Sn vacancy is much easier to form than oxygen vacancy in the presence of Yb substitution. The ferromagnetism of the doped system is greatly enhanced in the presence of Sn vacancies. - Highlights: • Room-temperature ferromagnetism can be expected in Yb-doped SnO{sub 2}. • The origin of ferromagnetism can be attributed to the p–f hybridization between Yb and O atoms. • Oxygen vacancies are much hard to form and contribute little to the ferromagnetism. • Sn vacancies are easy to form under oxygen-rich condition and stabilize the ferromagnetism effectively.

  14. High coercivity rare earth-transition metal magnets

    Croat, J.J.

    1982-01-01

    Ferromagnetic compositions having intrinsic magnetic coercivities at room temperature of at least 1,000 Oersteds are formed by the controlled quenching of molten rare earth -transition metal alloys. Hard magnets may be inexpensively formed from the lower atomic weight lanthanide elements and iron. The preferable compositions lie within: at least one of Fe, Ni, Co (20 to 70 atomic percent); and at least one of Ce, Pr, Na, Sm, Eu, Tb, Dy, Ho, Er, Tm, Y (80 to 30 atomic percent). (author)

  15. High coercivity rare earth-transition metal magnets

    Croat, J.J.

    1982-01-01

    Ferromagnetic compositions having intrinsic magnetic coercivities at room temperature of at least 1,000 Oersteds are formed by the controlled quenching of molten rare earth-transition metal alloys. Hard magnets may be inexpensively formed from the lower atomic weight lanthanide elements and iron. The preferable compositions lie within: at least one of Fe, Ni, Co; 20 - 70 atomic percent: at least one of Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Y; 80 - 30 atomic percent. (author)

  16. Room temperature p-type conductivity and coexistence of ferroelectric order in ferromagnetic Li doped ZnO nanoparticles

    Awan, Saif Ullah

    2014-10-28

    Memory and switching devices acquired new materials which exhibit ferroelectric and ferromagnetic order simultaneously. We reported multiferroic behavior in Zn1-yLiyO(0.00≤y≤0.10) nanoparticles. The analysis of transmission electron micrographs confirmed the hexagonal morphology and wurtzite crystalline structure. We investigated p-type conductivity in doped samples and measured hole carriers in range 2.4×1017/cc to 7.3×1017/cc for different Li contents. We found that hole carriers are responsible for long range order ferromagnetic coupling in Li doped samples. Room temperature ferroelectric hysteresis loops were observed in 8% and 10% Li doped samples. We demonstrated ferroelectric coercivity (remnant polarization) 2.5kV/cm (0.11 μC/cm2) and 2.8kV/cm (0.15 μC/cm2) for y=0.08 and y=0.10 samples. We propose that the mechanism of Li induced ferroelectricity in ZnO is due to indirect dipole interaction via hole carriers. We investigated that if the sample has hole carriers ≥5.3×1017/cc, they can mediate the ferroelectricity. Ferroelectric and ferromagnetic measurements showed that higher electric polarization and larger magnetic moment is attained when the hole concentration is larger and vice versa. Our results confirmed the hole dependent coexistence of ferromagnetic and ferroelectric behavior at room temperature, which provide potential applications for switchable and memory devices.

  17. A short review of theoretical and empirical models for characterization of optical materials doped with the transition metal and rare earth ions

    Su, P.; Ma, C.-G.; Brik, M. G.; Srivastava, A. M.

    2018-05-01

    In this paper, a brief retrospective review of the main developments in crystal field theory is provided. We have examined how different crystal field models are applied to solve the problems that arise in the spectroscopy of optically active ions. Attention is focused on the joint application of crystal field and density functional theory (DFT) based models, which takes advantages of strong features of both individual approaches and allows for obtaining a complementary picture of the electronic properties of a doped crystal with impurity energy levels superimposed onto the host band structure.

  18. Optical Properties of Malachite Green Dye Doped SiO2 Glasses: Effect of Transition Metal (Fe-I Used as a Codopant

    Dulen Bora

    2014-01-01

    Full Text Available Enhanced luminescence properties of Malachite Green (MG (oxalate in Fe-MG codoped SiO2 glasses compared to its values in MG doped SiO2 glasses are reported here. The enhancement is chiefly attributed to a resonance nonradiative energy transfer between Fe and MG. The quantum yield of Malachite Green (MG, in presence of Iron, trapped in sol-gel derived SiO2 glass increases by an order of ~103 compared to that in low viscous solvent while a lifetime of 3.29 ns is reported.

  19. Persistent luminescence of transition metal (Co, Ni...)-doped ZnGa2O4 phosphors for applications in the near-infrared range

    Pellerin, Morgane; Castaing, Victor; Gourier, Didier; Chanéac, Corinne; Viana, Bruno

    2018-02-01

    Persistent luminescence materials present many applications including security lighting and bio-imaging. Many progresses have been made in the elaboration of persistent luminescent nanoparticles suitable for the first NIR partial transparency window (650 - 950 nm). Moving to the second and third near-infrared partial transparency windows (1000 nm - 1800 nm) allows further reducing of scattering, absorption and tissue autofluorescence effects. In this work, we present the synthesis of Co2+ and Ni2+ doped zinc-gallate nanoparticles with broad emission covering the NIR-II range. Site occupancy, energy levels, optical features and persistent phenomena are presented.

  20. Effect of transition metal ions on the conductivity and stability of stabilized zirconia

    Lybye, D.; Mogensen, Mogens Bjerg

    2007-01-01

    the effect of co-doping with smaller transition metal ions such as Ti-, Fe- and Mn-ions. Many of the ionic radii of the transition metal ions are too small compared to the host lattice ionic radius of zirconium. Here we explore the effect of a) the small ionic radii compared to the large ionic radii...

  1. Rational Design of Two-Dimensional Metallic and Semiconducting Spintronic Materials Based on Ordered Double-Transition-Metal MXenes

    Dong, Liang; Kumar, Hemant; Anasori, Babak; Gogotsi, Yury; Shenoy, Vivek B.

    2016-01-01

    double-transition-metal MXene structures to achieve such a goal. On the basis of the analysis of electron filling in transition-metal cations and first-principles simulations, we demonstrate robust ferromagnetism in Ti2MnC2Tx monolayers regardless

  2. Transition metal nuclear magnetic resonance

    Pregosin, P.S.

    1991-01-01

    Transition metal NMR spectroscopy has progressed enormously in recent years. New methods, and specifically solid-state methods and new pulse sequences, have allowed access to data from nuclei with relatively low receptivities with the result that chemists have begun to consider old and new problems, previously unapproachable. Moreover, theory, computational science in particular, now permits the calculation of not just 13 C, 15 N and other light nuclei chemical shifts, but heavy main-group element and transition metals as well. These two points, combined with increasing access to high field pulsed spectrometer has produced a wealth of new data on the NMR transition metals. A new series of articles concerned with measuring, understanding and using the nuclear magnetic resonance spectra of the metals of Group 3-12 is presented. (author)

  3. Strategies to prepare TiO2 thin films, doped with transition metal ions, that exhibit specific physicochemical properties to support osteoblast cell adhesion and proliferation

    Dhayal, Marshal; Kapoor, Renu; Sistla, Pavana Goury; Pandey, Ravi Ranjan; Kar, Satabisha; Saini, Krishan Kumar; Pande, Gopal

    2014-01-01

    Metal ion doped titanium oxide (TiO 2 ) thin films, as bioactive coatings on metal or other implantable materials, can be used as surfaces for studying the cell biological properties of osteogenic and other cell types. Bulk crystallite phase distribution and surface carbon–oxygen constitution of thin films, play an important role in determining the biological responses of cells that come in their contact. Here we present a strategy to control the polarity of atomic interactions between the dopant metal and TiO 2 molecules and obtain surfaces with smaller crystallite phases and optimal surface carbon–oxygen composition to support the maximum proliferation and adhesion of osteoblast cells. Our results suggest that surfaces, in which atomic interactions between the dopant metals and TiO 2 were less polar, could support better adhesion, spreading and proliferation of cells. - Highlights: • Electrochemical properties of dopants control the nature of TiO 2 thin films. • A model explains the correlation of dopant properties and behaviour of TiO 2 films. • Dopants with less polar interaction with TiO 2 exhibit better biological activity

  4. Room temperature ferromagnetism in Eu-doped ZnO nanoparticulate powders prepared by combustion reaction method

    Franco, A.; Pessoni, H.V.S.; Soares, M.P.

    2014-01-01

    Nanoparticulate powders of Eu-doped ZnO with 1.0, 1.5, 2.0 and 3.0 at% Eu were synthesized by combustion reaction method using zinc nitrate, europium nitrate and urea as fuel without subsequent heat treatments. X-ray diffraction patterns (XRD) of all samples showed broad peaks consistent with the ZnO wurtzite structure. The absence of extra reflections in the diffraction patterns ensures the phase purity, except for x=0.03 that exhibits small reflection corresponding to Eu 2 O 3 phase. The average crystallite size determined from the most prominent (1 0 1) peak of the diffraction using Scherrer's equation was in good agreement with those determined by transmission electron microscopy (TEM); being ∼26 nm. The magnetic properties measurements were performed using a vibrating sample magnetometer (VSM) in magnetic fields up to 2.0 kOe at room temperature. The hysteresis loops, typical of magnetic behaviors, indicating that the presence of an ordered magnetic structure can exist in the Eu-doped ZnO wurtzite structure at room temperature. The room temperature ferromagnetism behavior increases with the Eu 3+ doping concentration. All samples exhibited the same Curie temperature (T C ) around ∼726 K, except for x=0.01; T C ∼643 K. High resolution transmission electron microscopy (HRTEM) images revealed defects/strain in the lattice and grain boundaries of Eu-doped ZnO nanoparticulate powders. The origin of room temperature ferromagnetism in Eu-doped ZnO nanoparticulate powders was discussed in terms of these defects, which increase with the Eu 3+ doping concentration. - Highlights: • Room-temperature ferromagnetism. • Structural and magnetic properties of nanoparticulate powders of Zn 1−x Eu x O. • Combustion reaction method

  5. Intrinsic and Extrinsic Ferromagnetism in Co-Doped Indium Tin Oxide Revealed Using X-Ray Magnetic Circular Dichroism

    A. M. H. R. Hakimi

    2017-01-01

    Full Text Available The effects of high-temperature annealing on ferromagnetic Co-doped Indium Tin Oxide (ITO thin films have been investigated using X-ray diffraction (XRD, magnetometry, and X-Ray Magnetic Circular Dichroism (XMCD. Following annealing, the magnetometry results indicate the formation of Co clusters with a significant increase in the saturation magnetization of the thin films arising from defects introduced during cluster formation. However, sum rule analysis of the element-specific XMCD results shows that the magnetic moment at the Co sites is reduced after annealing. The effects of annealing demonstrate that the ferromagnetism observed in the as-deposited Co-doped ITO films arises from intrinsic defects and cannot be related to the segregation of metallic Co clusters.

  6. Hole-doping effects on the magnetic properties of the La4Ba2Cu2O10 ferromagnet

    Mizuno, F.; Masuda, H.; Hirabayashi, I.; Tanaka, S.; Mochiku, T.; Asano, H.; Izumi, F.

    1992-01-01

    Hole-doping effects by Ba substitution for La in La 4-x Ba 2+x Cu 2 O 10 (0 ≤ x ≤ 1) have been studied to explore the possibilities of its metal-insulator transition and superconductivity. We have not detected any symptoms for metal-insulator transition, but found certain evidence for the hole-doping effect. We observed the dilution effect of Cu 2+ spin by non-magnetic Cu 3+ on the ferromagnetic transition temperature and the reduction of effective magnetic moment. (orig.)

  7. Electrical Conductivity in Transition Metals

    Talbot, Christopher; Vickneson, Kishanda

    2013-01-01

    The aim of this "Science Note" is to describe how to test the electron-sea model to determine whether it accurately predicts relative electrical conductivity for first-row transition metals. In the electron-sea model, a metal crystal is viewed as a three-dimensional array of metal cations immersed in a sea of delocalised valence…

  8. Transition Metal Complexes and Catalysis

    approaches towards the study of bonding in transition metal complexes. Despite .... industrial scale reactions for the production of organic compounds using transition ..... It has found several applications as an engineering thermoplastic. .... and processes of interest to the company, that is, applied research. It is this very ...

  9. Defect-band mediated ferromagnetism in Gd-doped ZnO thin films

    Venkatesh, S.; Franklin, J. B.; Ryan, M. P.; Lee, J.-S.; Ohldag, Hendrik; McLachlan, M. A.; Alford, N. M.; Roqan, Iman S.

    2015-01-01

    . %) at low oxygen deposition pressure (<25 mTorr) were ferromagnetic at room temperature. Negative magnetoresistance, electric transport properties showed that the ferromagnetic exchange is mediated by a spin-split defect band formed due to oxygen deficiency

  10. Thickness-modulated anisotropic ferromagnetism in Fe-doped epitaxial HfO2 thin films

    Liu, Wenlong; Liu, Ming; Zhang, Ruyi; Ma, Rong; Wang, Hong

    2017-10-01

    Epitaxial tetragonal Fe-doped Hf0.95Fe0.05O2 (FHO) thin films with various thicknesses were deposited on (001)-oriented NdCaAlO4 (NCAO) substrates by using a pulsed laser deposition (PLD) system. The crystal structure and epitaxial nature of the FHO thin films were confirmed by typical x-ray diffraction (XRD) θ-2θ scan and reciprocal space mapping (RSM). The results indicate that two sets of lattice sites exist with two different crystal orientations [(001) and (100)] in the thicker FHO thin films. Further, the intensity of the (100) direction increases with the increase in thicknesses, which should have a significant effect on the anisotropic magnetization of the FHO thin films. Meanwhile, all the FHO thin films possess a tetragonal phase structure. An anisotropy behavior in magnetization has been observed in the FHO thin films. The anisotropic magnetization of the FHO thin films is slowly weakened as the thickness increases. Meanwhile, the saturation magnetization (Ms) of both in-plane and out-of-plane decreases with the increase in the thickness. The change in the anisotropic magnetization and Ms is attributed to the crystal lattice and the variation in the valence of Fe ions. These results indicate that the thickness-modulated anisotropic ferromagnetism of the tetragonal FHO epitaxial thin films is of potential use for the integration of metal-oxide semiconductors with spintronics.

  11. Half-metallic ferromagnetism in Fe, Co and Ni doped BaS: First principles calculations

    Maurya, Savita; Sharma, Ramesh; Bhamu, K. C.

    2018-04-01

    The first principle investigation of structural, electronic, magnetic and optical properties of Ba1-xTMxS (x = 0.25) have been done using FPLAW method within the density functional theory (DFT) using generalized gradient approximation (GGA) for exchange correlation potential using two different functionals which are the PBE-sol and the modified Becke and Johnson local (spin) density approximation (mBJLDA). It was found that mBJLDA functional offer better account for the electronic structure of the Fe, Co and Ni-doped BaS. It was also observed that Fe/Co/Ni d, S p and Ba d states play a major role in determining the electronic properties of this alloy system. Investigation results shows that Ba0.75(Fe/Co/Ni)0.25S is ferromagnetic with magnetic moment of 3.72 µB, 2.73908 µB and 1.74324 µB at Fe, Co and Ni sites respectively. Complex dielectric constant ɛ(ω) and normal incidence reflectivity R(ω) are also been investigate for broad range of photon energies. These results are compared with the some reported existing experimental values.

  12. Tuning the competition between ferromagnetism and antiferromagnetism in a half-doped manganite through magnetoelectric coupling

    Yi, Di [University of California; Liu, Jian [University of California, Berkeley & LBNL; Okamoto, Satoshi [ORNL; Jagannatha, Suresha [Lawrence Berkeley National Laboratory (LBNL); Chen, Yi-Chun [National Cheng Kung University, Tainan, Taiwan; Yu, Pu [Tsinghua University; Chu, Ying-Hao [National Chiao Tung University, Hsinchu, Taiwan; Arenholz, Elke [Lawrence Berkeley National Laboratory (LBNL); Ramesh, Ramamoorthy [University of California, Berkeley

    2013-01-01

    We investigate the possibility of controlling the magnetic phase transition of the heterointerface between a half-doped manganite La0:5Ca0:5MnO3 and a multiferroic BiFeO3 (BFO) through magnetoelectric coupling. Using macroscopic magnetometry and element-selective x-ray magnetic circular dichroism at the Mn and Fe L edges, we discover that the ferroelectric polarization of BFO controls simultaneously the magnetization of BFO and La0.5Ca0.5MnO3 (LCMO). X-ray absorption spectra at the oxygen K edge and linear dichroism at the Mn L edge suggest that the interfacial coupling is mainly derived from the superexchange between Mn and Fe t2g spins. The combination of x-ray absorption spectroscopy and mean-field theory calculations reveals that the d-electron modulation of Mn cations changes the magnetic coupling in LCMO, which controls the enhanced canted moments of interfacial BFO via the interfacial coupling. Our results demonstrate that the competition between ferromagnetic and antiferromagnetic instability can be modulated by an electric field at the heterointerface, providing another pathway for the electrical field control of magnetism.

  13. Enhanced room temperature ferromagnetism in Cr-doped ZnO nanoparticles prepared by auto-combustion method

    Haq, Khizar-ul; Irfan, M.; Masood, Muhammad; Saleem, Murtaza; Iqbal, Tahir; Ahmad, Ishaq; Khan, M. A.; Zaffar, M.; Irfan, Muhammad

    2018-04-01

    Zn1‑x Cr x O (x = 0.00, 0.01, 0.03, 0.05, 0.07, and 0.09) nanoparticles were synthesized, by an auto-combustion method. Structural, optical, and magnetic characteristics of Cr-doped ZnO samples calcined at 600 °C have been analyzed by using X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), UV–Vis spectroscopy and vibrating sample magnetometer (VSM). The XRD data confirmed the hexagonal wurtzite structure of pure and Cr-doped ZnO nanoparticles. The calculated values of grain size using Scherrer's formula are in the range of 30.7–9.2 nm. The morphology of nanopowders has been observed by FESEM, and EDS results confirmed a systematic increase of Cr content in the samples and clearly indicate with no impurity element. The band gaps, computed by UV–Vis spectroscopy, are in the range of 2.83–2.35 eV for different doping concentrations. By analyzing VSM data, significantly enhanced room temperature ferromagnetism is identified in Cr-doped ZnO samples. The value of magnetization is a 12 times increased of the value reported by Daunet al. (2010). Room temperature ferromagnetism of the nanoparticles is of vital prominence for spintronics applications. Project supported by the Office of Research, Innovation, and Commercialization (ORIC), MUST Mirpur (AJK).

  14. Room temperature ferromagnetism in undoped and Ni doped In{sub 2}O{sub 3} thin films

    Krishna, N. Sai; Kaleemulla, S., E-mail: skaleemulla@gmail.com; Rao, N. Madhusudhana; Krishnamoorthi, C.; Begam, M. Rigana [Thin Films Laboratory, School of Advanced Sciences, VIT University, Vellore – 632014 (India); Amarendra, G. [Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam – 603102 (India); UGC-DAE-CSR, Kalpakkam Node, Kokilamedu-603104 (India)

    2015-06-24

    Undoped and Ni (5 at.%) doped In{sub 2}O{sub 3} thin films were deposited on glass substrate using electron beam evaporation technique and Ni doped In{sub 2}O{sub 3} thin films were annealed at 450 oC. A systematic study was carried out on the structural, chemical and magnetic properties of the as deposited and annealed thin films. X-ray diffraction analysis revealed that all the films were cubic in structure and exhibied ferromagnetism at room temperature. The undoped In{sub 2}O{sub 3} thin films exhibited a saturation magnetization of 24.01 emu/cm3. Ni doped In{sub 2}O{sub 3} thin films annealed at 450 oC showed a saturation magnetization of 53.81 emu/cm3.

  15. Enhancement of ferromagnetic properties in Zn0.98Cu0.02O by additional Co doping

    Liu, Huilian; Zhang, Xu; Liu, Hongbo; Yang, Jinghai; Liu, Yang; Liu, Xiaoyan; Gao, Ming; Wei, Maobin; Cheng, Xin; Wang, Jian

    2013-01-01

    Highlights: •The samples were synthesized by sol–gel technology to dope up to 3% Co in ZnCuO. •After Co doped into Zn 0.98 Cu 0.02 O sample photoluminescence shows an increase in green emission. •The saturation magnetization increased with Co doping. -- Abstract: Zn 0.98 Cu 0.02 O and Zn 0.95 Cu 0.02 Co 0.03 O powders were synthesized by sol–gel method, and the effects of Co codoping on the structure, optical and magnetic properties of the Zn 0.98 Cu 0.02 O powders were studied in detail. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurement shows the Zn 0.98 Cu 0.02 O and Zn 0.95 Cu 0.02 Co 0.03 O powders were single phase with the ZnO wurtzite structure, and there was no ferromagnetic-related secondary phase in these powders. Moreover, these powders exhibited ferromagnetism at the room temperature investigated by the magnetic measurement, and the ferromagnetism of the Zn 0.98 Cu 0.02 O and Zn 0.95 Cu 0.02 Co 0.03 O samples were originated from the fact that the Cu ions and Co, Cu ions doped into the ZnO lattices, respectively. In addition, the saturation magnetization (Ms) was significantly increased with Co codoping due to the increased density of oxygen vacancies

  16. Spectroscopic investigation of an intrinsic room temperature ferromagnetism in Co doped ZnO nanoparticles

    N, Srinatha [Department of Physics, JB Campus, Bangalore University, Bangalore 560056 (India); Angadi, Basavaraj, E-mail: brangadi@gmail.com [Department of Physics, JB Campus, Bangalore University, Bangalore 560056 (India); Nair, K.G.M. [UGC-DAE-CSR, Kalpakkam Node, Kalpakkam, Kokilamedu 603 102 (India); Deshpande, Nishad G.; Shao, Y.C.; Pong, Way-Faung [Department of Physics, Tamkang University, Tamsui, Taipei 251, Taiwan (China)

    2014-08-15

    Highlights: • For the first time L-Valine was used as a fuel to synthesize Co:ZnO nanoparticles by solution combustion method. • Single phase and ferromagnetic nature were confirmed through XRD, SQUID, NEXAFS and XMCD. • Through NEXAFS and XMCD, the effect of ‘Co’ substitution at O K-edge, Co L{sub 3,2} edge, Zn L{sub 3,2} edge have been investigated. • Spectral features of NEXAFS and XMCD confirms an intrinsic RTFM by substitution of ‘Co{sup 2+}’ at ‘Zn{sup 2+}’ site and rules out the presence of secondary phases. - Abstract: Pure and Co substituted ZnO nano crystalline particles were prepared by solution combustion technique using L-Valine as a fuel. As synthesized powder samples were characterized by X-ray diffractometer and SQUID magnetometer to confirm the formation of single phase wurtzite structure and to study the bulk magnetic response of the sample, respectively. Magnetic studies show that Co doped ZnO nanoparticles exhibit ferromagnetism (FM) at room temperature (RT). Furthermore, the electronic structure and element specific magnetic properties were investigated by near-edge X-ray absorption fine structure (NEXAFS) and X-ray magnetic circular dichroism (XMCD) measurements, respectively. The effect of Co substitution on the spectral features of Co–ZnO at O K-edge, Co L{sub 3,2} edge, Zn L{sub 3,2} edge have been investigated. The spectral features of NEXAFS at Co L{sub 3,2} edge is entirely different from the spectral features of metallic clusters and other impurity phases, which rules out the presence of impurity phases. The valence state of ‘Co’ ion is found to be in +2 state. The FM nature of the sample was confirmed through XMCD spectra, which is due to the incorporation of divalent ‘Co’ ions. Hence the presented results confirm the substitution of ‘Co’ ions at ‘Zn’ site in the host lattice, which is responsible for the RTFM.

  17. Preparation of Boron Nitride Nanoparticles with Oxygen Doping and a Study of Their Room-Temperature Ferromagnetism.

    Lu, Qing; Zhao, Qi; Yang, Tianye; Zhai, Chengbo; Wang, Dongxue; Zhang, Mingzhe

    2018-04-18

    In this work, oxygen-doped boron nitride nanoparticles with room-temperature ferromagnetism have been synthesized by a new, facile, and efficient method. There are no metal magnetic impurities in the nanoparticles analyzed by X-ray photoelectron spectroscopy. The boron nitride nanoparticles exhibit a parabolic shape with increase in the reaction time. The saturation magnetization value reaches a maximum of 0.2975 emu g -1 at 300 K when the reaction time is 12 h, indicating that the Curie temperature ( T C ) is higher than 300 K. Combined with first-principles calculation, the coupling between B 2p orbital, N 2p orbital, and O 2p orbital in the conduction bands is the main origin of room-temperature ferromagnetism and also proves that the magnetic moment changes according the oxygen-doping content change. Compared with other room temperature ferromagnetic semiconductors, boron nitride nanoparticles have widely potential applications in spintronic devices because of high temperature oxidation resistance and excellent chemical stability.

  18. Structural and room temperature ferromagnetic properties of Ni doped ZnO nanoparticles via low-temperature hydrothermal method

    Xu, Kun; Liu, Changzhen, E-mail: liuchangzhen94@163.com; Chen, Rui; Fang, Xiaoxiang; Wu, Xiuling; Liu, Jie

    2016-12-01

    A series of Zn{sub 1−x}Ni{sub x}O (x=0, 1%, 3%, 5%) nanoparticles have been synthesized via a low-temperature hydrothermal method. Influence of Ni doping concentration on the structure, morphology, optical properties and magnetism of the samples was investigated by means of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, UV–vis spectrophotometer and vibrating sample magnetometer instruments. The results show that the undoped and doped ZnO nanoparticles are both hexagonal wurtzite structures. The surface analysis was performed using X-ray photoelectron spectroscopic studies. The images of SEM reveal that the structure of pure ZnO and Ni doped samples are nanoparticles which intended to form flakes with thickness of few nanometers, being overlain with each one to develop the network with some pores and voids. Based on the ultraviolet–visible (UV–vis) spectroscopy analysis, it indicates that the band gap energy decreases with the increasing concentration of Ni. Furthermore, The Ni doped ZnO samples didn't exhibit higher ultraviolet-light-driven photocatalytic activity compared to the undoped ZnO sample. Vibrating sample magnetometer was used for the magnetic property investigations, and the result indicates that room temperature ferromagnetism property of 3% Ni doped sample is attributed to oxygen vacancy and interaction between doped ions.

  19. Room temperature ferromagnetism in nano-crystalline Co:ThO2 powders

    Bhide, M.K.; Kadam, R.M.; Godbole, S.V.; Tyagi, A.K.; Salunke, H.G.

    2012-01-01

    The major interest in dilute magnetic semiconductors (DMS's) had been directed towards the synthesis of room temperature ferromagnetic (RTF) materials for their potential applications in spintronic devices. Room temperature (RT) ferromagnetism was initially reported in Co doped TiO 2 , ZnO 2 and SnO 2 thin films and in the recent past in transition metal doped wide band gap materials. In the present paper we report the synthesis of Co doped ThO 2 nano powders by urea combustion method. The XRD characterization of 300℃ annealed samples confirmed formation of ThO 2 in the cubic phase and the average crystallite size obtained using Scherrer's formula was around 6 nm

  20. Positive magnetoresistance in ferromagnetic Nd-doped In2O3 thin films grown by pulse laser deposition

    Xing, G. Z.

    2014-05-23

    We report the magnetic and magnetotransport properties of (In 0.985Nd0.015)2O2.89 thin films grown by pulse laser deposition. The clear magnetization hysteresis loops with the complementary magnetic domain structure reveal the intrinsic room temperature ferromagnetism in the as-prepared films. The strong sp-f exchange interaction as a result of the rare earth doping is discussed as the origin of the magnetotransport behaviours. A positive magnetoresistance (∼29.2%) was observed at 5 K and ascribed to the strong ferromagnetic sp-f exchange interaction in (In0.985Nd0.015)2O 2.89 thin films due to a large Zeeman splitting in an external magnetic field of 50 KOe. © 2014 AIP Publishing LLC.

  1. Ab initio calculations of half-metallic ferromagnetism in Cr-doped MgSe and MgTe semiconductors

    Noor, N.A. [Department of Physics, University of the Punjab, Quaid-e-Azam Campus, 54590 Lahore (Pakistan); Alay-e-Abbas, S.M. [Department of Physics, University of Sargodha, Sargodha 40100 (Pakistan); Department of Physics, GC University Faisalabad, Allama Iqbal Road, Faisalabad 38000 (Pakistan); Sohaib, M.U. [Lahore Development Authority, 54590 Lahore (Pakistan); Ghulam Abbas, S.M. [Department of Chemistry, University of Agriculture, Faisalabad 38040 (Pakistan); Shaukat, A., E-mail: schaukat@gmail.com [Department of Physics, University of Sargodha, Sargodha 40100 (Pakistan)

    2015-01-15

    The full-potential linear-augmented-plane-waves plus local-orbitals (FP-LAPW+lo) method has been employed for investigation of half-metallic ferromagnetism in Cr-doped ordered zinc-blende MgSe and MgTe semiconductors. Calculations of exchange and correlation (XC) effects have been carried out using generalized gradient approximation (GGA) and orbital independent modified Becke–Johnson potential coupled with local (spin) density approximation (mBJLDA). The thermodynamic stability of the compounds and their preferred magnetic orders have been analyzed in terms of the heat of formation and minimum total energy difference in ferromagnetic (FM) and anti-ferromagnetic (AFM) ordering, respectively. Calculated electronic properties reveal that the Cr-doping induces ferromagnetism in MgSe and MgTe which gives rise to a half-metallic (HM) gap at Fermi level (E{sub F}). Further, the electronic band structure is discussed in terms of s (p)–d exchange constants that are consistent with typical magneto-optical experiment and the behavior of charge spin densities is presented for understanding the bonding nature. Our results demonstrate that the higher effective potential for the spin-down case is responsible for p–d exchange splitting. Total magnetic moment (mainly due to Cr-d states) of these compounds is 4µ{sub B}. Importantly, the electronic properties and HM gap obtained using mBJLDA show remarkable improvement as compared to the results obtained using standard GGA functional. - Highlights: • Spin effect theoretical study on Cr-doped MgSe and MgTe is performed. • Half-metallic ferromagnetism in Cr{sub x}Mg{sub 1−x}Se and Cr{sub x}Mg{sub 1−x}Te is established. • Results of WC-GGA and mBJLDA are compared for performance. • HM gaps for Cr{sub x}Mg{sub 1−x}Se and Cr{sub x}Mg{sub 1−x}Te show nonlinear variation with x. • Important values of exchange splitting/constants and moments are reported.

  2. Different magnetic properties of rhombohedral and cubic Ni2+ doped indium oxide nanomaterials

    Qingbo Sun

    2011-12-01

    Full Text Available Transition metal ions doped indium oxide nanomaterials were potentially used as a kind of diluted magnetic semiconductors in transparent spintronic devices. In this paper, the influences of Ni2+ doped contents and rhombohedral or cubic crystalline structures of indium oxide on magnetic properties were investigated. We found that the magnetic properties of Ni2+ doped indium oxide could be transferred from room temperature ferromagnetisms to paramagnetic properties with increments of doped contents. Moreover, the different crystalline structures of indium oxide also greatly affected the room temperature ferromagnetisms due to different lattice constants and almost had no effects on their paramagnetic properties. In addition, both the ferromagnetic and paramagnetic properties were demonstrated to be intrinsic and not caused by impurities.

  3. Electrochromism in transition metal oxides

    Estrada, W.

    1993-01-01

    Electrochromism is discussed for transition metal oxides. Particularly tungsten oxide and nickel oxide are reviewed, in order to put forth the different aspects of the field. Since this phenomena has been reviewed by several authors, it is not tried to be comprehensive but rather pedagogical. The basic requirements for a material -in both non-emissive displays and energy efficiency applications- to be electrochromic, a general view of electrochromic mechanism, anodic and cathodic electrochromic materials, and current problems for a electrochromic theory are presented. (author) 45 refs., 8 figs

  4. Heterostructures of transition metal dichalcogenides

    Amin, Bin

    2015-08-24

    The structural, electronic, optical, and photocatalytic properties of out-of-plane and in-plane heterostructures of transition metal dichalcogenides are investigated by (hybrid) first principles calculations. The out-of-plane heterostructures are found to be indirect band gap semiconductors with type-II band alignment. Direct band gaps can be achieved by moderate tensile strain in specific cases. The excitonic peaks show blueshifts as compared to the parent monolayer systems, whereas redshifts occur when the chalcogen atoms are exchanged along the series S-Se-Te. Strong absorption from infrared to visible light as well as excellent photocatalytic properties can be achieved.

  5. OBSERVATION OF MAGNETIC DOMAINS IN IRRADIATED TRANSITION METALS BY HIGH VOLTAGE ELECTRON MICROSCOPY

    Ono , F.; Jakubovics , J.; Maeta , H.

    1988-01-01

    The effect of irradiation on the movement of domain walls was studied in ferromagnetic transition metals by using a high voltage electron microscope. In iron, a domain wall became easily movable at a 300 kV irradiation. The mobility was less affected in cobalt, while in nickel the effect was the greatest.

  6. Effects of iron deficiency on anisotropy and ferromagnetic resonance linewidth in Bi-doped LiZn ferrite

    Xiaona Jiang

    2017-05-01

    Full Text Available Bi-doped LiZn ferrites with different iron deficiencies were fabricated by a conventional ceramic method. Anisotropy constant (K1 was calculated and ferromagnetic resonance (FMR linewidth (ΔH was investigated. Crystalline anisotropy broadening linewidth (ΔHa and porosity broadening linewidth (ΔHp were derived by an approximate calculation based on dipolar narrowing theory, which play a significant role in contributions to FMR linewidth and occupy more than 90 % of ΔH. Physical and static magnetic properties of LiZn ferrite with iron deficiency are presented, which supports a decline in linewidths with increasing iron deficiency. Iron deficiency makes K1, ΔHa and ΔHp reduce. The results also show that ΔHp is the majority of contributions to ΔH in Bi-doped LiZn ferrite and densification is an effective method to decrease ΔH.

  7. Some ENDOR studies of 3d transition metal ions in semiconductors

    Engelen, P.P.J.

    1980-01-01

    The author considers 3d transition metal ions substituted in covalent semiconducting crystals. The magnitude of the contact hyperfine field at the 59 Co nucleus in cobalt doped CdS is determined. The results of an ENDOR study of supertransferred hyperfine interactions with nearest neighbour Ga ions in Mn doped GaP are presented. (G.T.H.)

  8. Effects of hydrogen annealing on the room temperature ferromagnetism and optical properties of Cr-doped ZnO nanoparticles

    Tong Liuniu; Wang Yichao; He Xianmei; Han Huaibin; Xia Ailin; Hu Jinlian

    2012-01-01

    We explore the effects of hydrogen annealing on the room temperature ferromagnetism and optical properties of Cr-doped ZnO nanoparticles synthesized by the sol-gel method. X-ray diffraction and x-ray photoelectron spectroscopy data show evidence that Cr has been incorporated into the wurtzite ZnO lattice as Cr 2+ ions substituting for Zn 2+ ions without any detectable secondary phase in as-synthesized Zn 0.97 Cr 0.03 O nanopowders. The room temperature magnetization measurements reveal a large enhancement of saturation magnetization M s as well as an increase of coercivity of H 2 -annealed Zn 0.97 Cr 0.03 O:H samples. It is found that the field-cooled magnetization curves as a function of temperature from 40 to 400 K can be well fitted by a combination of a standard Bloch spin-wave model and Curie–Weiss law. The values of the fitted parameters of the ferromagnetic exchange interaction constant a and the Curie constant C of H 2 -annealed Zn 0.97 Cr 0.03 O:H nanoparticles are almost doubled upon H 2 -annealing. Photoluminescence measurements show evidence that the shallow donor defect or/and defect complexes such as hydrogen occupying an oxygen vacancy H o may play an important role in the origin of H 2 -annealing induced enhancement of ferromagnetism in Cr-H codoped ZnO nanoparticles. - Graphical Abstract: The H 2 -annealing induced enhancement of room temperature ferromagnetism in Cr-doped ZnO nanoparticles is observed. It is found that the field-cooled M-T curves can be well fitted by a combination of a standard Bloch spin-wave model and Curie–Weiss law. The values of the fitted parameters of the ferromagnetic exchange interaction constant a and the Curie constant C of H 2 -annealed Zn 0.97 Cr 0.03 O:H nanoparticles are almost doubled upon H 2 -annealing. The PL data show evidence that the hydrogen related shallow donor defect or/and defect complexes may be responsible for it. Display Omitted Highlights: ► The H 2 -annealing induced a large enhancement of

  9. Ferromagnetic coupling strength and electron-doping effects in double perovskites

    Fontcuberta, J.; Rubi, D.; Frontera, C.; Garcia-Munoz, J.L.; Wojcik, M.; Jedryka, E.; Nadolski, S.; Izquierdo, M.; Avila, J.; Asensio, M.C.

    2005-01-01

    We review experiments and results on ferromagnetic and metallic A 2 FeMoO 6 double perovskites that made it possible to obtain a detailed understanding of the nature of the ferromagnetic coupling and paved the way for further enhancement of the Curie temperature. We show that appropriate chemical substitutions, combined with detailed structural, magnetotransport and spectroscopic data allow us to map quite a complete picture of the properties of these oxides

  10. Positron annihilation studies of vacancy-type defects and room temperature ferromagnetism in chemically synthesized Li-doped ZnO nanocrystals

    Ghosh, S.; Khan, Gobinda Gopal; Mandal, K.; Thapa, Samudrajit; Nambissan, P.M.G.

    2014-01-01

    Highlights: • Evidence of zinc vacancy-induced intrinsic ferromagnetism in Li-doped ZnO. • Modification of defects and properties through alkali metal substitution. • Study of defect-modification using positron annihilation spectroscopy. • New way to prepare ZnO-based magnetic semiconductor for spintronic applications. -- Abstract: In this article, we have investigated the effects of Li incorporation on the lattice defects and room-temperature d 0 ferromagnetic behaviour in ZnO nanocrystals by correlating X-ray photoelectron, photoluminescence and positron annihilation spectroscopic study in details. It is found that at low doping level ( 1+ is an effective substituent of Zn site, but it prefers to occupy the interstitial positions when Li-doping exceeds 7 at.% resulting in lattice expansion and increase of particle sizes. The pristine ZnO nanocrystals exhibit ferromagnetic behaviour which is further enhanced significantly after few percentage of Li-doping in ZnO. The magnitude of both saturation magnetizations (M S ) as well as the Curie temperature (T C ) are found to increase considerably up to Li concentration of 10 at.% and then started to decrease on further Li-doping. The gradual enhancement of Zn vacancy (V Zn ) defects in ZnO nanocrystals due to Li substitution as confirmed from photoluminescence and positron annihilation spectroscopy measurements might be responsible to induce paramagnetic moments within ZnO host. The ferromagnetic exchange interaction between the localised moments of V Zn defects can be mediated though the holes arising due to Li-substitutional (Li Zn ) acceptor defects within ZnO. Hence, Li doping in ZnO favours in stabilizing considerable V Zn defects and thus helps to sustain long-range high-T C ferromagnetism in ZnO which can be a promising material in future spintronics

  11. Positron annihilation studies of vacancy-type defects and room temperature ferromagnetism in chemically synthesized Li-doped ZnO nanocrystals

    Ghosh, S., E-mail: sghoshphysics@gmail.com [S.N. Bose National Centre for Basic Sciences, Block JD, Sector III, Salt Lake, Kolkata 700098 (India); Khan, Gobinda Gopal [Centre for Research in Nanoscience and Nanotechnology, University of Calcutta, Technology Campus, Block JD2, Sector III, Salt Lake City, Kolkata 700098 (India); Mandal, K. [S.N. Bose National Centre for Basic Sciences, Block JD, Sector III, Salt Lake, Kolkata 700098 (India); Thapa, Samudrajit; Nambissan, P.M.G. [Centre for Research in Nanoscience and Nanotechnology, University of Calcutta, Technology Campus, Block JD2, Sector III, Salt Lake City, Kolkata 700098 (India); Saha Institute of Nuclear Physics, Sector 1, Block AF, Bidhannagar, Kolkata 700064 (India)

    2014-03-25

    Highlights: • Evidence of zinc vacancy-induced intrinsic ferromagnetism in Li-doped ZnO. • Modification of defects and properties through alkali metal substitution. • Study of defect-modification using positron annihilation spectroscopy. • New way to prepare ZnO-based magnetic semiconductor for spintronic applications. -- Abstract: In this article, we have investigated the effects of Li incorporation on the lattice defects and room-temperature d{sup 0} ferromagnetic behaviour in ZnO nanocrystals by correlating X-ray photoelectron, photoluminescence and positron annihilation spectroscopic study in details. It is found that at low doping level (<7 at.%), Li{sup 1+} is an effective substituent of Zn site, but it prefers to occupy the interstitial positions when Li-doping exceeds 7 at.% resulting in lattice expansion and increase of particle sizes. The pristine ZnO nanocrystals exhibit ferromagnetic behaviour which is further enhanced significantly after few percentage of Li-doping in ZnO. The magnitude of both saturation magnetizations (M{sub S}) as well as the Curie temperature (T{sub C}) are found to increase considerably up to Li concentration of 10 at.% and then started to decrease on further Li-doping. The gradual enhancement of Zn vacancy (V{sub Zn}) defects in ZnO nanocrystals due to Li substitution as confirmed from photoluminescence and positron annihilation spectroscopy measurements might be responsible to induce paramagnetic moments within ZnO host. The ferromagnetic exchange interaction between the localised moments of V{sub Zn} defects can be mediated though the holes arising due to Li-substitutional (Li{sub Zn}) acceptor defects within ZnO. Hence, Li doping in ZnO favours in stabilizing considerable V{sub Zn} defects and thus helps to sustain long-range high-T{sub C} ferromagnetism in ZnO which can be a promising material in future spintronics.

  12. The role of Co impurities and oxygen vacancies in the ferromagnetism of Co-doped SnO2: GGA and GGA+U studies

    Wang Hongxia; Yan Yu; Mohammed, Y. Sh.; Du Xiaobo; Li Kai; Jin Hanmin

    2009-01-01

    The electronic structure and ferromagnetic stability of Co-doped SnO 2 are studied using the first-principle density functional method within the generalized gradient approximation (GGA) and GGA+U schemes. The addition of effective U Co transforms the ground state of Co-doped SnO 2 to insulating from half-metallic and the coupling between the nearest neighbor Co spins to weak antimagnetic from strong ferromagnetic. GGA+U Co calculations show that the pure substitutional Co defects in SnO 2 cannot induce the ferromagnetism. Oxygen vacancies tend to locate near Co atoms. Their presence increases the magnetic moment of Co and induces the ferromagnetic coupling between two Co spins with large Co-Co distance. The calculated density of state and spin density distribution calculated by GGA+U Co show that the long-range ferromagnetic coupling between two Co spins is mediated by spin-split impurity band induced by oxygen vacancies. More charge transfer from impurity to Co-3d states and larger spin split of Co-3d and impurity states induced by the addition of U Co enhance the ferromagnetic stability of the system with oxygen vacancies. By applying a Coulomb U O on O 2 s orbital, the band gap is corrected for all calculations and the conclusions derived from GGA+U Co calculations are not changed by the correction of band gap.

  13. Competing exchange bias and field-induced ferromagnetism in La-doped BaFe O3

    Fita, I.; Wisniewski, A.; Puzniak, R.; Iwanowski, P.; Markovich, V.; Kolesnik, S.; Dabrowski, B.

    2017-04-01

    An exchange bias (EB) effect was observed in mixed valent L axB a1 -xFe O3 (x =0.125 , 0.25, 0.33) perovskites exhibiting the antiferromagnetic (AFM) helical order among F e4 + ions coexisting with the ferromagnetic (FM) cluster phase in the ground state. The L a3 + ions for B a2 + site substitution, associated with increase in number of the AFM coupled F e3 + - F e4 + pairs as well as some F e3 + - F e3 + pairs, leads to strengthening of the AFM phase and consequently to the alteration of the EB characteristics, which depend on level of the La doping x . At low doping x ≤0.25 , an abnormal dependence of the EB field, HEB, on the cooling field, Hcool, was found. The HEB increases rapidly with increasing cooling field at low Hcool, but it falls suddenly at cooling fields higher than 20 kOe, reducing by an order of magnitude at 90 kOe. The suppression of EB is caused by the field-induced increased volume of the FM phase, due to the transformation of the AFM helical spin structure into the FM one. Thus, low-doped L axB a1 -xFe O3 demonstrates a competition of two alternate cooling-field-induced effects, one of which leads to the EB anisotropy and another one to the enhanced ferromagnetism. In contrast, the x =0.33 sample, having a strong AFM constituent, shows no field-induced FM and no drop in the EB field. Accordingly, the HEB vs Hcool dependence was found to be well explained in the framework of a model describing phase-separated AFM-FM systems, namely, the model assuming isolated FM clusters of size ˜4 nm embedded in the AFM matrix.

  14. Defect-induced room temperature ferromagnetic properties of the Al-doped and undoped ZnO rod-like nanostructure

    Jule, L

    2017-07-01

    Full Text Available : 151-155 Defect-induced room temperature ferromagnetic properties of the Al-doped and undoped ZnO rod-like nanostructure Jule L Dejene F Ali AG Roro KT Mwakikunga BW ABSTRACT: In this work, electron paramagnetic resonance (EPR...

  15. Magnetism in V-/Mn-doped ZnO layers fabricated on sapphire

    Mofor, A.C.; El-Shaer, A.; Schlenker, E.; Bakin, A.; Waag, A. [Technical University Braunschweig, Institute of Semiconductor Technology, Braunschweig (Germany); Reuss, F.; Kling, R.; Schoch, W.; Limmer, W. [University Ulm, Department of Semiconductor Physics, Ulm (Germany); Ahlers, H.; Siegner, U.; Sievers, S.; Albrecht, M. [Physikalisch-Technische Bundesanstalt (PTB), Braunschweig (Germany); Eisenmenger, J.; Mueller, T.; Ziemann, P. [University Ulm, Department of Solid State Physics, Ulm (Germany); Huebel, A.; Denninger, G. [Universitaet Stuttgart, 2. Physkalisches Institut, Stuttgart (Germany)

    2007-07-15

    Doping ZnO with transition metals (TM) is an obvious approach to produce diluted magnetic semiconductors for magnetoelectronic and spintronic applications. We have carried out experimental studies on the fabrication and characterisation of Mn-doped ZnO layers and V-doped ZnO layers and nanorods, the results of which are reviewed in this paper. From SQUID measurements, both epitaxial and implanted ZnMnO layers show paramagnetic behaviour. Epitaxial ZnVO layers show ferromagnetic SQUID signals, but the presence of any secondary phases in the ZnVO layers may not be ruled out. We also show that the used Al{sub 2}O{sub 3} substrates produce a ferromagnetic SQUID signal, that complicates the analysis of magnetisation data and hence the confirmation of ferromagnetism only from SQUID results. (orig.)

  16. Scattering Effect on Anomalous Hall Effect in Ferromagnetic Transition Metals

    Zhang, Qiang

    2017-01-01

    , the side-jump contribution increases with 𝑛𝑛, which suggests an interfacial scattering-enhanced side jump. In the (Ni36/𝑛/Au12/𝑛)𝑛 samples, the side-jump contribution decreases with 𝑛 increases, which could be explained by the opposite sign

  17. Scattering Effect on Anomalous Hall Effect in Ferromagnetic Transition Metals

    Zhang, Qiang

    2017-11-30

    The anomalous Hall effect (AHE) has been discovered for over a century, but its origin is still highly controversial theoretically and experimentally. In this study, we investigated the scattering effect on the AHE for both exploring the underlying physics and technical applications. We prepared Cox(MgO)100-x granular thin films with different Co volume fraction (34≤≤100) and studied the interfacial scattering effect on the AHE. The STEM HAADF images confirmed the inhomogeneous granular structure of the samples. As decreases from 100 to 34, the values of longitudinal resistivity () and anomalous Hall resistivity (AHE) respectively increase by about four and three orders in magnitude. The linear scaling relation between the anomalous Hall coefficient () and the measured at 5 K holds in both the as-prepared and annealed samples, which suggests a skew scattering dominated mechanism in Cox(MgO)100-x granular thin films. We prepared (Fe36//Au12/), (Ni36//Au12/) and (Ta12//Fe36/) multilayers to study the interfacial scattering effect on the AHE. The multilayer structures were characterized by the XRR spectra and TEM images of cross-sections. For the three serials of multilayers, both the and AHE increase with , which clearly shows interfacial scattering effect. The intrinsic contribution decreases with increases in the three serials of samples, which may be due to the crystallinity decaying or the finite size effect. In the (Fe36//Au12/) samples, the side-jump contribution increases with , which suggests an interfacial scattering-enhanced side jump. In the (Ni36//Au12/) samples, the side-jump contribution decreases with increases, which could be explained by the opposite sign of the interfacial scattering and grain boundary scattering contributed side jump. In the (Ta12//Fe36/) multilayers, the side-jump contribution changed from negative to positive, which is also because of the opposite sign of the interfacial scattering and grain boundary scattering contributed side jump. The interfacial scattering effect on the AHE is much more complicated than surface scattering in thin films or scattering by delta-impurities in bulk-like samples.

  18. Magnetic behavior of clusters of ferromagnetic transition metals

    Khanna, S. N.; Linderoth, Søren

    1991-01-01

    The effective magnetic moments of small iron and cobalt clusters have been calculated by assuming that the clusters undergo superparamagnetic relaxation. The effective moments per atom are found to be much below the bulk values, even at low temperatures (100 K). They increase with particle size a...... moments in small clusters compared to bulk as being due to melting of surface spins....

  19. Low Temperature Ferromagnetism and Optical Properties of Fe Doped ZnO Nanoparticles Synthesized by Sol-Gel Method

    B. Sathya

    2017-06-01

    Full Text Available In this present investigation, pure and Fe doped Zinc oxide nanoparticles were successfully synthesized by sol gel method.The structural and optical properties were examined by using X-ray diffraction (XRD, Scanning electron microscope (SEM, Transmission electron microscope (TEM, Ultraviolet spectroscopy and Photoluminescence (PL techniques.The structural characterization of XRD analysis confirmed the phase purity of the samples and crystallite size can be decreased with increasing doping concentrations.SEM image show that nanoparticles in spherical shape. The optical band gap calculated through UV-visible spectroscopy is found to be increasing from 3.48 to 3.57eV. TEM analysis depicted the crystallinity of nanoparticles prepared and chemical composition conformed the EDAX analysis. The PL spectra reveal that, Fe doped ZnO exhibit a decrease in intensity of the band edge emission peak while the intensity of the deep level emission peak increases.The enhancement of low temperature ferromagnetism in ZnO: Fe was achieved.

  20. Transition metal implanted ZnO. A correlation between structure and magnetism

    Zhou, Shengqiang

    2008-07-01

    Nowadays ferromagnetism is often found in potential diluted magnetic semiconductor systems. However, many authors question the origin of this ferromagnetism, i.e. if the observed ferromagnetism stems from ferromagnetic precipitates rather than from carriermediated magnetic coupling of ionic impurities, as required for a diluted magnetic semiconductor. In this thesis, this question will be answered for transition-metal implanted ZnO single crystals. Magnetic secondary phases, namely metallic Fe, Co and Ni nanocrystals, are formed inside ZnO. They are - although difficult to detect by common approaches of structural analysis - responsible for the observed ferromagnetism. Particularly Co and Ni nanocrystals are crystallographically oriented with respect to the ZnO matrix. Their structure phase transformation and corresponding evolution of magnetic properties upon annealing have been established. Finally, an approach, pre-annealing ZnO crystals at high temperature before implantation, has been demonstrated to sufficiently suppress the formation of metallic secondary phases. (orig.)

  1. Nd and Sc co-doped BiFeO{sub 3} nanopowders displaying enhanced ferromagnetism at room temperature

    Hernández, N., E-mail: netzahualpille.hernandeznv@uanl.edu.mx [Centro de Innovación, Investigación y Desarrollo en Ingeniería y Tecnología, Km. 10 Nueva carretera al Aeropuerto Internacional de Monterrey, PIIT Monterrey, CP 66600 Apodaca, Nuevo León (Mexico); González-González, V.A. [Centro de Innovación, Investigación y Desarrollo en Ingeniería y Tecnología, Km. 10 Nueva carretera al Aeropuerto Internacional de Monterrey, PIIT Monterrey, CP 66600 Apodaca, Nuevo León (Mexico); Facultad de Ingeniería Mecánica y Eléctrica, Universidad Autónoma de Nuevo León, Pedro de Alba S/N, San Nicolás de los Garza, Nuevo León 66450 (Mexico); Dzul-Bautista, I.B. [Centro de Innovación, Investigación y Desarrollo en Ingeniería y Tecnología, Km. 10 Nueva carretera al Aeropuerto Internacional de Monterrey, PIIT Monterrey, CP 66600 Apodaca, Nuevo León (Mexico); Gutiérrez, J.; Barandiarán, J.M. [Basque Center for Materials, Applications and Nanostructures (BCMaterials), Universidad del País Vasco (UPV/EHU), Parque Tecnológico de Bizkaia, Ed. 500, Derio 48160 (Spain); and others

    2015-07-25

    Highlights: • Will study the structure of materials obtained. • A well crystallized BiFeO{sub 3} doped material was obtained without further annealing. • The obtained nanoparticles have sizes less than 60 nm. • Enhanced ferromagnetic materials was obtained. - Abstract: We have developed a novel synthetic route for the preparation of single phase Nd{sub x}Bi{sub 1−x}Fe{sub 0.95}Sc{sub 0.05}O{sub 3} (NBFSO) nanopowder materials by a surfactant-assisted combustion-derived method. Rietveld fitting of the Powder X-ray diffraction data showed the nanopowder structure evolves from a distorted rhombohedral BiFeO{sub 3} crystalline structure (R3c, x = 0) to a orthorhombic structure (Pbnm, x = 0.10). Differential thermal analysis and thermogravimetric analysis (DTA/TGA) showed a crystallization temperature of 200 °C. Transmission electron microscopy (TEM) images revealed the presence of clusters formed by fine nanoparticles less than 60 nm in diameter. From Raman spectroscopy, the change from rhombohedral structure to cubic structure was observed by a drastic intensity reduction of the A{sub 1}{sup −2} and A{sub 1}{sup −3} Raman modes, with the A{sub 1}{sup −1} and A{sub 1}{sup −2} modes gradually merging together, indicating the merge of the orthorhombic phase. Despite the antiferromagnetic nature of bulk BiFeO{sub 3}, the NBFSO nanopowders obtained displayed a ferromagnetic hysteresis loop, with coercivities of 0.08 T and remanent magnetizations of 0.65–4.05 Am{sup 2}/kg when measured at room temperature. The increasing and uncompensated spins at the surface of nanoparticles and the canted internal spin by the tilt of FeO{sub 6} octahedral units and the structure transition appear to be the main reason for observed this ferromagnetic behavior.

  2. Room-temperature ferromagnetic properties of Cu-doped ZnO rod ...

    We have investigated properties of the Cu-doped ZnO crystalline film synthesized by the hydrothermal method. X-ray diffraction and X-ray ... DMSs are semiconducting alloys whose lattice is made up in part of substitutional magnetic ... investigate Cu-doped ZnO system (Hou et al 2007a, b), as. Cu is a potential magnetic ion ...

  3. Explanation of ferromagnetism origin in N-doped ZnO by first ...

    Moreover, ZnO doped with. 3d TM elements has been studied widely since the model calculation by Dietl et al predicted the possibility of ferro- magnetism in ZnO with a small amount of Mn as an impurity. [4]. However, TM doping often suffers from the problems related to precipitates or secondary phase formation undesir-.

  4. Magnetic evolution of itinerant ferromagnetism and interlayer antiferromagnetism in cerium doped LaCo{sub 2}P{sub 2} crystals

    Tian, Yong; Kong, Yixiu; Liu, Kai; Zhang, Anmin [Department of Physics, Beijing Key Laboratory of Opto-electronic Functional Materials & Micro-nano Devices, Renmin University of China, Beijing 100872 (China); He, Rui [Department of Physics, University of Northern Iowa, Cedar Falls, Iowa 50614 (United States); Zhang, Qingming, E-mail: qmzhang@ruc.edu.cn [Department of Physics, Beijing Key Laboratory of Opto-electronic Functional Materials & Micro-nano Devices, Renmin University of China, Beijing 100872 (China)

    2017-05-01

    ThCr{sub 2}Si{sub 2}-type phosphide ACo{sub 2}P{sub 2} (A=Eu, La, Pr, Nd, Ce) has the same structure as iron arsenides, but their magnetic behaviors are quite distinct. In this paper, we grew a series of La{sub 1−x}Ce{sub x}Co{sub 2}P{sub 2} single crystals (x=0.0 to1.0), made structural and magnetic characterizations. We found the introduction of cerium induces a rapid decrease of c-axis and a change from ferromagnetic to antiferromagnetic states. Compared to other trivalent doped compounds, the enhancement of ferromagnetism with doping is suppressed and the transition from ferromagnetism to antiferromagnetism appear earlier. By employing first-principles band-structure calculations, we identify the increase of Ce valence suppress the itinerant ferromagnetism and leading to formation of P-P bonding with the shortening of c-axis. The bonding effectively drives an increase of interlayer antiferromagnetic interaction, eventually leads to antiferromagnetic ordering of cobalt in high-doping region.

  5. Defect evolution and its impact on the ferromagnetism of Cu-doped ZnO nanocrystals upon thermal treatment: A positron annihilation study

    Chen, Zhi-Yuan; Chen, Yuqian; Zhang, Q. K.; Qi, N.; Chen, Z. Q.; Wang, S. J.; Li, P. H.; Mascher, P.

    2017-01-01

    CuO/ZnO nanocomposites with 4 at. % CuO were annealed in air at various temperatures between 100 and 1200 °C to produce Cu-doped ZnO nanocrystals. X-ray diffraction shows that a CuO phase can be observed in the CuO/ZnO nanocomposites annealed at different temperatures, and the Cu-doped ZnO nanocrystals are identified to be of wurtzite structure. The main peak (101) appears at slightly lower diffraction angles with increasing annealing temperature from 400 up to 1200 °C, which confirms the successful doping of Cu into the ZnO lattice above 400 °C. Scanning electron microscopy indicates that most particles in the CuO/ZnO nanocomposites are isolated when annealing at 100-400 °C, but these particles have a tendency to form clusters or aggregates as the annealing temperature increases from 700 to 1000 °C. Positron annihilation measurements reveal a large number of vacancy defects in the interface region of the nanocomposites, and they are gradually recovered with increasing annealing temperature up to 1000 °C. Room-temperature ferromagnetism can be observed in the CuO/ZnO nanocomposites, and the magnetization decreases continuously with increasing annealing temperature. However, there may be several different origins of ferromagnetism in the CuO/ZnO nanocomposites. At low annealing temperatures, the ferromagnetism originates from the CuO nanograins, and the ferromagnetism of CuO nanograins decreases with an increase in the grain size after subsequent higher temperature annealing, which leads to the weakening of ferromagnetism in the CuO/ZnO nanocomposites. After annealing from 400 to 1000 °C, the ferromagnetism gradually vanishes. The ferromagnetism is probably induced by Cu substitution but is mediated by vacancy defects in the CuO/ZnO nanocomposites. The disappearance of ferromagnetism coincides well with the recovery of vacancy defects. It can be inferred that the ferromagnetism is mediated by vacancy defects that are distributed in the interface region.

  6. XRD and FTIR studies the effect of heat treatment and doping the transition metal oxide on LiNbO3 and LiNb3O8 nano-crystallite phases in lithium borate glass system.

    Kashif, Ismail; Soliman, Ashia A; Sakr, Elham M; Ratep, Asmaa

    2013-09-01

    Glasses of various compositions in the system 90 Li2B4O7-10 Nb2O5 mixed with T.M ions (where T.M is the transition metal) were prepared by quenching technique. Heat-treatment of the parent glasses was performed at 540, 570 and 620 °C, for 5 and 16 h. The glass structure evolution during the controlled crystallization was examined by XRD and FT-IR spectroscopy analysis. The crystalline phases present in the glass ceramics were identified via X-ray diffraction as a function of heat treatment. The FT-IR data propose for these glasses and heat-treated glass network structures mainly built by: di-, tri-, tetra-, penta-and ortho-borate groups. It was found that the quantitative evolution of these various borate species in the glass structures is influenced by the transition metal. A detailed discussion relating to the N4 evolution with the T.M content was made. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Doping Properties of Ferromagnetic Semiconductors Investigated by the Hyperfine Interaction of Implanted Radioisotopes

    2002-01-01

    One of the most promising prospective applications of semiconductors will be in the field of spinelectronics. Thereby polarized spins must be injected into semiconductor structures. Ferromagnetic semiconductors (FMS) have a potential for such applications because of the coexistence of semiconducting and ferromagnetic properties. A special group of such FMS are the chromium chalcogenides of type AB$_{2}$C$_{4}$ with B = Cr. They crystallise in the structure of normal spinel. In this Proposal the application of the perturbed angular correlation technique (= PAC) for the investigation of nuclear probes in these substances is described. The radioactive probes will be implanted at the ISOLDE separator. We will start these investigations with the substances CdCr$_{2}$Se$_{4}$, CdCr$_{2}$S$_{4}$, HgCr$_{2}$Se$_{4}$, CuCr$_{2}$Se$_{4}$ and CuCr$_{2}$S$_{4}$ which are ferromagnetic with Curie temperatures between 84.5 and 460 K. In addition to the popular $^{111}$In($^{111}$Cd), which we get from other facilities, we ...

  8. Dark excitations in monolayer transition metal dichalcogenides

    Deilmann, Thorsten; Thygesen, Kristian Sommer

    2017-01-01

    Monolayers of transition metal dichalcogenides (TMDCs) possess unique optoelectronic properties, including strongly bound excitons and trions. To date, most studies have focused on optically active excitations, but recent experiments have highlighted the existence of dark states, which are equally...

  9. Post-annealing effect on the room-temperature ferromagnetism in Cu-doped ZnO thin films

    Hu, Yu-Min; Kuang, Chein-Hsiun; Han, Tai-Chun; Yu, Chin-Chung; Li, Sih-Sian

    2015-01-01

    In this work, we investigated the structural and magnetic properties of both as-deposited and post-annealed Cu-doped ZnO thin films for better understanding the possible mechanisms of room-temperature ferromagnetism (RT-FM) in ZnO-based diluted magnetic oxides. All of the films have a c-axis-oriented wurtzite structure and display RT-FM. X-ray photoelectron spectroscopy results showed that the incorporated Cu ions in as-deposited films are in 1+ valence state merely, while an additional 2+ valence state occurs in post-annealed films. The presence of Cu 2+ state in post-annealed film accompanies a higher magnetization value than that of as-deposited film and, in particular, the magnetization curves at 10 K and 300 K of the post-annealed film separate distinctly. Since Cu 1+ ion has a filled 3d band, the RT-FM in as-deposited Cu-doped ZnO thin films may stem solely from intrinsic defects, while that in post-annealed films is enhanced due to the presence of CuO crystallites

  10. Study of antiferro – ferromagnetic phase coexistence in Ta doped HfFe{sub 2}

    Bag, Pallab, E-mail: pallab@csr.res.in [UGC-DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore 452001, MP (India); Singh, Sanjay [Saha Institute of Nuclear Physics, 1/AF Bidhan Nagar, Kolkata 700064 (India); Babu, P.D.; Siruguri, Vasudeva [UGC-DAE Consortium for Scientific Research, Mumbai Centre, R-5 Shed, BARC, Mumbai 400085 (India); Rawat, Rajeev [UGC-DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore 452001, MP (India)

    2014-09-01

    First order antiferromagnetic (AFM) to ferromagnetic (FM) transition in Hf{sub 1−x}Ta{sub x}Fe{sub 2} with x∼0.225 compounds was studied by resistivity, magnetization and X-ray diffraction (XRD) measurements at low temperature. Magnetization measurements as a function of temperature and magnetic field show path dependent FM phase fraction at 5 K for x=0.225. XRD measurements at 15 K show co-existing AFM and FM phases for this composition with ∼0.9% unit cell volume difference of FM and AFM phase.

  11. Efficient photocarrier injection in a transition metal oxide heterostructure

    Muraoka, Y; Ueda, Y; Hiroi, Z

    2002-01-01

    An efficient method for doping a transition metal oxide (TMO) with hole carriers is presented: photocarrier injection (PCI) in an oxide heterostructure. It is shown that an insulating vanadium dioxide (VO sub 2) film is rendered metallic under light irradiation by PCI from an n-type titanium dioxide (TiO sub 2) substrate doped with Nb. Consequently, a large photoconductivity, which is exceptional for TMOs, is found in the VO sub 2 /TiO sub 2 :Nb heterostructure. We propose an electronic band structure where photoinduced holes created in TiO sub 2 :Nb can be transferred into the filled V 3d band via the low-lying O 2p band of VO sub 2. (letter to the editor)

  12. Lattice vibrational properties of transition metal carbides (TiC, ZrC

    Lattice vibrational properties of transition metal carbides (TiC, ZrC and HfC) have been presented by including the effects of free-carrier doping and three-body interactions in the rigid shell model. The short-range overlap repulsion is operative up to the second neighbour ions. An excellent agreement has been obtained ...

  13. Modeling and calculation of RKKY exchange coupling to explain Ti-vacancy-induced ferromagnetism in Ta-doped TiO2

    Majidi, Muhammad Aziz; Bupu, Annamaria; Fauzi, Angga Dito

    2017-12-01

    We present a theoretical study on Ti-vacancy-induced ferromagnetism in anatase TiO2. A recent experimental study has revealed room temperature ferromagnetism in Ta-doped anatase TiO2thin films (Rusydi et al., 2012) [7]. Ta doping assists the formation of Ti vacancies which then induce the formation of localized magnetic moments around the Ti vacancies. As neighboring Ti vacancies are a few unit cells apart, the ferromagnetic order is suspected to be mediated by itinerant electrons. We propose that such an electron-mediated ferromagnetism is driven by Ruderman-Kittel-Kasuya-Yosida (RKKY) exchange interaction. To examine our hypothesis, we construct a tight-binding based model Hamiltonian for the anatase TiO2 system. We calculate the RKKY exchange coupling constant of TiO2 as a function of distance between local magnetic moments at various temperatures. We model the system by taking only the layer containing a unit of TiO2, at which the Ti vacancy is believed to form, as our effective two-dimensional unit cell. Our model incorporates the Hubbard repulsive interactions between electrons occupying Ti d orbitals treated within mean-field approximation. The density of states profile resulting from the model captures the relevant electronic properties of TiO2, such as the energy gap of 3.4 eV and the n-type character, which may be a measure of the adequacy of the model. The calculated RKKY coupling constant shows that the ferromagnetic coupling extends up to 3-4 unit cells and enhances slightly as temperature is increased from 0 to 400 K. These results support our hypothesis that the ferromagnetism of this system is driven by RKKY mechanism.

  14. Microwave-assisted synthesis of transition metal phosphide

    Viswanathan, Tito

    2014-12-30

    A method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of preparing a transition metal lignosulfonate, mixing the transition metal lignosulfonate with phosphoric acid to form a mixture, and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.

  15. Inhibition of Neuroblastoma cancer cells viability by ferromagnetic Mn doped CeO_2 monodisperse nanoparticles mediated through reactive oxygen species

    Abbas, Fazal; Jan, Tariq; Iqbal, Javed; Haider Naqvi, M. Sajjad; Ahmad, Ishaq

    2016-01-01

    Here we report the Mn doping induced effects on structural, Raman, optical, magnetic and anticancer properties of CeO_2 nanoparticles prepared via soft chemical route. Structural and microstructural results infer that the synthesized nanoparticles have single phase cubic fluorite structure of CeO_2 and that Mn doping results in enhancement of the structural defects. Scanning electron microscopy results reveal the formation of monodisperse nanoparticles having average particle size ranging from 30 to 41 nm. The optical absorbance spectroscopy analysis discloses the band gap energy tailoring of CeO_2 nanoparticles via Mn doping. Room temperature ferromagnetism (RTFM) has been found in both as-prepared and Mn doped CeO_2 nanoparticles. This RTFM of the synthesized nanoparticles have been attributed to the Mn ions and surface defects such as oxygen vacancies. Finally, the influence of Mn dopant on the cell viability and reactive oxygen species (ROS) generation levels of CeO_2 nanoparticles in the presence of healthy and cancerous cells have been studied. It has been observed that the differential cytotoxicity of the synthesized nanoparticles is strongly correlated with level of ROS generation. - Highlights: • Mn doped CeO_2 nanoparticles with cubic fluorite structure were synthesized. • Mn dopant significantly tailored the band gap of CeO_2 nanoparticles. • The synthesized nanoparticles exhibited room temperature ferromagnetic behavior. • The cytotoxicity of these nanoparticles was reported for the first time. • The synthesized nanoparticles exhibited differential cytotoxicity.

  16. Electroplating lithium transition metal oxides

    Zhang, Huigang; Ning, Hailong; Busbee, John; Shen, Zihan; Kiggins, Chadd; Hua, Yuyan; Eaves, Janna; Davis, Jerome; Shi, Tan; Shao, Yu-Tsun; Zuo, Jian-Min; Hong, Xuhao; Chan, Yanbin; Wang, Shuangbao; Wang, Peng; Sun, Pengcheng; Xu, Sheng; Liu, Jinyun; Braun, Paul V.

    2017-01-01

    Materials synthesis often provides opportunities for innovation. We demonstrate a general low-temperature (260°C) molten salt electrodeposition approach to directly electroplate the important lithium-ion (Li-ion) battery cathode materials LiCoO2, LiMn2O4, and Al-doped LiCoO2. The crystallinities and electrochemical capacities of the electroplated oxides are comparable to those of the powders synthesized at much higher temperatures (700° to 1000°C). This new growth method significantly broadens the scope of battery form factors and functionalities, enabling a variety of highly desirable battery properties, including high energy, high power, and unprecedented electrode flexibility. PMID:28508061

  17. Mass fractionation processes of transition metal isotopes

    Zhu, X. K.; Guo, Y.; Williams, R. J. P.; O'Nions, R. K.; Matthews, A.; Belshaw, N. S.; Canters, G. W.; de Waal, E. C.; Weser, U.; Burgess, B. K.; Salvato, B.

    2002-06-01

    Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper and iron isotope fractionation during various inorganic and biological processes. These results demonstrate that: (1) naturally occurring inorganic processes can fractionate Fe isotope to a detectable level even at temperature ˜1000°C, which challenges the previous view that Fe isotope variations in natural system are unique biosignatures; (2) multiple-step equilibrium processes at low temperatures may cause large mass fractionation of transition metal isotopes even when the fractionation per single step is small; (3) oxidation-reduction is an importation controlling factor of isotope fractionation of transition metal elements with multiple valences, which opens a wide range of applications of these new isotope systems, ranging from metal-silicate fractionation in the solar system to uptake pathways of these elements in biological systems; (4) organisms incorporate lighter isotopes of transition metals preferentially, and transition metal isotope fractionation occurs stepwise along their pathways within biological systems during their uptake.

  18. Evidence of dilute ferromagnetism in rare-earth doped yttrium aluminium garnet

    Farr, Warrick G.; Goryachev, Maxim; Le Floch, Jean-Michel; Tobar, Michael E. [ARC Centre of Excellence for Engineered Quantum Systems, University of Western Australia, 35 Stirling Highway, Crawley, Western Australia 6009 (Australia); Bushev, Pavel [Experimentalphysik, Universität des Saarlandes, D-66123 Saarbrücken (Germany)

    2015-09-21

    This work demonstrates strong coupling regime between an erbium ion spin ensemble and microwave hybrid cavity-whispering gallery modes in a yttrium aluminium garnet dielectric crystal. Coupling strengths of 220 MHz and mode quality factors in excess of 10{sup 6} are demonstrated. Moreover, the magnetic response of high-Q modes demonstrates behaviour which is unusual for paramagnetic systems. This behaviour includes hysteresis and memory effects. Such qualitative change of the system's magnetic field response is interpreted as a phase transition of rare earth ion impurities. This phenomenon is similar to the phenomenon of dilute ferromagnetism in semiconductors. The clear temperature dependence of the phenomenon is demonstrated.

  19. Preparation of Photo catalytic Materials Based on Bi{sub 4}Ti{sub 3}O{sub 1}2 Doped with Transition Metals; Preparacion de Materiales Fotocatalizadores Basados en Bi{sub 4}Ti{sub 3}O{sub 1}2 Dopados con Metales de Transicion

    Calatalyud, D. G.; Rodriguez, M.; Gallego, B.; Fernandez-Hevia, D.; Jardiel, T.

    2012-07-01

    The production of hydrogen from water using ceramic semiconductors with photo catalytic properties has gained special relevance in the last years, due to their potential use for the generation of hydrogen in a direct and clean way. Doping with transition metals has demonstrated to be an effective method to obtain new active photo catalysts in the visible range of the solar spectrum by changing the band gap of the material. In this paper we study the effect of the addition of various dopants (Fe, Ni, Cr, Mn, Co, Cu) in the structure and band gap of Bi{sub 4}Ti{sub 3}O{sub 1}2, in order to improve its photo catalytic activity and make it visible light active. Accordingly, doped BIT based materials have been obtained by solid state processing and different amounts of an additional phase with sillenite structure, Bi{sub 1}2TiO{sub 2}0, have been detected. With the dopant a shift of the absorption spectra is produced towards higher wavelengths and consequently towards lower band gap values. The band gap values obtained for many of the prepared compositions are quite promising, promoting the study of their catalytic properties.. (Author)

  20. Defect-induced ferromagnetism in semiconductors: A controllable approach by particle irradiation

    Zhou, Shengqiang

    2014-01-01

    Making semiconductors ferromagnetic has been a long dream. One approach is to dope semiconductors with transition metals (TM). TM ions act as local moments and they couple with free carriers to develop collective magnetism. However, there are no fundamental reasons against the possibility of local moment formation from localized sp states. Recently, ferromagnetism was observed in nonmagnetically doped, but defective semiconductors or insulators including ZnO and TiO 2 . This kind of observation challenges the conventional understanding of ferromagnetism. Often the defect-induced ferromagnetism has been observed in samples prepared under non-optimized condition, i.e. by accident or by mistake. Therefore, in this field theory goes much ahead of experimental investigation. To understand the mechanism of the defect-induced ferromagnetism, one needs a better controlled method to create defects in the crystalline materials. As a nonequilibrium and reproducible approach of inducing defects, ion irradiation provides such a possibility. Energetic ions displace atoms from their equilibrium lattice sites, thus creating mainly vacancies, interstitials or antisites. The amount and the distribution of defects can be controlled by the ion fluence and energy. By ion irradiation, we have generated defect-induced ferromagnetism in ZnO, TiO 2 and SiC. In this short review, we also summarize some results by other groups using energetic ions to introduce defects, and thereby magnetism in various materials. Ion irradiation combined with proper characterizations of defects could allow us to clarify the local magnetic moments and the coupling mechanism in defective semiconductors. Otherwise we may have to build a new paradigm to understand the defect-induced ferromagnetism

  1. Ferromagnetism versus slow paramagnetic relaxation in Fe-doped Li3N

    Fix, M.; Jesche, A.; Jantz, S. G.; Bräuninger, S. A.; Klauss, H.-H.; Manna, R. S.; Pietsch, I. M.; Höppe, H. A.; Canfield, P. C.

    2018-02-01

    We report on isothermal magnetization, Mössbauer spectroscopy, and magnetostriction as well as temperature-dependent alternating-current (ac) susceptibility, specific heat, and thermal expansion of single crystalline and polycrystalline Li2(Li1 -xFex) N with x =0 and x ≈0.30 . Magnetic hysteresis emerges at temperatures below T ≈50 K with coercivity fields of up to μ0H =11.6 T at T =2 K and magnetic anisotropy energies of 310 K (27 meV). The ac susceptibility is strongly frequency-dependent (f =10 -10 000 Hz) and reveals an effective energy barrier for spin reversal of Δ E ≈1100 K (90 meV). The relaxation times follow Arrhenius behavior for T >25 K . For T <10 K , however, the relaxation times of τ ≈1010 s are only weakly temperature-dependent, indicating the relevance of a quantum tunneling process instead of thermal excitations. The magnetic entropy amounts to more than 25 J molFe-1 K-1, which significantly exceeds R ln 2 , the value expected for the entropy of a ground-state doublet. Thermal expansion and magnetostriction indicate a weak magnetoelastic coupling in accordance with slow relaxation of the magnetization. The classification of Li2(Li1 -xFex) N as ferromagnet is stressed and contrasted with highly anisotropic and slowly relaxing paramagnetic behavior.

  2. A primary exploration to quasi-two-dimensional rare-earth ferromagnetic particles: holmium-doped MoS2 sheet as room-temperature magnetic semiconductor

    Chen, Xi; Lin, Zheng-Zhe

    2018-05-01

    Recently, two-dimensional materials and nanoparticles with robust ferromagnetism are even of great interest to explore basic physics in nanoscale spintronics. More importantly, room-temperature magnetic semiconducting materials with high Curie temperature is essential for developing next-generation spintronic and quantum computing devices. Here, we develop a theoretical model on the basis of density functional theory calculations and the Ruderman-Kittel-Kasuya-Yoshida theory to predict the thermal stability of two-dimensional magnetic materials. Compared with other rare-earth (dysprosium (Dy) and erbium (Er)) and 3 d (copper (Cu)) impurities, holmium-doped (Ho-doped) single-layer 1H-MoS2 is proposed as promising semiconductor with robust magnetism. The calculations at the level of hybrid HSE06 functional predict a Curie temperature much higher than room temperature. Ho-doped MoS2 sheet possesses fully spin-polarized valence and conduction bands, which is a prerequisite for flexible spintronic applications.

  3. The electronic structure and magnetic interactions in the mixed transition-metal oxide La(Co,Ni)O{sub 3} studied by X-ray absorption spectroscopies

    Huang, Meng-Jie

    2016-11-11

    Transition-metal oxides have attracted a lot of attention because they exhibit a variety of intriguing physical properties. Among the transition-metal oxides, LaCoO{sub 3} is a very special compound which shows different spin states and spin-state transitions. Further, the physical properties can be controlled by changing temperature, replacement of rare-earth element, electron- or hole-doping, or by applying strain. The ground state of LaCoO{sub 3} is a non-magnetic insulator because the lowest energy configuration is t{sub 2g}{sup 6}e{sub g}{sup 0} (S = 0). However, the partial substitution of Co by Ni in La(Co,Ni)O{sub 3} (LCNO) will induce a ferromagnetic behavior. A number of models have been proposed for explaining the nature of the magnetic behavior in the past decades, but it is still a puzzle. In order to understand the origin of the ferromagnetism in La(Co,Ni)O{sub 3}, I have studied the electronic structure and magnetic interaction in this compound in a very direct way: by using X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) along with multiplet simulations. Samples were synthesized by the sol-gel method and structurally and magnetically characterized by XRD and SQUID. XAS clearly indicates a mixed-valence state for both Co and Ni, with both valences increasing monotonously with Ni content, x. While the gradual spin-state transition of Co{sup 3+} from low-spin (LS) to high-spin (HS) is preserved for low x it is suppressed in the high Ni-content samples. Regarding the spin configuration of Ni we find it stabilized in a ''mixed'' spin state, unlike the purely LS state of Ni in LaNiO{sub 3}. XMCD identifies the element-specific contributions to the magnetic moment and interactions. In particular, we find that it must be the coexistence of the HS state in both Co{sup 3+} and Ni{sup 3+} that induces t{sub 2g}-based ferromagnetic interaction via a ''double-exchange-like'' mechanism. Other species

  4. First-Principle Predictions of Electronic Properties and Half-Metallic Ferromagnetism in Vanadium-Doped Rock-Salt SrO

    Berber, Mohamed; Doumi, Bendouma; Mokaddem, Allel; Mogulkoc, Yesim; Sayede, Adlane; Tadjer, Abdelkader

    2018-01-01

    We have used first-principle methods of density functional theory within the full potential linearized augmented plane wave scheme to investigate the electronic and magnetic properties of cubic rock-salt, SrO, doped with vanadium (V) impurity as Sr1- x V x O at various concentrations, x = 0.25, 0.5, and 0.75. We have found that the ferromagnetic state arrangement of Sr1- x V x O is more stable compared to the anti-ferromagnetic state configuration. The electronic structures have a half-metallic (HM) ferromagnetic (F) behavior for Sr0.75V0.25O and Sr0.5V0.5O. This feature results from the metallic and semiconducting natures of majority-spin and minority-spin bands, respectively. The HMF gap decreases with the increasing concentration of vanadium atoms due to the broadening of 3 d (V) levels in the gap, and hence the Sr0.25V0.75O becomes metallic ferromagnetic. The Sr0.75V0.25O revealed a large HM gap with spin polarization of 100%. The Sr1- x V x O compound at low concentrations seems a better candidate to explore the half-metallicity for practical spintronics applications.

  5. Elucidation of the enhanced ferromagnetic origin in Mn-doped ZnO nanocrystals embedded into a SiO2 matrix

    Lee, Sejoon; Lee, Youngmin; Kim, Deukyoung

    2013-01-01

    The origin of the enhanced room temperature ferromagnetism in Mn-doped ZnO (ZnO:Mn) nanocrystals is investigated. ZnO:Mn nanocrystals, which were fabricated by using a laser irradiation method with a 248-nm KrF excimer laser, exhibited two-times increase in the spontaneous magnetization (∼0.4 emu/cm 3 at 300 K) compared to the ZnO:Mn thin film (∼0.2 emu/cm 3 at 300 K). The increased exchange integral of J 1 /k B = 51.6 K in ZnO:Mn nanocrystals, in comparison with the ZnO:Mn thin film (J 1 /k B = 46.9 K), is indicative of the enhanced ferromagnetic exchange interaction. This is attributed to the large number of acceptor defects in the SiO 2 -capped ZnO:Mn nanocrystals. Namely, the holes bound to the acceptor defects form microscopic bound-magnetic-polarons with Mn ions; hence, long-range ferromagnetic coupling is enhanced. The results suggest that ferromagnetism in ZnO-based dilute magnetic semiconductors can be controlled by modulating the density of native point defects, which can be chemically and thermodynamically modified during the material synthesis or preparation.

  6. Elucidation of the enhanced ferromagnetic origin in Mn-doped ZnO nanocrystals embedded into a SiO₂ matrix

    Lee, Sejoon; Lee, Youngmin; Kim, Deukyoung [Dongguk University, Seoul (Korea, Republic of)

    2013-01-01

    The origin of the enhanced room temperature ferromagnetism in Mn-doped ZnO (ZnO:Mn) nanocrystals is investigated. ZnO:Mn nanocrystals, which were fabricated by using a laser irradiation method with a 248-nm KrF excimer laser, exhibited two-times increase in the spontaneous magnetization (∼0.4 emu/cm³ at 300 K) compared to the ZnO:Mn thin film (∼0.2 emu/cm³ at 300 K). The increased exchange integral of J₁/k{sub B} = 51.6 K in ZnO:Mn nanocrystals, in comparison with the ZnO:Mn thin film (J₁/k{sub B} = 46.9 K), is indicative of the enhanced ferromagnetic exchange interaction. This is attributed to the large number of acceptor defects in the SiO₂-capped ZnO:Mn nanocrystals. Namely, the holes bound to the acceptor defects form microscopic bound-magnetic-polarons with Mn ions; hence, long-range ferromagnetic coupling is enhanced. The results suggest that ferromagnetism in ZnO-based dilute magnetic semiconductors can be controlled by modulating the density of native point defects, which can be chemically and thermodynamically modified during the material synthesis or preparation.

  7. Effects of Cr-doping on the photoluminescence and ferromagnetism at room temperature in ZnO nanomaterials prepared by soft chemistry route

    Wang Baiqi; Iqbal, Javed; Shan Xudong; Huang Guowei; Fu Honggang; Yu Ronghai; Yu Dapeng

    2009-01-01

    The pure and Cr-doped ZnO nanomaterials were prepared by soft chemistry route. The crystallinity and morphology of as-prepared ZnO nanomaterials were studied by X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM), which show that Cr-doping could influence crystal and improve the oriented growth of ZnO nanomaterials. The amount of contents and valence state of Cr ions were investigated by energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS), which demonstrate that the Cr ions are uniformly doped about 2 atm% in each nanowire and are in +3 valence state in doped ZnO nanomaterials. The effect of Cr-doping on the photoluminescence (PL) and magnetic properties of as-prepared ZnO nanomaterials were principally investigated at room temperature. The Cr-doping can adjust the energy level of ZnO nanocrystal and increase the amount of defects and oxygen vacancies, which lead to shift in the emission peak position in ultraviolet (UV) region and enhance the PL performance in visible light (VL) region of ZnO nanomaterials. In addition, the presence of Cr dopant in ZnO structures establishes the room-temperature ferromagnetism, which is possibly related to the existence of defects and oxygen vacancies as well as due to exchange interaction between Cr 3d and O 2p spin moments

  8. Modulating the electronic and magnetic properties of bilayer borophene via transition metal atoms intercalation: from metal to half metal and semiconductor.

    Zhang, Xiuyun; Sun, Yi; Ma, Liang; Zhao, Xinli; Yao, Xiaojing

    2018-07-27

    Borophene, a two-dimensional monolayer made of boron atoms, has attracted wide attention due to its appealing properties. Great efforts have been devoted to fine tuning its electronic and magnetic properties for desired applications. Herein, we theoretically investigate the versatile electronic and magnetic properties of bilayer borophene (BLB) intercalated by 3d transition metal (TM) atoms, TM@BLBs (TM = Ti-Fe), using ab initio calculations. Four allotropes of AA-stacking (α 1 -, β-, β 12 - and χ 3 -) BLBs with different intercalation concentrations of TM atoms are considered. Our results show that the TM atoms are strongly bonded to the borophene layers with fairly large binding energies, around 6.31 ∼ 15.44 eV per TM atom. The BLBs with Cr and Mn intercalation have robust ferromagnetism, while for the systems decorated with Fe atoms, fruitful magnetic properties, such as nonmagnetic, ferromagnetic or antiferromagnetic, are identified. In particular, the α 1 - and β-BLBs intercalated by Mn or Fe atom can be transformed into a semiconductor, half metal or graphene-like semimetal. Moreover, some heavily doped TM@BLBs expose high Curie temperatures above room temperature. The attractive properties of TM@BLBs entail an efficient way to modulate the electronic and magnetic properties of borophene sheets for advanced applications.

  9. Enhanced room temperature ferromagnetism in electrodeposited Co-doped ZnO nanostructured thin films by controlling the oxygen vacancy defects

    Simimol, A. [Nanomaterials Research Lab, Surface Engineering Division, CSIR-National Aerospace Laboratories, Post Bag No. 1779, Bangalore 560017 (India); Department of Physics, National Institute of Technology Calicut, Calicut 673601 (India); Anappara, Aji A. [Department of Physics, National Institute of Technology Calicut, Calicut 673601 (India); Greulich-Weber, S. [Department of Physics, Nanophotonic Materials, Faculty of Science, University of Paderborn, 33095 Paderborn (Germany); Chowdhury, Prasanta [Nanomaterials Research Lab, Surface Engineering Division, CSIR-National Aerospace Laboratories, Post Bag No. 1779, Bangalore 560017 (India); Barshilia, Harish C., E-mail: harish@nal.res.in

    2015-06-07

    We report the growth of un-doped and cobalt doped ZnO nanostructures fabricated on FTO coated glass substrates using electrodeposition method. A detailed study on the effects of dopant concentration on morphology, structural, optical, and magnetic properties of the ZnO nanostructures has been carried out systematically by varying the Co concentration (c.{sub Co}) from 0.01 to 1 mM. For c.{sub Co }≤ 0.2 mM, h-wurtzite phase with no secondary phases of Co were present in the ZnO nanostructures. For c.{sub Co} ≤ 0.2 mM, the photoluminescence spectra exhibited a decrease in the intensity of ultraviolet emission as well as band-gap narrowing with an increase in dopant concentration. All the doped samples displayed a broad emission in the visible range and its intensity increased with an increase in Co concentration. It was found that the defect centers such as oxygen vacancies and zinc interstitials were the source of the visible emission. The X-ray photoelectron spectroscopy studies revealed, Co was primarily in the divalent state, replacing the Zn ion inside the tetrahedral crystal site of ZnO without forming any cluster or secondary phases of Co. The un-doped ZnO nanorods exhibited diamagnetic behavior and it remained up to a c.{sub Co} of 0.05 mM, while for c.{sub Co }> 0.05 mM, the ZnO nanostructures exhibited ferromagnetic behavior at room temperature. The coercivity increased to 695 G for 0.2 mM Co-doped sample and then it decreased for c.{sub Co }> 0.2 mM. Our results illustrate that up to a threshold concentration of 0.2 mM, the strong ferromagnetism is due to the oxygen vacancy defects centers, which exist in the Co-doped ZnO nanostructures. The origin of strong ferromagnetism at room temperature in Co-doped ZnO nanostructures is attributed to the s-d exchange interaction between the localized spin moments resulting from the oxygen vacancies and d electrons of Co{sup 2+} ions. Our findings provide a new insight for tuning the

  10. Exciton fission in monolayer transition metal dichalcogenide semiconductors.

    Steinhoff, A; Florian, M; Rösner, M; Schönhoff, G; Wehling, T O; Jahnke, F

    2017-10-27

    When electron-hole pairs are excited in a semiconductor, it is a priori not clear if they form a plasma of unbound fermionic particles or a gas of composite bosons called excitons. Usually, the exciton phase is associated with low temperatures. In atomically thin transition metal dichalcogenide semiconductors, excitons are particularly important even at room temperature due to strong Coulomb interaction and a large exciton density of states. Using state-of-the-art many-body theory, we show that the thermodynamic fission-fusion balance of excitons and electron-hole plasma can be efficiently tuned via the dielectric environment as well as charge carrier doping. We propose the observation of these effects by studying exciton satellites in photoemission and tunneling spectroscopy, which present direct solid-state counterparts of high-energy collider experiments on the induced fission of composite particles.

  11. Understanding lattice defects to influence ferromagnetic order of ZnO nanoparticles by Ni, Cu, Ce ions

    Verma, Kuldeep Chand, E-mail: dkuldeep.physics@gmail.com [Department of Physics, Panjab University, Chandigarh 160014 (India); Kotnala, R.K., E-mail: rkkotnala@gmail.com [CSIR-National Physical Laboratory, New Delhi 110012 (India)

    2017-02-15

    Future spintronics technologies based on diluted magnetic semiconductors (DMS) will rely heavily on a sound understanding of the microscopic origins of ferromagnetism in such materials. It remains unclear, however, whether the ferromagnetism in DMS is intrinsic - a precondition for spintronics - or due to dopant clustering. For this, we include a simultaneous doping from transition metal (Ni, Cu) and rare earth (Ce) ions in ZnO nanoparticles that increase the antiferromagnetic ordering to achieve high-T{sub c} ferromagnetism. Rietveld refinement of XRD patterns indicate that the dopant ions in ZnO had a wurtzite structure and the dopants, Ni{sup 2+}, Cu{sup 2+}, Ce{sup 3+} ions, are highly influenced the lattice constants to induce lattice defects. The Ni, Cu, Ce ions in ZnO have nanoparticles formation than nanorods was observed in pure sample. FTIR involve some organic groups to induce lattice defects and the metal-oxygen bonding of Zn, Ni, Cu, Ce and O atoms to confirm wurtzite structure. Raman analysis evaluates the crystalline quality, structural disorder and defects in ZnO lattice with doping. Photoluminescence spectra have strong near-band-edge emission and visible emission bands responsible for defects due to oxygen vacancies. The energy band gap is calculated using Tauc relation. Room temperature ferromagnetism has been described due to bound magnetic polarons formation with Ni{sup 2+}, Cu{sup 2+}, Ce{sup 3+} ions in ZnO via oxygen vacancies. The zero field and field cooling SQUID measurement confirm the strength of antiferromagnetism in ZnO. The field cooling magnetization is studied by Curie-Weiss law that include antiferromagnetic interactions up to low temperature. The XPS spectra have involve +3/+4 oxidation states of Ce ions to influence the observed ferromagnetism. - Graphical abstract: The lattice defects/vacancies attributed by Ni and Ce ions in the wurtzite ZnO structure are responsible in high T{sub c} -ferromagnetism due to long-range magnetic

  12. Ion-beam-induced ferromagnetism in Mn-doped PrFeO{sub 3} thin films grown on Si (100)

    Sultan, Khalid; Ikram, M.; Mir, Sajad Ahmad; Habib, Zubida; Aarif ul Islam, Shah [National Institute of Technology, Solid State Physics Lab. Department of Physics, Srinagar, J and K (India); Ali, Yasir [Saint Longwal Institute of Engineering and Technology, Sangrur, Punjab (India); Asokan, K. [Inter University Accelerator Centre, Materials Science Division, New Delhi (India)

    2016-01-15

    The present study shows that the ion beam irradiation induces room-temperature ferromagnetic ordering in pulsed laser-deposited Mn-doped PrFeO{sub 3} thin films on Si (100) apart from change in the morphological, structural and electrical properties. Dense electronic excitation produced by high-energy 120 MeV Ag{sup 9+} ion irradiation causes change in surface roughness, crystallinity and strain. It is also evident that these excitations induce the magnetic ordering in this system. The observed modifications are due to the large electronic energy deposited by swift heavy ions irradiation. The appearance of ferromagnetism at 300 K in these samples after irradiation may be attributed to the canting of the antiferromagnetically ordered spins due to the structural distortion. (orig.)

  13. First-row transition metal hydrogenation and hydrosilylation catalysts

    Trovitch, Ryan J.; Mukhopadhyay, Tufan K.; Pal, Raja; Levin, Hagit Ben-Daat; Porter, Tyler M.; Ghosh, Chandrani

    2017-07-18

    Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

  14. Inhibition of Neuroblastoma cancer cells viability by ferromagnetic Mn doped CeO{sub 2} monodisperse nanoparticles mediated through reactive oxygen species

    Abbas, Fazal; Jan, Tariq [Laboratory of Nanoscience and Technology (LNT), Department of Physics, International Islamic University Islamabad (Pakistan); Iqbal, Javed, E-mail: javed.saggu@iiu.edu.pk [Laboratory of Nanoscience and Technology (LNT), Department of Physics, International Islamic University Islamabad (Pakistan); Haider Naqvi, M. Sajjad [Department of Biochemistry, University of Karachi, Karachi (Pakistan); Ahmad, Ishaq [Experimental Physics Labs, National Center for Physics, Islamabad (Pakistan)

    2016-04-15

    Here we report the Mn doping induced effects on structural, Raman, optical, magnetic and anticancer properties of CeO{sub 2} nanoparticles prepared via soft chemical route. Structural and microstructural results infer that the synthesized nanoparticles have single phase cubic fluorite structure of CeO{sub 2} and that Mn doping results in enhancement of the structural defects. Scanning electron microscopy results reveal the formation of monodisperse nanoparticles having average particle size ranging from 30 to 41 nm. The optical absorbance spectroscopy analysis discloses the band gap energy tailoring of CeO{sub 2} nanoparticles via Mn doping. Room temperature ferromagnetism (RTFM) has been found in both as-prepared and Mn doped CeO{sub 2} nanoparticles. This RTFM of the synthesized nanoparticles have been attributed to the Mn ions and surface defects such as oxygen vacancies. Finally, the influence of Mn dopant on the cell viability and reactive oxygen species (ROS) generation levels of CeO{sub 2} nanoparticles in the presence of healthy and cancerous cells have been studied. It has been observed that the differential cytotoxicity of the synthesized nanoparticles is strongly correlated with level of ROS generation. - Highlights: • Mn doped CeO{sub 2} nanoparticles with cubic fluorite structure were synthesized. • Mn dopant significantly tailored the band gap of CeO{sub 2} nanoparticles. • The synthesized nanoparticles exhibited room temperature ferromagnetic behavior. • The cytotoxicity of these nanoparticles was reported for the first time. • The synthesized nanoparticles exhibited differential cytotoxicity.

  15. (Electronic structure and reactivities of transition metal clusters)

    1992-01-01

    The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

  16. The phosphorus and the transition metals chemistry

    Mathey, F.

    1988-01-01

    The 1988 progress report, concerning the Polytechnic School unit (France), which studies the phosphorus and the transition metals chemistry, is presented. The laboratory activities are related to the following topics: the phosporus heterocyclic chemistry, the phosphorus-carbon double bonds chemistry, the new transition metals phosphorus compounds, the phosphonates and their uses. Some practical applications of homogeneous catalysis and new materials synthesis are investigated. The main results obtained are: the discovery of the tetra-phosphafulvalenes, the utilization of a new synthesis method of the phosphorus-carbon double bonds and the stabilization of the α-phosphonyled carbanions by the lithium diisopropylamidourea. The papers, the congress communications and the thesis are also shown [fr

  17. Spin-Orbitronics at Transition Metal Interfaces

    Manchon, Aurelien

    2017-11-09

    The presence of large spin–orbit interaction at transition metal interfaces enables the emergence of a variety of fascinating phenomena that have been at the forefront of spintronics research in the past 10 years. The objective of the present chapter is to offer a review of these various effects from a theoretical perspective, with a particular focus on spin transport, chiral magnetism, and their interplay. After a brief description of the orbital hybridization scheme at transition metal interfaces, we address the impact of spin–orbit coupling on the interfacial magnetic configuration, through the celebrated Dzyaloshinskii–Moriya interaction. We then discuss the physics of spin transport and subsequent torques occurring at these interfaces. We particularly address the spin Hall, spin swapping, and inverse spin-galvanic effects. Finally, the interplay between flowing charges and chiral magnetic textures and their induced dynamics are presented. We conclude this chapter by proposing some perspectives on promising research directions.

  18. Lattice Location of Transition Metals in Semiconductors

    2002-01-01

    %IS366 %title\\\\ \\\\Transition metals (TMs) in semiconductors have been the subject of considerable research for nearly 40 years. This is due both to their role as important model impurities for deep centers in semiconductors, and to their technological impact as widespread contaminants in Si processing, where the miniaturization of devices requires to keep their sheet concentration below 10$^{10}$ cm$^{-2}$. As a consequence of the low TM solubility, conventional ion beam methods for direct lattice location have failed completely in identifying the lattice sites of isolated transition metals. Although electron paramagnetic resonance (EPR) has yielded valuable information on a variety of TM centers, it has been unable to detect certain defects considered by theory, e.g., isolated interstitial or substitutional Cu in Si. The proposed identity of other EPR centers such as substitutional Fe in Si, still needs confirmation by additional experimental methods. As a consequence, the knowledge on the structural propert...

  19. Spin-Orbitronics at Transition Metal Interfaces

    Manchon, Aurelien; Belabbes, Abderrezak

    2017-01-01

    The presence of large spin–orbit interaction at transition metal interfaces enables the emergence of a variety of fascinating phenomena that have been at the forefront of spintronics research in the past 10 years. The objective of the present chapter is to offer a review of these various effects from a theoretical perspective, with a particular focus on spin transport, chiral magnetism, and their interplay. After a brief description of the orbital hybridization scheme at transition metal interfaces, we address the impact of spin–orbit coupling on the interfacial magnetic configuration, through the celebrated Dzyaloshinskii–Moriya interaction. We then discuss the physics of spin transport and subsequent torques occurring at these interfaces. We particularly address the spin Hall, spin swapping, and inverse spin-galvanic effects. Finally, the interplay between flowing charges and chiral magnetic textures and their induced dynamics are presented. We conclude this chapter by proposing some perspectives on promising research directions.

  20. Rational Design of Two-Dimensional Metallic and Semiconducting Spintronic Materials Based on Ordered Double-Transition-Metal MXenes

    Dong, Liang

    2016-12-30

    Two-dimensional (2D) materials that display robust ferromagnetism have been pursued intensively for nanoscale spintronic applications, but suitable candidates have not been identified. Here we present theoretical predictions on the design of ordered double-transition-metal MXene structures to achieve such a goal. On the basis of the analysis of electron filling in transition-metal cations and first-principles simulations, we demonstrate robust ferromagnetism in Ti2MnC2Tx monolayers regardless of the surface terminations (T = O, OH, and F), as well as in Hf2MnC2O2 and Hf2VC2O2 monolayers. The high magnetic moments (3–4 μB/unit cell) and high Curie temperatures (495–1133 K) of these MXenes are superior to those of existing 2D ferromagnetic materials. Furthermore, semimetal-to-semiconductor and ferromagnetic-to-antiferromagnetic phase transitions are predicted to occur in these materials in the presence of small or moderate tensile in-plane strains (0–3%), which can be externally applied mechanically or internally induced by the choice of transition metals.

  1. Mesoporous Transition Metal Oxides for Supercapacitors

    Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

    2015-01-01

    Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are result...

  2. Mesoporous Transition Metal Oxides for Supercapacitors.

    Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

    2015-10-14

    Recently, transition metal oxides, such as ruthenium oxide (RuO₂), manganese dioxide (MnO₂), nickel oxides (NiO) and cobalt oxide (Co₃O₄), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO₂, MnO₂, NiO, Co₃O₄ and nickel cobaltite (NiCo₂O₄), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

  3. Mesoporous Transition Metal Oxides for Supercapacitors

    Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

    2015-01-01

    Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors. PMID:28347088

  4. Mesoporous Transition Metal Oxides for Supercapacitors

    Yan Wang

    2015-10-01

    Full Text Available Recently, transition metal oxides, such as ruthenium oxide (RuO2, manganese dioxide (MnO2, nickel oxides (NiO and cobalt oxide (Co3O4, have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4, and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

  5. Effect of oxygen vacancy induced by pulsed magnetic field on the room-temperature ferromagnetic Ni-doped ZnO synthesized by hydrothermal method

    Zhong, Min [Shanghai University, Laboratory for Microstructures, School of Materials Science and Engineering, 149 Yanchang Road, 200072 Shanghai (China); Li, Ying, E-mail: liying62@shu.edu.cn [Shanghai University, Laboratory for Microstructures, School of Materials Science and Engineering, 149 Yanchang Road, 200072 Shanghai (China); Tariq, Muhammad; Hu, Yemin; Li, Wenxian; Zhu, Mingyuan; Jin, Hongmin [Shanghai University, Laboratory for Microstructures, School of Materials Science and Engineering, 149 Yanchang Road, 200072 Shanghai (China); Li, Yibing [School of Chemistry, The University of New South Wales, Sydney, NSW, 2052 (Australia)

    2016-08-05

    Room temperature ferromagnetic 2% Ni doped ZnO rods were synthesized by high pulsed magnetic field-assisted hydrothermal method. A detailed study on the effect of high pulsed magnetic field on morphology, structural and magnetic properties of the ZnO rods has been carried out systematically by varying the intensity of field from 0 to 4 T. X-ray diffraction, Energy-dispersive spectroscopy measurements, and Raman spectra analysis suggest that all the samples have hexagonal wurtzite structure without detectable impurity. Field emission scanning electron microscopy images indicate that the particle size of samples decrease with increasing intensity of field. High resolution transmission electron microscopy observation ensures that the Ni ions addition do not change the wurtzite host matrix. X-ray photoelectron spectroscopy confirms the incorporation of Ni elements as divalent state and the dominant presence of oxygen vacancies in samples fabricated under 4 T pulsed magnetic field. Hysteresis loops demonstrate that the saturation magnetization increased regularly with the mounting magnetic field. On the framework of bound magnetic polaron model, the rising content of oxygen vacancies, as donor defect, lead to the stronger ferromagnetism in samples with pulsed magnetic field. Our findings provide a new insight for tuning the defect density by precisely controlling the intensity of field in order to get the desired magnetic behavior at room temperature. - Graphical abstract: This figure shows the magnetization versus magnetic field curves for 2%Ni doped ZnO as prepared with 0, 1, 2, 3 and 4 T pulsed magnetic field at 290 K. For 0 T sample, no ferromagnetic response is observed. But all the samples synthesized with field were well-defined hysteresis loops. The saturation magnetization estimated from the hysteresis loop come out to be ∼0.0024, 0.0023, 0.0036 and 0.0061 emu/g for 1 T, 2 T, 3 T and 4 T samples, respectively. As shown in the curves, the room

  6. Effect of Co and O defects on ferromagnetism in Co-doped ZnO: An X-ray absorption spectroscopic investigation

    Singhal, Rishi K.; Jakhar, Narendra; Samariya, A.; Dolia, S. N.; Kumar, Sudhish

    2018-02-01

    Understanding of origin of ferromagnetism in dilute magnetic oxides (DMO's) has become one of the most challenging research problems in condensed matter physics. Here we are reporting a detailed study of magnetic properties and electronic structure of two 5% Co-doped ZnO samples (the as-prepared sample Zn0.95Co0.05O and the hydrogenated sample Zn0.95Co0.05O:H). The as-prepared sample is found to be paramagnetic while through hydrogenation, we observed inducement of remarkable ferromagnetism in it. The H-mediated magnetic transition is accompanied by electronic structure modifications with no structural deviations. To get in-depth information into electronic structure correlations of the observed ferromagnetism, we have investigated their electronic properties in detail. For this purpose, we have employed the site-selective and element-sensitive X-ray-absorption spectroscopy (XAS) in the vicinity of the Cobalt L2,3 edge, the oxygen K edge, and the Zinc L3 edge using synchrotron radiation. The Co L2,3 edge spectra clearly show that Co dopants reside at the Zn sites for both these samples and that they are tetrahedrally coordinated with the ligand O atoms. Very minor changes are observed in the Zn L3 edge spectra. However, the O 1s edge spectra display dominant additional components in the ferromagnetic hydrogenated sample Zn0.95Co0.05O:H, not observed in the as-prepared non-magnetic sample Zn0.95Co0.05O. We conclude that the observed spectral features can be attributed to the presence of O vacancies and the hybridization of Co 3d states with O 2p vacancy states. These two factors together are likely to play important role in inducement of ferromagnetic ordering in this Co-doped ZnO system. However, which of these two weighs more in this mechanism, cannot be pinpointed and more studies are required in this regard.

  7. Half-metallic ferromagnetism in (Z B, Al, Ga, and In) Heusler alloys ...

    K H SADEGHI

    2018-01-03

    11], and zincblende (ZB) transition-metal pnictides and chalcogenides [12–17]. Among HM ferromagnets, Heusler alloys are attractive because of their technical applications (in spin-injection devices [18], spin-filters [19], ...

  8. Solubility of hydrogen in transition metals

    Lee, H.M.

    1976-01-01

    Correlations exist between the heat of solution of hydrogen and the difference in energy between the lowest lying energy levels of the trivalent d/sup n-1/s electronic configuration and the divalent d/sup n-2/s 2 (or the tetravalent d/sup n/) configuration of the neutral gaseous atoms. The trends observed in the transition metal series are discussed in relation to the number of valence electrons per atom in the transition elements in their metallic and neutral states

  9. Microscopic effects of Dy doping in the topological insulator Bi2Te3

    Duffy, L. B.; Steinke, N.-J.; Krieger, J. A.; Figueroa, A. I.; Kummer, K.; Lancaster, T.; Giblin, S. R.; Pratt, F. L.; Blundell, S. J.; Prokscha, T.; Suter, A.; Langridge, S.; Strocov, V. N.; Salman, Z.; van der Laan, G.; Hesjedal, T.

    2018-05-01

    Magnetic doping with transition metal ions is the most widely used approach to break time-reversal symmetry in a topological insulator (TI)—a prerequisite for unlocking the TI's exotic potential. Recently, we reported the doping of Bi2Te3 thin films with rare-earth ions, which, owing to their large magnetic moments, promise commensurately large magnetic gap openings in the topological surface states. However, only when doping with Dy has a sizable gap been observed in angle-resolved photoemission spectroscopy, which persists up to room temperature. Although disorder alone could be ruled out as a cause of the topological phase transition, a fundamental understanding of the magnetic and electronic properties of Dy-doped Bi2Te3 remained elusive. Here, we present an x-ray magnetic circular dichroism, polarized neutron reflectometry, muon-spin rotation, and resonant photoemission study of the microscopic magnetic and electronic properties. We find that the films are not simply paramagnetic but that instead the observed behavior can be well explained by the assumption of slowly fluctuating, inhomogeneous, magnetic patches with increasing volume fraction as the temperature decreases. At liquid helium temperatures, a large effective magnetization can be easily introduced by the application of moderate magnetic fields, implying that this material is very suitable for proximity coupling to an underlying ferromagnetic insulator or in a heterostructure with transition-metal-doped layers. However, the introduction of some charge carriers by the Dy dopants cannot be excluded at least in these highly doped samples. Nevertheless, we find that the magnetic order is not mediated via the conduction channel in these samples and therefore magnetic order and carrier concentration are expected to be independently controllable. This is not generally the case for transition-metal-doped topological insulators, and Dy doping should thus allow for improved TI quantum devices.

  10. The atomic structure of transition metal clusters

    Riley, S.J.

    1995-01-01

    Chemical reactions are used to probe the atomic (geometrical) structure of isolated clusters of transition metal atoms. The number of adsorbate molecules that saturate a cluster, and/or the binding energy of molecules to cluster surfaces, are determined as a function of cluster size. Systematics in these properties often make it possible to propose geometrical structures consistent with the experimental observations. We will describe how studies of the reactions of cobalt and nickel clusters with ammonia, water, and nitrogen provide important and otherwise unavailable structural information. Specifically, small (less than 20 atoms) clusters of cobalt and nickel atoms adopt entirely different structures, the former having packing characteristic of the bulk and the latter having pentagonal symmetry. These observations provide important input for model potentials that attempt to describe the local properties of transition metals. In particular, they point out the importance of a proper treatment of d-orbital binding in these systems, since cobalt and nickel differ so little in their d-orbital occupancy

  11. Janus monolayers of transition metal dichalcogenides

    Lu, Ang-Yu

    2017-05-15

    Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

  12. Edge Delamination of Monolayer Transition Metal Dichalcogenides.

    Ly, Thuc Hue; Yun, Seok Joon; Thi, Quoc Huy; Zhao, Jiong

    2017-07-25

    Delamination of thin films from the supportive substrates is a critical issue within the thin film industry. The emergent two-dimensional, atomic layered materials, including transition metal dichalcogenides, are highly flexible; thus buckles and wrinkles can be easily generated and play vital roles in the corresponding physical properties. Here we introduce one kind of patterned buckling behavior caused by the delamination from a substrate initiated at the edges of the chemical vapor deposition synthesized monolayer transition metal dichalcogenides, led by thermal expansion mismatch. The atomic force microscopy and optical characterizations clearly showed the puckered structures associated with the strain, whereas the transmission electron microscopy revealed the special sawtooth-shaped edges, which break the geometrical symmetry for the buckling behavior of hexagonal samples. The condition of the edge delamination is in accordance with the fracture behavior of thin film interfaces. This edge delamination and buckling process is universal for most ultrathin two-dimensional materials, which requires more attention in various future applications.

  13. Magnetic and electronic properties of La3 M O7 and possible polaron formation in hole-doped La3 M O7 (M   =  Ru and Os)

    Gao, Bin; Weng, Yakui; Zhang, Jun-Jie; Zhang, Huimin; Zhang, Yang; Dong, Shuai

    2017-01-01

    Oxides with 4 d /5 d transition metal ions are physically interesting for their particular crystalline structures as well as the spin–orbit coupled electronic structures. Recent experiments revealed a series of 4 d /5 d transition metal oxides R 3 M O 7 (R : rare earth; M : 4 d /5 d transition metal) with unique quasi-one-dimensional M chains. Here first-principles calculations have been performed to study the electronic structures of La 3 OsO 7 and La 3 RuO 7 . Our study confirm both of them to be Mott insulating antiferromagnets with identical magnetic order. The reduced magnetic moments, which are much smaller than the expected value for ideal high-spin state (3 t 2g orbitals occupied), are attributed to the strong p   −   d hybridization with oxygen ions, instead of the spin–orbit coupling. The Ca-doping to La 3 OsO 7 and La 3 RuO 7 can not only modulate the nominal carrier density but also affect the orbital order as well as the local distortions. The Coulombic attraction and particular orbital order would prefer to form polarons, which might explain the puzzling insulating behavior of doped 5 d transition metal oxides. In addition, our calculations predict that the Ca-doping can trigger ferromagnetism in La 3 RuO 7 but not in La 3 OsO 7 . (paper)

  14. Anomalous electron doping independent two-dimensional superconductivity

    Zhou, Wei; Xing, Xiangzhuo; Zhao, Haijun; Feng, Jiajia; Pan, Yongqiang; Zhou, Nan; Zhang, Yufeng; Qian, Bin; Shi, Zhixiang

    2017-07-01

    Transition metal (Co and Ni) co-doping effects are investigated on an underdoped Ca0.94La0.06Fe2As2 compound. It is discovered that electron doping from substituting Fe with transition metal (TM = Co, Ni) can trigger high-{T}{{c}} superconductivity around 35 K, which emerges abruptly before the total suppression of the innate spin-density-wave/anti-ferromagnetism (SDW/AFM) state. Remarkably, the critical temperature for the high-{T}{{c}} superconductivity remains constant against a wide range of TM doping levels. And the net electron doping density dependence of the superconducting {T}{{c}} based on the rigid band model can be nicely scaled into a single curve for Co and Ni substitutions, in stark contrast to the case of Ba(Fe1-x TM x )2As2. This carrier density independent superconductivity and the unusual scaling behavior are presumably resulted from the interface superconductivity based on the similarity with the interface superconductivity in a La2-x Sr x CuO4-La2CuO4 bilayer. Evidence of the two-dimensional character of the superfluid by angle-resolved magneto-resistance measurements can further strengthen the interface nature of the high-{T}{{c}} superconductivity.

  15. Magnetic and luminescent properties of vanadium-doped ZnSe crystals

    Radevici, Ivan, E-mail: ivarad@utu.fi [Wihuri Physical Laboratory, Department of Physics and Astronomy, University of Turku, FI-20014 Turku (Finland); Faculty of Physics and Engineering, Moldova State University, 60 A. Mateevici str., MD-2009 Chisinau (Moldova, Republic of); Nedeoglo, Natalia; Sushkevich, Konstantin [Faculty of Physics and Engineering, Moldova State University, 60 A. Mateevici str., MD-2009 Chisinau (Moldova, Republic of); Huhtinen, Hannu [Wihuri Physical Laboratory, Department of Physics and Astronomy, University of Turku, FI-20014 Turku (Finland); Nedeoglo, Dmitrii [Faculty of Physics and Engineering, Moldova State University, 60 A. Mateevici str., MD-2009 Chisinau (Moldova, Republic of); Paturi, Petriina [Wihuri Physical Laboratory, Department of Physics and Astronomy, University of Turku, FI-20014 Turku (Finland)

    2016-12-15

    Magnetic and photoluminescence properties of vanadium-doped ZnSe crystals with impurity concentrations varied by changing the V amount in the source material from 0.03 to 0.30 at% are studied in 5–300 K temperature range. Investigation of magnetic properties shows that the studied concentrations of vanadium impurity that should not disturb crystal lattice are insignificant for observing ferromagnetic behaviour even at low temperatures. The contribution of V impurity to edge emission and its influence on infra-red emission are discussed. Similarities of magnetic and luminescent properties induced by vanadium and other transition metal impurities are discussed.

  16. Using Dopants to Tune Oxygen Vacancy Formation in Transition Metal Oxide Resistive Memory.

    Jiang, Hao; Stewart, Derek A

    2017-05-17

    Introducing dopants is an important way to tailor and improve electronic properties of transition metal oxides used as high-k dielectric thin films and resistance switching layers in leading memory technologies, such as dynamic and resistive random access memory (ReRAM). Ta 2 O 5 has recently received increasing interest because Ta 2 O 5 -based ReRAM demonstrates high switching speed, long endurance, and low operating voltage. However, advances in optimizing device characteristics with dopants have been hindered by limited and contradictory experiments in this field. We report on a systematic study on how various metal dopants affect oxygen vacancy formation in crystalline and amorphous Ta 2 O 5 from first principles. We find that isoelectronic dopants and weak n-type dopants have little impact on neutral vacancy formation energy and that p-type dopants can lower the formation energy significantly by introducing holes into the system. In contrast, n-type dopants have a deleterious effect and actually increase the formation energy for charged oxygen vacancies. Given the similar doping trend reported for other binary transition metal oxides, this doping trend should be universally valid for typical binary transition metal oxides. Based on this guideline, we propose that p-type dopants (Al, Hf, Zr, and Ti) can lower the forming/set voltage and improve retention properties of Ta 2 O 5 ReRAM.

  17. Synthesis and structural, magnetic, thermal, and transport properties of several transition metal oxides and aresnides

    Das, Supriyo [Iowa State Univ., Ames, IA (United States)

    2010-01-01

    Oxide compounds containing the transition metal vanadium (V) have attracted a lot of attention in the field of condensed matter physics owing to their exhibition of interesting properties including metal-insulator transitons, structural transitions, ferromagnetic and an- tiferromagnetic orderings, and heavy fermion behavior. Binary vanadium oxides VnO2n-1 where 2 ≤ n ≤ 9 have triclinic structures and exhibit metal-insulator and antiferromagnetic transitions.[1–6] The only exception is V7O13 which remains metallic down to 4 K.[7] The ternary vanadium oxide LiV2O4 has the normal spinel structure, is metallic, does not un- dergo magnetic ordering and exhibits heavy fermion behavior below 10 K.[8] CaV2O4 has an orthorhombic structure[9, 10] with the vanadium spins forming zigzag chains and has been suggested to be a model system to study the gapless chiral phase.[11, 12] These provide great motivation for further investigation of some known vanadium compounds as well as to ex- plore new vanadium compounds in search of new physics. This thesis consists, in part, of experimental studies involving sample preparation and magnetic, transport, thermal, and x- ray measurements on some strongly correlated eletron systems containing the transition metal vanadium. The compounds studied are LiV2O4, YV4O8, and YbV4O8. The recent discovery of superconductivity in RFeAsO1-xFx (R = La, Ce, Pr, Gd, Tb, Dy, Sm, and Nd), and AFe2As2 (A = Ba, Sr, Ca, and Eu) doped with K, Na, or Cs at the A site with relatively high Tc has sparked tremendous activities in the condensed matter physics community and a renewed interest in the area of superconductivity as occurred following the discovery of the layered cuprate high Tc superconductors in 1986. To discover more supercon- ductors

  18. Neutron irradiation damage in transition metal carbides

    Matsui, Hisayuki; Nesaki, Kouji; Kiritani, Michio

    1991-01-01

    Effects of neutron irradiation on the physical properties of light transition metal carbides, TiC x , VC x and NbC x , were examined, emphasizing the characterization of irradiation induced defects in the nonstoichiometric composition. TiC x irradiated with 14 MeV (fusion) neutrons showed higher damage rates with increasing C/Ti (x) ratio. A brief discussion is made on 'cascade damage' in TiC x irradiated with fusion neutrons. Two other carbides (VC x and NbC x ) were irradiated with fission reactor neutrons. The irradiation effects on VC x were not so simple, because of the complex irradiation behavior of 'ordered' phases. For instance, complete disordering was revealed in an ordered phase, 'V 8 C 7 ', after an irradiation dose of 10 25 n/m 2 . (orig.)

  19. Defect-Tolerant Monolayer Transition Metal Dichalcogenides

    Pandey, Mohnish; Rasmussen, Filip Anselm; Kuhar, Korina

    2016-01-01

    Localized electronic states formed inside the band gap of a semiconductor due to crystal defects can be detrimental to the material's optoelectronic properties. Semiconductors with a lower tendency to form defect induced deep gap states are termed defect-tolerant. Here we provide a systematic first...... the gap. These ideas are made quantitative by introducing a descriptor that measures the degree of similarity of the conduction and valence band manifolds. Finally, the study is generalized to nonpolar nanoribbons of the TMDs where we find that only the defect sensitive materials form edge states within......-principles investigation of defect tolerance in 29 monolayer transition metal dichalcogenides (TMDs) of interest for nanoscale optoelectronics. We find that the TMDs based on group VI and X metals form deep gap states upon creation of a chalcogen (S, Se, Te) vacancy, while the TMDs based on group IV metals form only...

  20. Versatile two-dimensional transition metal dichalcogenides

    Canulescu, Stela; Affannoukoué, Kévin; Döbeli, Max

    ), a strategy for the fabrication of 2D heterostructures must be developed. Here we demonstrate a novel approach for the bottom-up synthesis of TMDC monolayers, namely Pulsed Laser Deposition (PLD) combined with a sulfur evaporation beam. PLD relies on the use of a pulsed laser (ns pulse duration) to induce...... material transfer from a solid source (such as a sintered target of MoS2) to a substrate (such as Si or sapphire). The deposition rate in PLD is typically much less than a monolayer per pulse, meaning that the number of MLs can be controlled by a careful selection of the number of laser pulses......Two-dimensional transition metal dichalcogenides (2D-TMDCs), such as MoS2, have emerged as a new class of semiconducting materials with distinct optical and electrical properties. The availability of 2D-TMDCs with distinct band gaps allows for unlimited combinations of TMDC monolayers (MLs...

  1. Electronic structure of hcp transition metals

    Jepsen, O.; Andersen, O. Krogh; Mackintosh, A. R.

    1975-01-01

    Using the linear muffin-tin-orbital method described in the previous paper, we have calculated the electronic structures of the hcp transition metals, Zr, Hf, Ru, and Os. We show how the band structures of these metals may be synthesized from the sp and d bands, and illustrate the effects...... of hybridization, relativistic band shifts, and spin-orbit coupling by the example of Os. By making use of parameters derived from the muffin-tin potential, we discuss trends in the positions and widths of the energy bands, especially the d bands, as a function of the location in the periodic table. The densities...... of states of the four metals are presented, and the calculated heat capacities compared with experiment. The Fermi surfaces of both Ru and Os are found to be in excellent quantitative agreement with de Haas-van Alphen measurements, indicating that the calculated d-band position is misplaced by less than 10...

  2. Elastic properties of some transition metal arsenides

    Nayak, Vikas; Verma, U. P.; Bisht, P. S.

    2018-05-01

    The elastic properties of transition metal arsenides (TMAs) have been studied by employing Wien2K package based on density functional theory in the zinc blende (ZB) and rock salt (RS) phase treating valance electron scalar relativistically. Further, we have also treated them non-relativistically to find out the relativistic effect. We have calculated the elastic properties by computing the volume conservative stress tensor for small strains, using the method developed by Charpin. The obtained results are discussed in paper. From the obtained results, it is clear that the values of C11 > C12 and C44 for all the compounds. The values of shear moduli of these compounds are also calculated. The internal parameter for these compounds shows that ZB structures of these compounds have high resistance against bond order. We find that the estimated elastic constants are in good agreement with the available data.

  3. On monosubstituted cyanurate complexes of transition metals

    Sejfer, G.B.; Tarasova, Z.A.

    1995-01-01

    Complex monosubstituted cyanurates of transition metals K 2 [Eh(H 2 C 3 N 3 O 3 ) 4 ]x4H 2 ) where Eh = Mn, Co, Ni, Cu, Zn, Cd are synthesized and investigated by means of IR - spectroscopy and thermal analysis methods. It is shown that only thermal decomposition of a manganese complex leads to the production of this metal oxide. All other derivatives decompose with the production of a free metal, because decomposition of these substances in argon atmosphere occurs through an intermediate production of their nitrides. An assumption is made that nitroduction of yttrium or rare earth element salts (instead of transition or alkali metal derivatives) as accelerating additions will facilitate increase of polyisocyanurate resin thermal stability. 25 refs.; 2 figs.; 3 tabs

  4. Localized versus collective behaviour of d-electrons in transition metal oxide systems of perovskite systems

    Rao, C N.R. [Indian Inst. of Tech., Kanpur

    1974-12-01

    The behavior of d-electrons in perovskites of the type LnZO/sub 3/ (Z = trivalent transition metal ion and Ln = rare earth or yttrium) depends on the spin configuration of the transition metal ion. LaTiO/sub 3/ and LaNiO/sub 3/ with low-spin transition metal ions (S = 1/2) are metallic while LaCrO/sub 3/, LnMnO/sub 3/ and LnFeO/sub 3/ with high-spin ions are poor semiconductors exhibiting localized behavior of d-electrons. In rare earth cobaltites, the cobalt ions are present mainly in the diamagnetic low-spin Co /sup III/ state at low temperatures. The Co/sup III/ ions transform to high-spin Co/sup 3 +/ ions with increase in temperature. At higher temperatures, there is electron-transfer from Co/sup 3 +/ to Co/sup III/ions producing intermetallic states. Spin-state transitions are seen in these cobaltites in the range 150-870/sup 0/K. At high temperatures, the cobaltites show evidence for localized-itinerant electron transitions. In La/sub 1-x/ Sr/sub x/CoO/sub 3/ there is onset of ferromagnetism at x > 0.125, at which point there is a structural dicontinuity and electrons become itinerant. The composition with x = 0.5 is metallic and T/sub c/ = 230/sup 0/K. The ferromagnetic component in La/sub 1-x/Sr/sub x/ CoO/sub 3/ increases with x in the range 0.125-0.50. Catalytic properties of rare earth cobaltites appear to be related to the spin state equilibria. (auth)

  5. Transition-metal dichalcogenides heterostructure saturable absorbers for ultrafast photonics.

    Chen, Hao; Yin, Jinde; Yang, Jingwei; Zhang, Xuejun; Liu, Mengli; Jiang, Zike; Wang, Jinzhang; Sun, Zhipei; Guo, Tuan; Liu, Wenjun; Yan, Peiguang

    2017-11-01

    In this Letter, high-quality WS 2 film and MoS 2 film were vertically stacked on the tip of a single-mode fiber in turns to form heterostructure (WS 2 -MoS 2 -WS 2 )-based saturable absorbers with all-fiber integrated features. Their nonlinear saturable absorption properties were remarkable, such as a large modulation depth (∼16.99%) and a small saturable intensity (6.23  MW·cm -2 ). Stable pulses at 1.55 μm with duration as short as 296 fs and average power as high as 25 mW were obtained in an erbium-doped fiber laser system. The results demonstrate that the proposed heterostructures own remarkable nonlinear optical properties and offer a platform for adjusting nonlinear optical properties by stacking different transition-metal dichalcogenides or modifying the thickness of each layer, paving the way for engineering functional ultrafast photonics devices with desirable properties.

  6. Polar-antipolar transition and weak ferromagnetism in Mn-doped Bi0.86La0.14FeO3

    Khomchenko, V. A.; Karpinsky, D. V.; Troyanchuk, I. O.; Sikolenko, V. V.; Többens, D. M.; Ivanov, M. S.; Silibin, M. V.; Rai, R.; Paixão, J. A.

    2018-04-01

    Having been considered as a prime example of a room-temperature magnetoelectric multiferroic, BiFeO3 continues to attract much interest. Since functional properties of this material can be effectively influenced by chemical, electrical, magnetic, mechanical and thermal stimuli, it can serve as a model for the investigation of cross-coupling phenomena in solids. Special attention is currently paid to the study of chemical pressure-driven magneto-structural transformations. In this paper, we report on the effect of the Mn doping on the crystal structure and magnetic behavior of the Bi1‑x La x FeO3 multiferroics near their polar-antipolar (antiferromagnetic-weak ferromagnetic) phase boundary. Synchrotron x-ray and neutron powder diffraction measurements of the Bi0.86La0.14Fe1‑x Mn x O3 (x  =  0.05, 0.1, 0.15) compounds have been performed. The diffraction data suggest that the Mn substitution results in the suppression of the ferroelectric polarization and gives rise to the appearance of the antiferroelectric (generally, PbZrO3-related) phase characteristic of the phase diagrams of the Bi1‑x RE x FeO3 (RE  =  rare-earth) systems. Depending on the Mn concentration (determining phase composition of the Bi0.86La0.14Fe1‑x Mn x O3 samples at room temperature), either complete or partial revival of the polar phase can be observed with increasing temperature. Magnetic measurements of the samples indicate that the Mn doping affects the stability of the cycloidal antiferromagnetic order specific to the polar phase, thus resulting in the formation of a ferroelectric and weak ferromagnetic state.

  7. Ferromagnetism in 4H-GaN polytype doped by non-magnetic light elements Li, Be, B, C, O, F, Ne, Na, and Mg: Ab-initio study

    Torrichi, M.; Ferhat, M.; Bouhafs, B.

    2016-01-01

    Using density-functional theory within the generalized-gradient approximation, we explore the magnetic behavior induced by nonmagnetic impurity X atoms, such as Li, Be, B, C, O, F, Ne, Na, and Mg on cation site in 4H-GaN polytype. The results reveal that Ne doped 4H-GaN has the highest magnetic moment of 3µ B , whereas Mg doped 4H-GaN has the lowest magnetic moment of 0.75µ B . Among the systems studied 4H-GaN doped Ne has been found to be half-metallic, whereas 4H-GaN doped F and Na are found to be nearly half-metallic. The partial density of states evidence that magnetism is achieved through a p-p like coupling between the impurity and the host 2p states. Furthermore, we inspect whether there exists a relationship between the spin-polarization and the local structure around the doping X atoms. It is found that for all the compounds studied, the total magnetic moment increases with increasing the X–N bond lengths. Interestingly, 4H-GaN:Be becomes ferromagnetic with increasing the Be–N bond length, whereas 4H-GaN:Na and 4H-GaN:F become half-metallic with increasing Na–N and F–N bond lengths. - Highlights: • The partial densities of states of 4H-GaN polytype doped light nonmagnetic elements have been investigated. • We found that 4H-GaN:Ne is half metallic. • We found that N atoms induced strong local magnetic. • We found that doping with half-filled X-s impurity states promotes ferromagnetism. • We found that doping with full-filled X-s impurity annihilates ferromagnetism.

  8. Theoretical studies of transition metal complexes with nitriles and isocyanides

    Kuznetsov, Maksim L

    2002-01-01

    Theoretical studies of transition metal complexes with nitriles and isocyanides are reviewed. The electronic structures and the nature of coordination bonds in these complexes are discussed. The correlation between the electronic structures of transition metal complexes with nitriles and isocyanides and their structural properties, spectroscopic characteristics, and reactivities are considered. The bibliography includes 121 references.

  9. Textural and morphological studies of transition metal doped SBA ...

    J. Chem. Sci. Vol. 127, No. 5, May 2015, pp. 909–919. c Indian Academy of Sciences. ... The difference in hydrolysis rates of metal and silica precursors have led to textural ... tures of mesoporous SBA-15.13 General shape-selective.

  10. Magnetism in 3d transition metal doped SnO

    Albar, Arwa; Schwingenschlö gl, Udo

    2016-01-01

    of the dopant atoms is found to be complex because of interplay between strong structural relaxation, spin-lattice coupling, and crystal field splitting. The interaction between dopant atoms is analyzed as a function of their separation, showing that clustering

  11. Mn-doped Ga(As,P) and (Al,Ga)As ferromagnetic semiconductors: electronic structure calculations

    Mašek, Jan; Kudrnovský, Josef; Máca, František; Sinova, J.; MacDonald, A. H.; Champion, R.P.; Gallagher, B. L.; Jungwirth, Tomáš

    2007-01-01

    Roč. 75, č. 4 (2007), 045202/1-045202/6 ISSN 1098-0121 R&D Projects: GA ČR GA202/05/0575; GA ČR GA202/04/0583 Institutional research plan: CEZ:AV0Z10100521; CEZ:AV0Z10100520 Keywords : ferromagnetic semiconductors * electronic structure calculations Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.172, year: 2007

  12. On the possibility of contact-induced spin polarization in interfaces of armchair nanotubes with transition metal substrates

    Kuzubov, Alexander A. [Siberian Federal University, 79 Svobodny Prospect, 660041 Krasnoyarsk (Russian Federation); Kirensky Institute of Physics, 50 Akademgorodok, 660036 Krasnoyarsk (Russian Federation); Kovaleva, Evgenia A., E-mail: kovaleva.evgeniya1991@mail.ru [Siberian Federal University, 79 Svobodny Prospect, 660041 Krasnoyarsk (Russian Federation); Kirensky Institute of Physics, 50 Akademgorodok, 660036 Krasnoyarsk (Russian Federation); Tomilin, Felix N.; Mikhaleva, Natalya S.; Kuklin, Artem V. [Siberian Federal University, 79 Svobodny Prospect, 660041 Krasnoyarsk (Russian Federation); Kirensky Institute of Physics, 50 Akademgorodok, 660036 Krasnoyarsk (Russian Federation)

    2015-12-15

    The interaction between armchair carbon and boron nitride nanotubes (NT) with ferromagnetic transition metal (TM) surfaces, namely, Ni(111) and Co(0001), was studied by means of density functional theory. Different configurations of composite compartments mutual arrangement were considered. Partial densities of states and spin density spatial distribution of optimized structures were investigated. Influence of ferromagnetic substrate on nanotubes’ electronic properties was discussed. The values of spin polarization magnitude at the Fermi level are also presented and confirm the patterns of spin density spatial distribution. - Highlights: • Interaction of armchair nanotubes with ferromagnetic metal surfaces was investigated. • Different configurations of nanotube's location were considered. • For all nanotubes the energy difference between configurations is negligible. • Nanotubes were found to be more or less spin-polarized regarding to the configuration. • BN nanotubes demonstrate vanishing of the band gap and contact-induced conductivity.

  13. Electronic specific heat of transition metal carbides

    Conte, R.

    1964-07-01

    The experimental results that make it possible to define the band structure of transition metal carbides having an NaCI structure are still very few. We have measured the electronic specific heat of some of these carbides of varying electronic concentration (TiC, either stoichiometric or non-stoichiometric, TaC and mixed (Ti, Ta) - C). We give the main characteristics (metallography, resistivity, X-rays) of our samples and we describe the low temperature specific heat apparatus which has been built. In one of these we use helium as the exchange gas. The other is set up with a mechanical contact. The two use a germanium probe for thermometer. The measurement of the temperature using this probe is described, as well as the various measurement devices. The results are presented in the form of a rigid band model and show that the density of the states at the Fermi level has a minimum in the neighbourhood of the group IV carbides. (author) [fr

  14. Phase stability of transition metals and alloys

    Hixson, R.S.; Schiferl, D.; Wills, J.M.; Hill, M.A.

    1997-01-01

    This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This project was focused on resolving unexplained differences in calculated and measured phase transition pressures in transition metals. Part of the approach was to do new, higher accuracy calculations of transmission pressures for group 4B and group 6B metals. Theory indicates that the transition pressures for these baseline metals should change if alloyed with a d-electron donor metal, and calculations done using the Local Density Approximation (LDA) and the Virtual Crystal Approximation (VCA) indicate that this is true. Alloy systems were calculated for Ti, Zr and Hf based alloys with various solute concentrations. The second part of the program was to do new Diamond Anvil Cell (DAC) measurements to experimentally verify calculational results. Alloys were prepared for these systems with grain size suitable for Diamond Anvil Cell experiments. Experiments were done on pure Ti as well as Ti-V and Ti-Ta alloys. Measuring unambiguous transition pressures for these systems proved difficult, but a new technique developed yielded good results

  15. Electrical valley filtering in transition metal dichalcogenides

    Hsieh, Tzu-Chi; Chou, Mei-Yin; Wu, Yu-Shu

    2018-03-01

    This work investigates the feasibility of electrical valley filtering for holes in transition metal dichalcogenides. We look specifically into the scheme that utilizes a potential barrier to produce valley-dependent tunneling rates, and perform the study with both a k .p -based analytic method and a recursive Green's function-based numerical method. The study yields the transmission coefficient as a function of incident energy and transverse wave vector, for holes going through lateral quantum barriers oriented in either armchair or zigzag directions, in both homogeneous and heterogeneous systems. The main findings are the following: (1) The tunneling current valley polarization increases with increasing barrier width or height; (2) both the valley-orbit interaction and band structure warping contribute to valley-dependent tunneling, with the former contribution being manifest in structures with asymmetric potential barriers, and the latter being orientation dependent and reaching maximum for transmission in the armchair direction; and (3) for transmission ˜0.1 , a tunneling current valley polarization of the order of 10 % can be achieved.

  16. Gas phase structure of transition metal dihydrides

    Demuynck, J.; Schaefer, H.F. III

    1980-01-01

    ESR and infrared spectroscopic measurements on matrix isolated MnH 2 and CrH 2 have recently suggested that these simple molecules may be bent. This result would be the opposite of that found experimentally for the transition metal dihalides MX 2 , known to be linear. Here the geometrical structure of MnH 2 has been investigated by molecular electronic structure theory. A large contracted Gaussian basis set [Mn(14s11p6p/9s8p3d), H(5s1p/3s1p)] was used in conjunction with self-consistent field and configuration interaction methods. These suggest that the 6 A 1 ground state of MnH 2 is linear. Further studies of the 3 A 1 state (one of several low-lying states) of TiH 2 also favor linearity, although this potential energy surface is extremely flat with respect to bending. Thus it appears probable that most MH 2 molecules, like the related MX 2 family, are linear

  17. Dark excitons in transition metal dichalcogenides

    Malic, Ermin; Selig, Malte; Feierabend, Maja; Brem, Samuel; Christiansen, Dominik; Wendler, Florian; Knorr, Andreas; Berghäuser, Gunnar

    2018-01-01

    Monolayer transition metal dichalcogenides (TMDs) exhibit a remarkably strong Coulomb interaction that manifests in tightly bound excitons. Due to the complex electronic band structure exhibiting several spin-split valleys in the conduction and valence band, dark excitonic states can be formed. They are inaccessibly by light due to the required spin-flip and/or momentum transfer. The relative position of these dark states with respect to the optically accessible bright excitons has a crucial impact on the emission efficiency of these materials and thus on their technological potential. Based on the solution of the Wannier equation, we present the excitonic landscape of the most studied TMD materials including the spectral position of momentum- and spin-forbidden excitonic states. We show that the knowledge of the electronic dispersion does not allow to conclude about the nature of the material's band gap since excitonic effects can give rise to significant changes. Furthermore, we reveal that an exponentially reduced photoluminescence yield does not necessarily reflect a transition from a direct to a nondirect gap material, but can be ascribed in most cases to a change of the relative spectral distance between bright and dark excitonic states.

  18. Photocatalysis of Modified Transition Metal Oxide Surfaces

    Batzill, Matthias [Univ. of South Florida, Tampa, FL (United States). Dept. of Physics

    2018-02-28

    The goal of this project has been to establish a cause-effect relationship for photocatalytic activity variations of different structures of the same material; and furthermore gain fundamental understanding on modification of photocatalysts by compositional or surface modifications. The reasoning is that gaining atomic scale understanding of how surface and bulk modifications alter the photo reactivity will lead to design principles for next generation photocatalysts. As a prototypical photocatalyst the research focused on TiO2 synthesized in well-defined single crystalline form to enable fundamental characterizations.We have obtained results in the following areas: (a) Preparation of epitaxial anatase TiO2 samples by pulsed laser deposition. (b) Comparison of hydrogen diffusion on different crystallographic surface. (c) Determining the stability of the TiO2(011)-2x1 reconstruction upon interactions with adsorbates. (d) Characterization of adsorption and (thermal and photo) reaction of molecules with nitro-endgroups, (e) Exploring the possibility of modifying planar model photocatalyst surfaces with graphene to enable fundamental studies on reported enhanced photocatalytic activities of graphene modified transition metal oxides, (f) gained fundamental understanding on the role of crystallographic polymorphs of the same material for their photocatalytic activities.

  19. Ab initio investigations of magnetic properties of ultrathin transition-metal films on 4d substrates

    Al-Zubi, Ali

    2010-12-22

    In this thesis, we investigate the magnetic properties of 3d transition-metal monolayers on 4d transition-metal substrates by means of state of the art first-principles quantum theory. In order to reveal the underlying physics of these systems we study trends by performing systematic investigations across the transition-metal series. Case studies are presented for which Rh has been chosen as exemplary 4d substrate. We consider two substrate orientations, a square lattice provided by Rh(001) and a hexagonal lattice provided by Rh(111). We find, all 3d transition-metal (V, Cr, Mn, Fe, Co and Ni) monolayers deposited on the Rh substrate are magnetic and exhibit large local moments which follow Hund's rule with a maximum magnetic moment for Mn of about 3.7 {mu}{sub B} depending on the substrate orientation. The largest induced magnetic moment of about 0.46 {mu}{sub B} is found for Rh atoms adjacent to the Co(001)-film. On Rh(001) we predict a ferromagnetic (FM) ground state for V, Co and Ni, while Cr, Mn and Fe monolayers favor a c(2 x 2) antiferromagnetic (AFM) state, a checkerboard arrangement of up and down magnetic moments. The magnetic anisotropy energies of these ultrathin magnetic films are calculated for the FM and the AFM states. With the exception of V and Cr, the easy axis of the magnetization is predicted to be in the film plane. With the exception of Fe, analogous results are obtained for the 3d-metal monolayers on Rh(111). For Fe on Rh(111) a novel magnetic ground state is predicted, a double-row-wise antiferromagnetic state along the [11 anti 2] direction, a sequence of ferromagnetic double-rows of atoms, whose magnetic moments couple antiferromagnetically from double row to double row. The magnetic structure can be understood as superposition of a left- and right-rotating flat spin spiral. In a second set of case studies the properties of an Fe monolayer deposited on varies hexagonally terminated hcp (0001) and fcc (111) surfaces of 4d-transition

  20. Ab initio investigations of magnetic properties of ultrathin transition-metal films on 4d substrates

    Al-Zubi, Ali

    2010-12-22

    In this thesis, we investigate the magnetic properties of 3d transition-metal monolayers on 4d transition-metal substrates by means of state of the art first-principles quantum theory. In order to reveal the underlying physics of these systems we study trends by performing systematic investigations across the transition-metal series. Case studies are presented for which Rh has been chosen as exemplary 4d substrate. We consider two substrate orientations, a square lattice provided by Rh(001) and a hexagonal lattice provided by Rh(111). We find, all 3d transition-metal (V, Cr, Mn, Fe, Co and Ni) monolayers deposited on the Rh substrate are magnetic and exhibit large local moments which follow Hund's rule with a maximum magnetic moment for Mn of about 3.7 {mu}{sub B} depending on the substrate orientation. The largest induced magnetic moment of about 0.46 {mu}{sub B} is found for Rh atoms adjacent to the Co(001)-film. On Rh(001) we predict a ferromagnetic (FM) ground state for V, Co and Ni, while Cr, Mn and Fe monolayers favor a c(2 x 2) antiferromagnetic (AFM) state, a checkerboard arrangement of up and down magnetic moments. The magnetic anisotropy energies of these ultrathin magnetic films are calculated for the FM and the AFM states. With the exception of V and Cr, the easy axis of the magnetization is predicted to be in the film plane. With the exception of Fe, analogous results are obtained for the 3d-metal monolayers on Rh(111). For Fe on Rh(111) a novel magnetic ground state is predicted, a double-row-wise antiferromagnetic state along the [11 anti 2] direction, a sequence of ferromagnetic double-rows of atoms, whose magnetic moments couple antiferromagnetically from double row to double row. The magnetic structure can be understood as superposition of a left- and right-rotating flat spin spiral. In a second set of case studies the properties of an Fe monolayer deposited on varies hexagonally terminated hcp (0001) and fcc (111) surfaces of 4d-transition metals

  1. Ab initio investigations of magnetic properties of ultrathin transition-metal films on 4d substrates

    Al-Zubi, Ali

    2010-01-01

    In this thesis, we investigate the magnetic properties of 3d transition-metal monolayers on 4d transition-metal substrates by means of state of the art first-principles quantum theory. In order to reveal the underlying physics of these systems we study trends by performing systematic investigations across the transition-metal series. Case studies are presented for which Rh has been chosen as exemplary 4d substrate. We consider two substrate orientations, a square lattice provided by Rh(001) and a hexagonal lattice provided by Rh(111). We find, all 3d transition-metal (V, Cr, Mn, Fe, Co and Ni) monolayers deposited on the Rh substrate are magnetic and exhibit large local moments which follow Hund's rule with a maximum magnetic moment for Mn of about 3.7 μ B depending on the substrate orientation. The largest induced magnetic moment of about 0.46 μ B is found for Rh atoms adjacent to the Co(001)-film. On Rh(001) we predict a ferromagnetic (FM) ground state for V, Co and Ni, while Cr, Mn and Fe monolayers favor a c(2 x 2) antiferromagnetic (AFM) state, a checkerboard arrangement of up and down magnetic moments. The magnetic anisotropy energies of these ultrathin magnetic films are calculated for the FM and the AFM states. With the exception of V and Cr, the easy axis of the magnetization is predicted to be in the film plane. With the exception of Fe, analogous results are obtained for the 3d-metal monolayers on Rh(111). For Fe on Rh(111) a novel magnetic ground state is predicted, a double-row-wise antiferromagnetic state along the [11 anti 2] direction, a sequence of ferromagnetic double-rows of atoms, whose magnetic moments couple antiferromagnetically from double row to double row. The magnetic structure can be understood as superposition of a left- and right-rotating flat spin spiral. In a second set of case studies the properties of an Fe monolayer deposited on varies hexagonally terminated hcp (0001) and fcc (111) surfaces of 4d-transition metals (Tc, Ru, Rh

  2. Critical current oscillations in superconductor-ferromagnet-superconductor structure taking into account s-d scattering

    Vedyaev, A.V.; Ryzhanova, N.V.; Pugach, N.G.

    2007-01-01

    One calculated the critical current in the Josephson contact with the transition metal slightly ferromagnetic alloy interlayer. One solved the Gorkov equations taking into account s-d-scattering in a ferromagnet. The account of the mentioned scattering breaking down the Cooper pairs is shown to enable to ensure the conformity with the experiment [ru

  3. Microstructural properties of over-doped GaN-based diluted magnetic semiconductors grown by MOCVD

    Tao Zhikuo; Zhang Rong; Xiu Xiangqian; Cui Xugao; Li Xin; Xie Zili; Zheng Youdou; Li Li; Zheng Rongkun; Ringer, Simon P

    2012-01-01

    We have grown transition metal (Fe, Mn) doped GaN thin films on c-oriented sapphire by metal-organic chemical vapor deposition. By varying the flow of the metal precursor, a series of samples with different ion concentrations are synthesized. Microstructural properties are characterized by using a high-resolution transmission electron microscope. For Fe over-doped GaN samples, hexagonal Fe 3 N clusters are observed with Fe 3 N(0002) parallel to GaN (0002) while for Mn over-doped GaN, hexagonal Mn 6 N 2.58 phases are observed with Mn 6 N 2.58 (0002) parallel to GaN(0002). In addition, with higher concentration ions doping into the lattice matrix, the partial lattice orientation is distorted, leading to the tilt of GaN(0002) planes. The magnetization of the Fe over-doped GaN sample is increased, which is ascribed to the participation of ferromagnetic iron and Fe 3 N. The Mn over-doped sample displays very weak ferromagnetic behavior, which probably originates from the Mn 6 N 2.58 . (semiconductor materials)

  4. Nucleic acid-functionalized transition metal nanosheets for biosensing applications.

    Mo, Liuting; Li, Juan; Liu, Qiaoling; Qiu, Liping; Tan, Weihong

    2017-03-15

    In clinical diagnostics, as well as food and environmental safety practices, biosensors are powerful tools for monitoring biological or biochemical processes. Two-dimensional (2D) transition metal nanomaterials, including transition metal chalcogenides (TMCs) and transition metal oxides (TMOs), are receiving growing interest for their use in biosensing applications based on such unique properties as high surface area and fluorescence quenching abilities. Meanwhile, nucleic acid probes based on Watson-Crick base-pairing rules are also being widely applied in biosensing based on their excellent recognition capability. In particular, the emergence of functional nucleic acids in the 1980s, especially aptamers, has substantially extended the recognition capability of nucleic acids to various targets, ranging from small organic molecules and metal ions to proteins and cells. Based on π-π stacking interaction between transition metal nanosheets and nucleic acids, biosensing systems can be easily assembled. Therefore, the combination of 2D transition metal nanomaterials and nucleic acids brings intriguing opportunities in bioanalysis and biomedicine. In this review, we summarize recent advances of nucleic acid-functionalized transition metal nanosheets in biosensing applications. The structure and properties of 2D transition metal nanomaterials are first discussed, emphasizing the interaction between transition metal nanosheets and nucleic acids. Then, the applications of nucleic acid-functionalized transition metal nanosheet-based biosensors are discussed in the context of different signal transducing mechanisms, including optical and electrochemical approaches. Finally, we provide our perspectives on the current challenges and opportunities in this promising field. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Surface segregation energies in transition-metal alloys

    Ruban, Andrei; Skriver, Hans Lomholt; Nørskov, Jens Kehlet

    1999-01-01

    We present a database of 24 x 24 surface segregation energies of single transition metal impurities in transition-metal hosts obtained by a Green's-function linear-muffin-tin-orbitals method in conjunction with the coherent potential and atomic sphere approximations including a multipole correction...... to the electrostatic potential and energy. We use the database to establish the major factors which govern surface segregation in transition metal alloys. We find that the calculated trends are well described by Friedel's rectangular state density model and that the few but significant deviations from the simple...

  6. Stable carbides in transition metal alloys

    Piotrkowski, R.

    1991-01-01

    In the present work different techniques were employed for the identification of stable carbides in two sets of transition metal alloys of wide technological application: a set of three high alloy M2 type steels in which W and/or Mo were total or partially replaced by Nb, and a Zr-2.5 Nb alloy. The M2 steel is a high speed steel worldwide used and the Zr-2.5 Nb alloy is the base material for the pressure tubes in the CANDU type nuclear reactors. The stability of carbide was studied in the frame of Goldschmidt's theory of interstitial alloys. The identification of stable carbides in steels was performed by determining their metallic composition with an energy analyzer attached to the scanning electron microscope (SEM). By these means typical carbides of the M2 steel, MC and M 6 C, were found. Moreover, the spatial and size distribution of carbide particles were determined after different heat treatments, and both microstructure and microhardness were correlated with the appearance of the secondary hardening phenomenon. In the Zr-Nb alloy a study of the α and β phases present after different heat treatments was performed with optical and SEM metallographic techniques, with the guide of Abriata and Bolcich phase diagram. The α-β interphase boundaries were characterized as short circuits for diffusion with radiotracer techniques and applying Fisher-Bondy-Martin model. The precipitation of carbides was promoted by heat treatments that produced first the C diffusion into the samples at high temperatures (β phase), and then the precipitation of carbide particles at lower temperature (α phase or (α+β)) two phase field. The precipitated carbides were identified as (Zr, Nb)C 1-x with SEM, electron microprobe and X-ray diffraction techniques. (Author) [es

  7. Transition metal modified bulk BiFeO{sub 3} with improved magnetization and linear magneto-electric coupling

    Puli, Venkata Sreenivas, E-mail: pvsri123@gmail.com [Department of Physics and Institute for Functional Nanomaterials, University of Puerto Rico, San Juan, PR 00936 (Puerto Rico); Kumar, A.; Panwar, N.; Panwar, I.C.; Katiyar, R.S. [Department of Physics and Institute for Functional Nanomaterials, University of Puerto Rico, San Juan, PR 00936 (Puerto Rico)

    2011-08-11

    Highlights: > Present composition (Bi{sub 0.9}Sm{sub 0.10}Fe{sub 0.95}Co{sub 0.05}O{sub 3} (BSFCO) have shown very high magnetization compared to parent BFO. > The magnetic hysteresis loops are well saturated with high saturation magnetization 2.89 emu/gm (unpoled and unleached) and 2.18 emu/gm (poled and unleached) respectively. > Converse ME coupling were found 0.8e-10 s m{sup -1} (H||E) and 0.6-0.8 x 10{sup -10} s m{sup -1} (H-perpendicular E) which are better than the single phase multiferroic obeying linear ME coupling. - Abstract: At present BiFeO{sub 3} (BFO) is the most attractive and sole example, which possesses low magnetization value, high leakage current and low polarization in ceramic form. Single-phase room temperature multiferroics are rare in nature. This paper deals with the improved magnetic and observed linear magneto-electric coupling in Co and Sm co-doped BiFeO{sub 3} ceramics synthesized by sol-gel process at low temperature {approx}600 deg. C. As synthesized Bi{sub 0.9}Sm{sub 0.10}Fe{sub 0.95}Co{sub 0.05}O{sub 3} (BSFCO) showed high impurities phases (20%) over wide range of calcination temperatures. Impurity phases reduced drastically from 20% to 5% after leaching with nitric acid. However the electrical and the magnetic properties were almost the same for both phases. Well-defined magnetic hysteresis with high magnetic moment was found at room temperature. Ferroelectric polarization studies demonstrated similar values and shape as reported in literature for the pure bulk BFO. Linear magneto-electric (ME) coupling and weak ME coefficient ({alpha}) {approx} 0.6 e-10 s m{sup -1} were observed in the co-doped BFO. The origin of the strong ferromagnetic property in our samples may be due to the presence of rare earth and transition metal ions at the lattice sites of BFO or due to impurity phase, since we have not seen any change in magnetization with reduction of impurity phase the later effect is more unlikely.

  8. Transition metal modified bulk BiFeO3 with improved magnetization and linear magneto-electric coupling

    Puli, Venkata Sreenivas; Kumar, A.; Panwar, N.; Panwar, I.C.; Katiyar, R.S.

    2011-01-01

    Highlights: → Present composition (Bi 0.9 Sm 0.10 Fe 0.95 Co 0.05 O 3 (BSFCO) have shown very high magnetization compared to parent BFO. → The magnetic hysteresis loops are well saturated with high saturation magnetization 2.89 emu/gm (unpoled and unleached) and 2.18 emu/gm (poled and unleached) respectively. → Converse ME coupling were found 0.8e-10 s m -1 (H||E) and 0.6-0.8 x 10 -10 s m -1 (H-perpendicular E) which are better than the single phase multiferroic obeying linear ME coupling. - Abstract: At present BiFeO 3 (BFO) is the most attractive and sole example, which possesses low magnetization value, high leakage current and low polarization in ceramic form. Single-phase room temperature multiferroics are rare in nature. This paper deals with the improved magnetic and observed linear magneto-electric coupling in Co and Sm co-doped BiFeO 3 ceramics synthesized by sol-gel process at low temperature ∼600 deg. C. As synthesized Bi 0.9 Sm 0.10 Fe 0.95 Co 0.05 O 3 (BSFCO) showed high impurities phases (20%) over wide range of calcination temperatures. Impurity phases reduced drastically from 20% to 5% after leaching with nitric acid. However the electrical and the magnetic properties were almost the same for both phases. Well-defined magnetic hysteresis with high magnetic moment was found at room temperature. Ferroelectric polarization studies demonstrated similar values and shape as reported in literature for the pure bulk BFO. Linear magneto-electric (ME) coupling and weak ME coefficient (α) ∼ 0.6 e-10 s m -1 were observed in the co-doped BFO. The origin of the strong ferromagnetic property in our samples may be due to the presence of rare earth and transition metal ions at the lattice sites of BFO or due to impurity phase, since we have not seen any change in magnetization with reduction of impurity phase the later effect is more unlikely.

  9. Alkylation and arylation of alkenes by transition metal complexes

    Volkova, L.G.; Levitin, I.Ya.; Vol'pin, M.E.

    1975-01-01

    In this paper are reviewed methods of alkylation and irylation of unsaturated compounds with complexes of transition metals (Rh, Pd). Analysis of alkylation and arylation of olefines with organic derivatives of transition metals, obtained as a result of exchange reactions between organic compounds of transition metals and salts of metals of the 8th group of the periodic system, allows a conclusion as to the wide possibilities of these reactions in the synthesis of various derivatives of unsaturated compounds. In all the reactions under consideration, intermediate formation of sigma-complexes is assumed. Also considered are alkylation and arylation of olefines with organic derivatives of halogens in the presence of compounds of metals of the 8th group of the periodic system, as well as arylation of olefines with aromatic compounds in the presence of salts of transition metals

  10. A review on transition-metal mediated synthesis of quinolines

    Rashmi Sharma

    2018-06-14

    Jun 14, 2018 ... Special Section on Transition Metal Catalyzed Synthesis of Medicinally Relevant Molecules. A review on ...... iron(III) chloride and TEMPO oxoammonium salt as an .... propyl-3-ethylquinoline (209) in presence of platinum.

  11. Metallacyclopentadienes: structural features and coordination in transition metal complexes

    Dolgushin, Fedor M; Yanovsky, Aleksandr I; Antipin, Mikhail Yu

    2004-01-01

    Results of structural studies of polynuclear transition metal complexes containing the metallacyclopentadiene fragment are overviewed. The structural features of the complexes in relation to the nature of the substituents in the organic moiety of the metallacycles, the nature of the transition metals and their ligand environment are analysed. The main structural characteristics corresponding to different modes of coordination of metallacyclopentadienes to one or two additional metal centres are revealed.

  12. Trends in catalytic NO decomposition over transition metal surfaces

    Falsig, Hanne; Bligaard, Thomas; Rass-Hansen, Jeppe

    2007-01-01

    The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional...... theory calculations. We show specifically why the key problem in using transition metal surfaces to catalyze direct NO decomposition is their significant relative overbinding of atomic oxygen compared to atomic nitrogen....

  13. Transition-Metal-Free Biomolecule-Based Flexible Asymmetric Supercapacitors.

    Yang, Yun; Wang, Hua; Hao, Rui; Guo, Lin

    2016-09-01

    A transition-metal-free asymmetric supercapacitor (ASC) is successfully fabricated based on an earth-abundant biomass derived redox-active biomolecule, named lawsone. Such an ASC exhibits comparable or even higher energy densities than most of the recently reported transition-metal-based ASCs, and this green ASC generation from renewable resources is promising for addressing current issues of electronic hazard processing, high cost, and unsustainability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Obtaining strong ferromagnetism in diluted Gd-doped ZnO thin films through controlled Gd-defect complexes

    Roqan, Iman S.

    2015-02-21

    We demonstrate the fabrication of reproducible long-range ferromagnetism (FM) in highly crystalline GdxZn1-xO thin films by controlling the defects. Films are grown on lattice-matched substrates by pulsed laser deposition at low oxygen pressures (≤25 mTorr) and low Gd concentrations (x ≤ 0.009). These films feature strong FM (10 μB per Gd atom) at room temperature. While films deposited at higher oxygen pressure do not exhibit FM, FM is recovered by post-annealing these films under vacuum. These findings reveal the contribution of oxygen deficiency defects to the long-range FM. We demonstrate the possible FM mechanisms, which are confirmed by density functional theory study, and show that Gd dopants are essential for establishing FM that is induced by intrinsic defects in these films.

  15. Obtaining strong ferromagnetism in diluted Gd-doped ZnO thin films through controlled Gd-defect complexes

    Roqan, Iman S.; Venkatesh, S.; Zhang, Z.; Hussain, S.; Bantounas, Ioannis; Franklin, J. B.; Flemban, Tahani H.; Zou, B.; Lee, J.-S.; Schwingenschlö gl, Udo; Petrov, P. K.; Ryan, M. P.; Alford, N. M.

    2015-01-01

    We demonstrate the fabrication of reproducible long-range ferromagnetism (FM) in highly crystalline GdxZn1-xO thin films by controlling the defects. Films are grown on lattice-matched substrates by pulsed laser deposition at low oxygen pressures (≤25 mTorr) and low Gd concentrations (x ≤ 0.009). These films feature strong FM (10 μB per Gd atom) at room temperature. While films deposited at higher oxygen pressure do not exhibit FM, FM is recovered by post-annealing these films under vacuum. These findings reveal the contribution of oxygen deficiency defects to the long-range FM. We demonstrate the possible FM mechanisms, which are confirmed by density functional theory study, and show that Gd dopants are essential for establishing FM that is induced by intrinsic defects in these films.

  16. Competing effects between intrinsic and extrinsic defects in pure and Mn-doped ZnO nanocrystals

    Ruf, Thomas; Repp, Sergej; Urban, Joanna [Albert-Ludwigs-Universität Freiburg, Institut für Physikalische Chemie (Germany); Thomann, Ralf [Albert-Ludwigs-Universität Freiburg, Freiburger Materialforschungszentrum (FMF) (Germany); Erdem, Emre, E-mail: emre.erdem@physchem.uni-freiburg.de [Albert-Ludwigs-Universität Freiburg, Institut für Physikalische Chemie (Germany)

    2016-05-15

    Nano-sized ZnO doped with transition metals is one of the most promising candidates in the field of diluted magnetic semiconductors unifying ferromagnetic and semiconductor properties. Promising is the exploitation of the magnetic spin of the electron and by that the application in spintronics. As the mechanism of spin coupling is still controversial, insight into the coexistence and interaction of intrinsic and extrinsic effects is vital for further technological progress. We report on the synthesis of a set of nano-sized Zn{sub 1−x}Mn{sub x}O samples with a nominal concentration of x = 0.000005–0.03 and structural (XRD, TEM, and AFM), as well as electronic (PL, UV–Vis, FTIR, and EPR) investigations. In this contribution, possible interaction effects were summarized in terms of Mn doping and size. PL quenching after doping was also discussed as another aspect for the interrelations of the defects.

  17. Characterization of transition metal-containing oxide systems by Mössbauer Spectroscopy

    Z. Homonnay

    2004-12-01

    Full Text Available High-temperature (high-Tc superconductors and colossal magnetoresistant (CMR materials belong to the most promising materials of the past 2-3 decades for technical applications. Most of them are oxides and the crucial element which determines their useful physical properties is often a transition metal (Cu, Co, Fe, Mn. 57Fe Mössbauer Spectroscopy can be used to characterize the electronic and structural properties of transition metal-containing oxides by providing information on the local electronic structure of the lattice site where the Mössbauer probe is accommodated. By reviewing several Mössbauer studies, it is demonstrated how the layered (2D electronic structure of high-Tc superconductors can be deduced from the analysis of the Mössbauer isomer shift and quadrupole splitting. We also show how the Mössbauer isomer shift indicates metallicity of the ferromagnetic phase in the CMR material LaxSr1-xCoO3.

  18. Theory of magnetic transition metal nanoclusters on surfaces

    Lounis, S.

    2007-04-17

    This thesis is motivated by the quest for the understanding and the exploration of complex magnetism provided by atomic scale magnetic clusters deposited on surfaces or embedded in the bulk. Use is made of the density functional theory (DFT). Acting within this framework, we have developed and implemented the treatment of non-collinear magnetism into the Juelich version of the full-potential Korringa-Kohn-Rostoker Green Function (KKR-GF) method. Firstly, the method was applied to 3d transition-metal clusters on different ferromagnetic surfaces. Different types of magnetic clusters where selected. In order to investigate magnetic frustration due to competing interactions within the ad-cluster we considered a (001) oriented surface of fcc metals, a topology which usually does not lead to non-collinear magnetism. We tuned the strength of the magnetic coupling between the ad-clusters and the ferromagnetic surface by varying the substrate from the case of Ni(001) with a rather weak hybridization of the Ni d-states with the adatom d-states to the case of Fe{sub 3ML}/Cu(001) with a much stronger hybridization due to the larger extend of the Fe wavefunctions. On Ni(001), the interaction between the Cr- as well as the Mn-dimer adatoms is of antiferromagnetic nature, which is in competition with the interaction with the substrate atoms. After performing total energy calculations we find that for Cr-dimer the ground state is collinear whereas the Mn-dimer prefers the non-collinear configuration as ground state. Bigger clusters are found to be magnetically collinear. These calculations were extended to 3d multimers on Fe{sub 3ML}/Cu(001). All neighboring Cr(Mn) moments in the compact tetramer are antiferromagnetically aligned in-plane, with the directions slightly tilted towards (outwards from) the substrate to gain some exchange interaction energy. The second type of frustration was investigated employing a Ni(111) surface, a surface with a triangular lattice of atoms, were

  19. Exploring the Room-Temperature Ferromagnetism and Temperature-Dependent Dielectric Properties of Sr/Ni-Doped LaFeO3 Nanoparticles Synthesized by Reverse Micelle Method

    Naseem, Swaleha; Khan, Shakeel; Husain, Shahid; Khan, Wasi

    2018-03-01

    This paper reports the thermal, microstructural, dielectric and magnetic properties of La0.75Sr0.25Fe0.65Ni0.35O3 nanoparticles (NPs) synthesized via reverse micelle technique. The thermogravimetric analysis of as-prepared NPs confirmed a good thermal stability of the sample. Powder x-ray diffraction data analyzed with a Rietveld refinement technique revealed single-phase and orthorhombic distorted perovskite crystal structure of the NPs having Pbnm space group. The transmission electron microscopy images show the crystalline nature and formation of nanostructures with a fairly uniform distribution of particles throughout the sample. Temperature-dependent dielectric properties of the NPs in accordance with the Kramers-Kronig transformation (KKT) model, universal dielectric response model and jump relaxation model have been discussed. Electrode or interface polarization is likely the cause of the observed dielectric behavior. Due to grain boundaries and Schottky barriers of the metallic electrodes of semiconductors, the depletion region is observed, which gives rise to Maxwell-Wagner relaxation and hence high dielectric constants. Magnetic studies revealed the ferromagnetic nature of the prepared NPs upon Sr and Ni doping in LaFeO3 perovskite at room temperature. Therefore, these NPs could be a potential candidate as electrode material in solid oxide fuel cells.

  20. High pressure and microwave based synthesis of transition metal pnictides

    Pobel, Roman Rupert

    2016-04-11

    The goal of this thesis was to explore the possibilities of synthetic methods that are not very common in current transition metal pnictide research. The substitution of the Ca-site in CaFe{sub 2}As{sub 2} with rare earth elements such as Pr the has been reported to induce superconductivity. However, some inconsistencies in the data suggested a non-intrinsic origin of the observed diamagnetic signal. Furthermore a solubility limit of 13% was found when prepared in an electrical furnace thus leaving a huge part of the physical phase diagram inaccessible. A high pressure/high temperature synthesis was developed to allow access to the whole doping range and an in-depth characterization of this compound was carried out. During the experiments concerning the high pressure synthesis of Ca{sub 1-x}Pr{sub x}Fe{sub 2}As{sub 2} the new ternary iron arsenide CaFe{sub 5}As{sub 3} was identified and classified as a member of the Ca{sub n(n+1)/2}(Fe{sub 1-x}M{sub x}){sub (2+3n)}M'{sub n(n-1)/2}As{sub (n+1)(n+2)/2} (n = 1-3; M =Nb, Pd, Pt; M' = □, Pd, Pt) family. The complete solid solution Ca{sub 1-x}Pr{sub x}Fe{sub 5}As{sub 3} (O ≤ x ≤ 1) was prepared and physically characterized. Furthermore, several useful techniques were developed to aid in future high pressure based investigations of transition metal pnictides. The second part of this thesis concerns a completely different, but equally promising synthetic approach. Microwave based synthesis is a well-established technique in many solution based fields, such as organic, medicinal or nano chemistry. For solid state and materials research several parameters and particularities have to be considered. But when successful, it allows for the reduction of reaction time by several orders of magnitude. It has very rarely been applied in the preparation of pnictides and on1y once in the context of pnictide superconductor research. The possibilities of this method were explored and employed in the preparation of several

  1. Rutile-type Co doped SnO{sub 2} diluted magnetic semiconductor nanoparticles: Structural, dielectric and ferromagnetic behavior

    Mehraj, Sumaira, E-mail: sumairamehraj07@gmail.com [Department of Applied Physics, Aligarh Muslim University, Aligarh-202002 (India); Shahnawaze Ansari, M. [Center of Nanotechnology, King Abdulaziz University, Jeddah-21589 (Saudi Arabia); Alimuddin [Department of Applied Physics, Aligarh Muslim University, Aligarh-202002 (India)

    2013-12-01

    Nanoparticles of basic composition Sn{sub 1−x}Co{sub x}O{sub 2} (x=0.00, 0.01, 0.03, 0.05 and 0.1) were synthesized through the citrate-gel method and were characterized for structural properties using X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FT-IR). XRD analysis of the powder samples sintered at 500 °C for 12 h showed single phase rutile type tetragonal structure and the crystallite size decreased as the cobalt content was increased. FT-IR spectrum displayed various bands that came due to fundamental overtones and combination of O–H, Sn–O and Sn–O–Sn entities. The effect of Co doping on the electrical and magnetic properties was studied using dielectric spectroscopy and vibrating sample magnetometer (VSM) at room temperature. The dielectric parameters (ε, tan δ and σ{sub ac}) show their maximum value for 10% Co doping. The dielectric loss shows anomalous behavior with frequency where it exhibits the Debye relaxation. The variation of dielectric properties and ac conductivity with frequency reveals that the dispersion is due to the Maxwell–Wagner type of interfacial polarization in general and hopping of charge between Sn{sup 2+} and Sn{sup 4+} as well as between Co{sup 2+} and Co{sup 3+} ions. The complex impedance analysis was used to separate the grain and grain boundary contributions in the system which shows that the conduction process in grown nanoparticles takes place predominantly through grain boundary volume. Hysteresis loops were observed clearly in M–H curves from 0.01 to 0.1% Co doped SnO{sub 2} samples. The saturation magnetization of the doped samples increased slightly with increase of Co concentration. However pure SnO{sub 2} displayed paramagnetism which vanished at higher values of magnetic field.

  2. A Simple, General Synthetic Route toward Nanoscale Transition Metal Borides.

    Jothi, Palani R; Yubuta, Kunio; Fokwa, Boniface P T

    2018-04-01

    Most nanomaterials, such as transition metal carbides, phosphides, nitrides, chalcogenides, etc., have been extensively studied for their various properties in recent years. The similarly attractive transition metal borides, on the contrary, have seen little interest from the materials science community, mainly because nanomaterials are notoriously difficult to synthesize. Herein, a simple, general synthetic method toward crystalline transition metal boride nanomaterials is proposed. This new method takes advantage of the redox chemistry of Sn/SnCl 2 , the volatility and recrystallization of SnCl 2 at the synthesis conditions, as well as the immiscibility of tin with boron, to produce crystalline phases of 3d, 4d, and 5d transition metal nanoborides with different morphologies (nanorods, nanosheets, nanoprisms, nanoplates, nanoparticles, etc.). Importantly, this method allows flexibility in the choice of the transition metal, as well as the ability to target several compositions within the same binary phase diagram (e.g., Mo 2 B, α-MoB, MoB 2 , Mo 2 B 4 ). The simplicity and wide applicability of the method should enable the fulfillment of the great potential of this understudied class of materials, which show a variety of excellent chemical, electrochemical, and physical properties at the microscale. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Molecular ferromagnetism

    Epstein, A.J.

    1990-01-01

    This past year has been one of substantial advancement in both the physics and chemistry of molecular and polymeric ferromagnets. The specific heat studies of (DMeFc)(TCNE) have revealed a cusp at the three-dimensional ferromagnetic transition temperature with a crossover to primarily 1-D behavior at higher temperatures. This paper discusses these studies

  4. Novel room temperature ferromagnetic semiconductors

    Gupta, Amita [KTH Royal Inst. of Technology, Stockholm (Sweden)

    2004-06-01

    Today's information world, bits of data are processed by semiconductor chips, and stored in the magnetic disk drives. But tomorrow's information technology may see magnetism (spin) and semiconductivity (charge) combined in one 'spintronic' device that exploits both charge and 'spin' to carry data (the best of two worlds). Spintronic devices such as spin valve transistors, spin light emitting diodes, non-volatile memory, logic devices, optical isolators and ultra-fast optical switches are some of the areas of interest for introducing the ferromagnetic properties at room temperature in a semiconductor to make it multifunctional. The potential advantages of such spintronic devices will be higher speed, greater efficiency, and better stability at a reduced power consumption. This Thesis contains two main topics: In-depth understanding of magnetism in Mn doped ZnO, and our search and identification of at least six new above room temperature ferromagnetic semiconductors. Both complex doped ZnO based new materials, as well as a number of nonoxides like phosphides, and sulfides suitably doped with Mn or Cu are shown to give rise to ferromagnetism above room temperature. Some of the highlights of this work are discovery of room temperature ferromagnetism in: (1) ZnO:Mn (paper in Nature Materials, Oct issue, 2003); (2) ZnO doped with Cu (containing no magnetic elements in it); (3) GaP doped with Cu (again containing no magnetic elements in it); (4) Enhancement of Magnetization by Cu co-doping in ZnO:Mn; (5) CdS doped with Mn, and a few others not reported in this thesis. We discuss in detail the first observation of ferromagnetism above room temperature in the form of powder, bulk pellets, in 2-3 mu-m thick transparent pulsed laser deposited films of the Mn (<4 at. percent) doped ZnO. High-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS) spectra recorded from 2 to 200nm areas showed homogeneous

  5. Ordering phenomena in transition-metal-oxide heterostructures

    Frano Pereira, Alex Manuel

    2014-01-27

    This doctoral work presents a study of ordered ground states of transition metal oxide compounds and multilayers using resonant elastic soft x-ray scattering. The technique has developed over the last decades and become especially useful when sample sizes are limited like the case of nanometer-scale films and superlattices. By scattering with photon energies on resonance with the element's electronic transitions, it is an element-specific, sensitive tool providing a combination of spectroscopic and spatial information. The thesis is divided into two central topics. The first part focuses on the investigation of perovskite-type, rare-earth nickelate heterostructures. X-rays tuned to the Ni L{sub 3}-edge were used to unveil unprecedented diffraction evidence of long range magnetic order in LaNiO{sub 3}-RXO{sub 3} (RXO{sub 3} = LaAlO{sub 3}, DyScO{sub 3}) superlattices. We report on the appearance of magnetic order in such systems with a propagation vector of Q{sub SDW} = ((1)/(4),(1)/(4),l) in pseudocubic notation, similar to bulk rare earth nickelates with R ≠ La. With LaNiO{sub 3} being paramagnetic in its bulk form, the magnetic Bragg peak is only present in superlattices where the thickness of the LaNiO{sub 3} layers approaches the 2-dimensional limit. Besides the thickness dependence, the magnetic order was probed on samples grown on varying strain-inducing substrates. Azimuthal scans around Q{sub SDW} were done to determine the orientation of the spin spiral under these different conditions. We will explain how the reorientation of the spins can be understood by the magneto-crystalline anisotropy which is determined by the relative occupation of the Ni d-orbitals via spin-orbit coupling. First steps towards control of the spin spiral's orientation will be outlined, and along with the high remanent conductivity found in the magnetic spiral state, an outlook for metallic antiferromagnetic spintronics will be discussed. The second part of this thesis

  6. Ordering phenomena in transition-metal-oxide heterostructures

    Frano Pereira, Alex Manuel

    2014-01-01

    This doctoral work presents a study of ordered ground states of transition metal oxide compounds and multilayers using resonant elastic soft x-ray scattering. The technique has developed over the last decades and become especially useful when sample sizes are limited like the case of nanometer-scale films and superlattices. By scattering with photon energies on resonance with the element's electronic transitions, it is an element-specific, sensitive tool providing a combination of spectroscopic and spatial information. The thesis is divided into two central topics. The first part focuses on the investigation of perovskite-type, rare-earth nickelate heterostructures. X-rays tuned to the Ni L 3 -edge were used to unveil unprecedented diffraction evidence of long range magnetic order in LaNiO 3 -RXO 3 (RXO 3 = LaAlO 3 , DyScO 3 ) superlattices. We report on the appearance of magnetic order in such systems with a propagation vector of Q SDW = ((1)/(4),(1)/(4),l) in pseudocubic notation, similar to bulk rare earth nickelates with R ≠ La. With LaNiO 3 being paramagnetic in its bulk form, the magnetic Bragg peak is only present in superlattices where the thickness of the LaNiO 3 layers approaches the 2-dimensional limit. Besides the thickness dependence, the magnetic order was probed on samples grown on varying strain-inducing substrates. Azimuthal scans around Q SDW were done to determine the orientation of the spin spiral under these different conditions. We will explain how the reorientation of the spins can be understood by the magneto-crystalline anisotropy which is determined by the relative occupation of the Ni d-orbitals via spin-orbit coupling. First steps towards control of the spin spiral's orientation will be outlined, and along with the high remanent conductivity found in the magnetic spiral state, an outlook for metallic antiferromagnetic spintronics will be discussed. The second part of this thesis will address the observation of charge density

  7. Synthesis of Mn doped ZnO nanoparticles with biocompatible capping

    Sharda; Jayanthi, K.; Chawla, Santa

    2010-01-01

    Free standing nanoparticles of ZnO doped with transition metal ion Mn have been prepared by solid state reaction method at 500 deg. C. X-ray diffraction (XRD) analysis confirmed high quality monophasic wurtzite hexagonal structure with particle size of 50 nm and no signature of dopant as separate phase. Incorporation of Mn has been confirmed with EDS. Bio-inorganic interface was created by capping the nanoparticles with heteromultifunctional organic stabilizer mercaptosuccinic acid (MSA). The surface morphological studies by scanning electron microscopy (SEM) showed formation of spherical particles and the nanoballs grow in size uniformly with MSA capping. MSA capping has been confirmed with thermo gravimetric analysis (TGA) and FTIR. Photoluminescence (PL) studies show that the ZnO:Mn 2+ particles are excitable by blue light and emits in orange and red. Occurrence of room temperature ferromagnetism in Mn doped ZnO makes such biocompatible luminescent magnetic nanoparticles very promising material.

  8. Electronic structure and magnetic properties of Sc doped EuO thin films

    Reisner, Andreas; Altendorf, Simone; Chang, Chun-Fu; Tjeng, Liu Hao [Max-Planck-Institute for Chemical Physics of Solids, Noethnitzer Str.40, 01187 Dresden (Germany); Lin, Hong-Ji; Chen, Chien-Te [National Synchrotron Radiation Research Center, Hsin-Ann Road, 30076 Hsinchu, Taiwan (China)

    2013-07-01

    Europium monoxide is a ferromagnetic semiconductor with a Curie temperature T{sub C} of 69 K. Upon doping the material can show an increase of the Curie temperature, a metal-to-insulator transition and a high spin polarization of the charge carriers. Applying pressure can also enhance T{sub C}. Mostly other trivalent rare earth metals are used as dopant. Here we set out to explore the possibility of using transition metals as dopants. As a start we focus on the non magnetic Sc ions. We are able to achieve excellent crystalline growth of Sc-doped EuO thin films on YSZ (001) substrates using molecular beam epitaxy. We report our results on the crystal structure as characterized by RHEED and LEED, the electronic structure as determined by XPS and ARPES, and on the magnetic properties as measured by SQUID.

  9. Correlated effective field theory in transition metal compounds

    Mukhopadhyay, Subhasis; Chatterjee, Ibha

    2004-01-01

    Mean field theory is good enough to study the physical properties at higher temperatures and in higher dimensions. It explains the critical phenomena in a restricted sense. Near the critical temperatures, when fluctuations become important, it may not give the correct results. Similarly in low dimensions, the correlations become important and the mean field theory seems to be inadequate to explain the physical phenomena. At low-temperatures too, the quantum correlations become important and these effects are to be treated in an appropriate way. In 1974, Prof. M.E. Lines of Bell Laboratories, developed a theory which goes beyond the mean field theory and is known as the correlated effective field (CEF) theory. It takes into account the fluctuations in a semiempirical way. Lines and his collaborators used this theory to explain the short-range correlations and their anisotropy in the paramagnetic phase. Later Suzuki et al., Chatterjee and Desai, Mukhopadhyay and Chatterjee applied this theory to the magnetically ordered phase and a tremendous success of the theory has been found in real systems. The success of the CEF theory is discussed in this review. In order to highlight the success of this theory, earlier effective field theories and their improvements over mean field theories e.g., Bethe-Peierls-Weiss method, reaction field approximation, etc., are also discussed in this review for completeness. The beauty of the CEF theory is that it is mean field-like, but captures the essential physics of real systems to a great extent. However, this is a weak correlated theory and as a result is inappropriate for the metallic phase when strong correlations become important. In recent times, transition metal oxides become important due to the discovery of the high-temperature superconductivity and the colossal magnetoresistance phenomena. These oxides seem to be Mott insulators and undergo an insulator to metal transition by applying magnetic field, pressure and by changing

  10. Tethered Transition Metals Promoted Photocatalytic System for Efficient Hydrogen Evolutions

    Takanabe, Kazuhiro; Isimjan, Tayirjan; Yu, Weili; Del Gobbo, Silvano; Xu, Wei

    2015-01-01

    The present invention is directed, at least in part, to a process for improving the efficiency of a photocatalyst (a semiconductor photocatalyst) by tethering (depositing) a metal (e.g., metal ions of a late transition metal, such as nickel) to the semiconductor (photocatalyst) surface through the use of an organic ligand. More specifically, 1,2-ethanedithiol (EDT) functions as an excellent molecular linker (organic ligand) to attach a transition metal complex (e.g., nickel (Ni.sup.2+ ions)) to the semiconductor surface, which can be in the form of a cadmium sulfide surface. The photocatalyst has particular utility in generating hydrogen from H.sub.2S.

  11. Tethered Transition Metals Promoted Photocatalytic System for Efficient Hydrogen Evolutions

    Takanabe, Kazuhiro

    2015-03-05

    The present invention is directed, at least in part, to a process for improving the efficiency of a photocatalyst (a semiconductor photocatalyst) by tethering (depositing) a metal (e.g., metal ions of a late transition metal, such as nickel) to the semiconductor (photocatalyst) surface through the use of an organic ligand. More specifically, 1,2-ethanedithiol (EDT) functions as an excellent molecular linker (organic ligand) to attach a transition metal complex (e.g., nickel (Ni.sup.2+ ions)) to the semiconductor surface, which can be in the form of a cadmium sulfide surface. The photocatalyst has particular utility in generating hydrogen from H.sub.2S.

  12. Transition metal carbide nanocomposite and amorphous thin films

    Tengstrand, Olof

    2014-01-01

    This thesis explores thin films of binary and ternary transition metal carbides, in the Nb-C, Ti-Si-C, Nb-Si-C, Zr-Si-C, and Nb-Ge-C systems. The electrical and mechanical properties of these systems are affected by their structure and here both nanocomposite and amorphous thin films are thus investigated. By appropriate choice of transition metal and composition the films can be designed to be multifunctional with a combination of properties, such as low electric resistivity, low contact res...

  13. Enhancment of ferromagnetism in Ba and Er co-doped BiFeO{sub 3} nanoparticles

    Naeimi, A.S., E-mail: naeimi.a.s@gmail.com [Department of Physics, Aliabad Katoul Branch, Islamic Azad University, Aliabad Katoul (Iran, Islamic Republic of); Dehghan, E.; Sanavi Khoshnoud, D. [Department of Physics, Semnan University, Semnan 35195-363 (Iran, Islamic Republic of); Gholizadeh, A. [School of Physics, Damghan University (DU), Damghan (Iran, Islamic Republic of)

    2015-11-01

    Bi{sub 1−y−x}Ba{sub y}Er{sub x}FeO{sub 3} [BB{sub y}E{sub x}FO, (0.13≤y≤0.17, 0≤x≤0.2)] nanoparticles were successfully synthesized by a sol–gel method. The structural, microstructural and magnetic properties have been investigated, using X-ray diffraction, Raman scattering, field emission scanning electron microscopy (FE-SEM) and magnetometry measurements at room temperature. The refinement of X-ray diffraction pattern of BB{sub 0.15}E{sub 0}FO indicates a phase transition from rhombohedral (R3c) to tetragonal (P4mm) with increasing Ba content and a transition from the coexistence of rhombohedral–tetragonal phase to orthorhombic (Pbnm) in BB{sub 0.15}E{sub x}FO samples with increasing Er concentration. The Raman analysis confirms crystal phase transition in BB{sub 0.15}E{sub x}FO compounds. The FE-SEM and TEM analysis show that the average nanoparticle size is about 50–100 nm and it decreases with Er concentration. The remnant magnetisation of BB{sub 0.15}E{sub 0.1}FO sample (M{sub r}=0.98 emu/g) is approximately two times greater than compared to BB{sub 0.15}E{sub 0}FO (M{sub r}=0.51 emu/g) that may be attributed to the collapse of spin structure and modifying exchange interactions because of Er{sup +3} doping. This enhancement in magnetic properties at room temperature can play an important role for the practical applications. - Highlights: • Bi{sub 1−y−x}Ba{sub y}Er{sub x}FeO{sub 3} nanoparticles were successfully synthesized by a sol–gel route. • X-ray diffraction and Raman spectroscopy measurements confirmed a phase transition from rhombohedral–orthorhombic. • Considerable enhancement in magnetisation of BiFeO{sub 3} is obtained with Ba and Er co-doping.

  14. Weak doping dependence of the antiferromagnetic coupling between nearest-neighbor Mn2 + spins in (Ba1 -xKx) (Zn1-yMny) 2As2

    Surmach, M. A.; Chen, B. J.; Deng, Z.; Jin, C. Q.; Glasbrenner, J. K.; Mazin, I. I.; Ivanov, A.; Inosov, D. S.

    2018-03-01

    Dilute magnetic semiconductors (DMS) are nonmagnetic semiconductors doped with magnetic transition metals. The recently discovered DMS material (Ba1 -xKx) (Zn1-yMny) 2As2 offers a unique and versatile control of the Curie temperature TC by decoupling the spin (Mn2 +, S =5 /2 ) and charge (K+) doping in different crystallographic layers. In an attempt to describe from first-principles calculations the role of hole doping in stabilizing ferromagnetic order, it was recently suggested that the antiferromagnetic exchange coupling J between the nearest-neighbor Mn ions would experience a nearly twofold suppression upon doping 20% of holes by potassium substitution. At the same time, further-neighbor interactions become increasingly ferromagnetic upon doping, leading to a rapid increase of TC. Using inelastic neutron scattering, we have observed a localized magnetic excitation at about 13 meV associated with the destruction of the nearest-neighbor Mn-Mn singlet ground state. Hole doping results in a notable broadening of this peak, evidencing significant particle-hole damping, but with only a minor change in the peak position. We argue that this unexpected result can be explained by a combined effect of superexchange and double-exchange interactions.

  15. Spin-polarized structural, elastic, electronic and magnetic properties of half-metallic ferromagnetism in V-doped ZnSe

    Monir, M. El Amine.; Baltache, H. [Laboratoire de Physique Quantique de la Matière et de la Modélisation Mathématique (LPQ3M), Faculté des Sciences, Université de Mascara, Mascara 29000 (Algeria); Murtaza, G., E-mail: murtaza@icp.edu.pk [Materials Modeling Lab, Department of Physics, Islamia College University, Peshawar (Pakistan); Khenata, R., E-mail: khenata_rabah@yahoo.fr [Laboratoire de Physique Quantique de la Matière et de la Modélisation Mathématique (LPQ3M), Faculté des Sciences, Université de Mascara, Mascara 29000 (Algeria); Ahmed, Waleed K. [ERU, Faculty of Engineering, United Arab Emirates University, Al Ain (United Arab Emirates); Bouhemadou, A. [Laboratory for Developing New Materials and their Characterization, Department of Physics, Faculty of Science, University of Setif, 19000 Setif (Algeria); Omran, S. Bin [Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451 (Saudi Arabia); Seddik, T. [Laboratoire de Physique Quantique de la Matière et de la Modélisation Mathématique (LPQ3M), Faculté des Sciences, Université de Mascara, Mascara 29000 (Algeria)

    2015-01-15

    Based on first principles spin-polarized density functional theory, the structural, elastic electronic and magnetic properties of Zn{sub 1−x}V{sub x}Se (for x=0.25, 0.50, 0.75) in zinc blende structure have been studied. The investigation was done using the full-potential augmented plane wave method as implemented in WIEN2k code. The exchange-correlation potential was treated with the generalized gradient approximation PBE-GGA for the structural and elastic properties. Moreover, the PBE-GGA+U approximation (where U is the Hubbard correlation terms) is employed to treat the “d” electrons properly. A comparative study between the band structures, electronic structures, total and partial densities of states and local moments calculated within both GGA and GGA+U schemes is presented. The analysis of spin-polarized band structure and density of states shows the half-metallic ferromagnetic character and are also used to determine s(p)-d exchange constants N{sub 0}α (conduction band ) and N{sub 0}β (valence band) due to Se(4p)–V(3d) hybridization. It has been clearly evidence that the magnetic moment of V is reduced from its free space change value of 3 µ{sub B} and the minor atomic magnetic moment on Zn and Se are generated. - Highlights: • Half metallicity origins by doping V in ZnSe. • PBE-GGA+U approximation is employed to treat the “d” electrons properly. • s(p)-d Exchange constants N{sub 0}α (conduction band ) and N{sub 0}β (valence band) are due to Se(4p)-V(3d) hybridization.

  16. Superconducting Ferromagnetic Nanodiamond.

    Zhang, Gufei; Samuely, Tomas; Xu, Zheng; Jochum, Johanna K; Volodin, Alexander; Zhou, Shengqiang; May, Paul W; Onufriienko, Oleksandr; Kačmarčík, Jozef; Steele, Julian A; Li, Jun; Vanacken, Johan; Vacík, Jiri; Szabó, Pavol; Yuan, Haifeng; Roeffaers, Maarten B J; Cerbu, Dorin; Samuely, Peter; Hofkens, Johan; Moshchalkov, Victor V

    2017-06-27

    Superconductivity and ferromagnetism are two mutually antagonistic states in condensed matter. Research on the interplay between these two competing orderings sheds light not only on the cause of various quantum phenomena in strongly correlated systems but also on the general mechanism of superconductivity. Here we report on the observation of the electronic entanglement between superconducting and ferromagnetic states in hydrogenated boron-doped nanodiamond films, which have a superconducting transition temperature T c ∼ 3 K and a Curie temperature T Curie > 400 K. In spite of the high T Curie , our nanodiamond films demonstrate a decrease in the temperature dependence of magnetization below 100 K, in correspondence to an increase in the temperature dependence of resistivity. These anomalous magnetic and electrical transport properties reveal the presence of an intriguing precursor phase, in which spin fluctuations intervene as a result of the interplay between the two antagonistic states. Furthermore, the observations of high-temperature ferromagnetism, giant positive magnetoresistance, and anomalous Hall effect bring attention to the potential applications of our superconducting ferromagnetic nanodiamond films in magnetoelectronics, spintronics, and magnetic field sensing.

  17. Recent advances in controlled synthesis of two-dimensional transition metal dichalcogenides via vapour deposition techniques

    Shi, Yumeng; Li, Henan; Li, Lain-Jong

    2014-01-01

    In recent years there have been many breakthroughs in two-dimensional (2D) nanomaterials, among which the transition metal dichalcogenides (TMDs) attract significant attention owing to their unusual properties associated with their strictly defined dimensionalities. TMD materials with a generalized formula of MX2, where M is a transition metal and X is a chalcogen, represent a diverse and largely untapped source of 2D systems. Semiconducting TMD monolayers such as MoS2, MoSe2, WSe2 and WS2 have been demonstrated to be feasible for future electronics and optoelectronics. The exotic electronic properties and high specific surface areas of 2D TMDs offer unlimited potential in various fields including sensing, catalysis, and energy storage applications. Very recently, the chemical vapour deposition technique (CVD) has shown great promise to generate high-quality TMD layers with a scalable size, controllable thickness and excellent electronic properties. Wafer-scale deposition of mono to few layer TMD films has been obtained. Despite the initial success in the CVD synthesis of TMDs, substantial research studies on extending the methodology open up a new way for substitution doping, formation of monolayer alloys and producing TMD stacking structures or superlattices. In this tutorial review, we will introduce the latest development of the synthesis of monolayer TMDs by CVD approaches.

  18. First-principles studies on 3d transition metal atom adsorbed twin graphene

    Li, Lele; Zhang, Hong; Cheng, Xinlu; Miyamoto, Yoshiyuki

    2018-05-01

    Twin graphene is a new two-dimensional semiconducting carbon allotrope which is proposed recently. The structural, magnetic and electronic properties are investigated for 3d transition metal (TM) atom adsorbed twin graphene by means of GGA+U calculations. The results show most of single 3d transition metal atom except Zn can make twin graphene magnetization. The adsorption of single TM atom can also make the twin graphene systems turn to half metal (V adsorption), half-semiconductor (Fe adsorption) or metal (Sc, Cr, Mn, Co and Cu adsorption). The semiconducting nature still exists for Ti, Ni and Zn adsorption. All the 3d TM adatoms belong to n-type doping for transferring charge to the neighboring C atoms and have strong covalent bond with these C atoms. The influence of Hubbard U value on half-metallic V adsorbed system is also considered. As the U increases, the system can gradually transform from metal to half metal and metal. The effect of the coverage is investigated for two TM atoms (Sc-Fe) adsorption, too. We can know TM atoms adsorbed twin graphene have potentials to be spintronic device and nanomagnets from the results.

  19. Recent advances in controlled synthesis of two-dimensional transition metal dichalcogenides via vapour deposition techniques

    Shi, Yumeng

    2014-10-20

    In recent years there have been many breakthroughs in two-dimensional (2D) nanomaterials, among which the transition metal dichalcogenides (TMDs) attract significant attention owing to their unusual properties associated with their strictly defined dimensionalities. TMD materials with a generalized formula of MX2, where M is a transition metal and X is a chalcogen, represent a diverse and largely untapped source of 2D systems. Semiconducting TMD monolayers such as MoS2, MoSe2, WSe2 and WS2 have been demonstrated to be feasible for future electronics and optoelectronics. The exotic electronic properties and high specific surface areas of 2D TMDs offer unlimited potential in various fields including sensing, catalysis, and energy storage applications. Very recently, the chemical vapour deposition technique (CVD) has shown great promise to generate high-quality TMD layers with a scalable size, controllable thickness and excellent electronic properties. Wafer-scale deposition of mono to few layer TMD films has been obtained. Despite the initial success in the CVD synthesis of TMDs, substantial research studies on extending the methodology open up a new way for substitution doping, formation of monolayer alloys and producing TMD stacking structures or superlattices. In this tutorial review, we will introduce the latest development of the synthesis of monolayer TMDs by CVD approaches.

  20. Integrating Transition Metals into Nanomaterials: Strategies and Applications

    Fhayli, Karim

    2016-04-14

    Transition metals complexes have been involved in various catalytic, biomedical and industrial applications, but only lately they have been associated with nanomaterials to produce innovative and well-defined new hybrid systems. The introduction of transition metals into nanomaterials is important to bear the advantages of metals to nanoscale and also to raise the stability of nanomaterials. In this dissertation, we study two approaches of associating transition metals into nanomaterials. The first approach is via spontaneous self-organization based assembly of small molecule amphiphiles and bulky hydrophilic polymers to produce organic-inorganic hybrid materials that have nanoscale features and can be precisely controlled depending on the experimental conditions used. These hybrid materials can successfully act as templates to design new porous material with interesting architecture. The second approach studied is via electroless reduction of transition metals on the surface of nanocarbons (nanotubes and nanodiamonds) without using any reducing agents or catalysts. The synthesis of these systems is highly efficient and facile resulting in stable and mechanically robust new materials with promising applications in catalysis.

  1. Superconductivity Series in Transition Metal Dichalcogenides by Ionic Gating

    Shi, Wu; Ye, Jianting; Zhang, Yijin; Suzuki, Ryuji; Yoshida, Masaro; Miyazaki, Jun; Inoue, Naoko; Saito, Yu; Iwasa, Yoshihiro

    2015-01-01

    Functionalities of two-dimensional (2D) crystals based on semiconducting transition metal dichalcogenides (TMDs) have now stemmed from simple field effect transistors (FETs) to a variety of electronic and opto-valleytronic devices, and even to superconductivity. Among them, superconductivity is the

  2. Fluorescence signalling of the transition metal ions: Design strategy ...

    Unknown

    strategy based on the choice of the fluorophore component. N B SANKARAN, S ... skill for the development of fluorosensors of this kind. Further, the ... salts of the transition metal ions have been used for studying the influence of the metal ions.

  3. Catalytic olefin polymerization with early transition metal compounds

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and

  4. Transition metal oxide loaded MCM catalysts for photocatalytic ...

    Transition metal oxide (TiO2, Fe2O3, CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step .... washed consecutively with water and ethanol, and cal- cined at 823 K for 5 .... conversion was observed in 1 h when the reaction was.

  5. Tris-diamine-derived transition metal complexes of flurbiprofen as ...

    admin

    butyrylcholinesterase (BChE) inhibitory activities. Method: Tris-diamine-derived transition metal complexes of Co(II), Ni(II), and Mn(II) were synthesized and characterized ... Conductance measurements indicated that diamine-derived metal complexes of ..... contributes to enhanced biological activity, and provides novel ...

  6. Charge transfer in chromium-transition metal alloys

    Kulakowski, K.; Maksymowicz, A.

    1984-07-01

    The average T-matrix approximation is applied for calculations of charge transfer of 3d-electrons in transition metal alloys. The role of concentration, long-range and short-range atomic order is investigated. The results are in reasonable agreement with experimental data. (author)

  7. Plasmons in metallic monolayer and bilayer transition metal dichalcogenides

    Andersen, Kirsten; Thygesen, Kristian S.

    2013-01-01

    We study the collective electronic excitations in metallic single-layer and bilayer transition metal dichalcogenides (TMDCs) using time dependent density functional theory in the random phase approximation. For very small momentum transfers (below q≈0.02 Å−1), the plasmon dispersion follows the √q...

  8. Reactions of transition metal complexes with cyclic ethers

    Milstein, D.

    1977-02-01

    Three novel reactions of epoxides with homogeneous transition-metal catalysts have been explored: (a) the selective rearrangement of internal epoxides to ketones; (b) the cleavage of C-C bond in epoxides having electron-attracting substituents; (c) the transformation of terminal epoxides into esters. Based on an intensive kinetic study, a general mechanism for the transformations of epoxides is postulated

  9. Direct NO decomposition over stepped transition-metal surfaces

    Falsig, Hanne; Bligaard, Thomas; Christensen, Claus H.

    2007-01-01

    We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition-metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Bronsted-Evans-Polanyi (BEP) relations for the activation barriers of dissociation...

  10. Integrating Transition Metals into Nanomaterials: Strategies and Applications

    Fhayli, Karim

    2016-01-01

    Transition metals complexes have been involved in various catalytic, biomedical and industrial applications, but only lately they have been associated with nanomaterials to produce innovative and well-defined new hybrid systems. The introduction of transition metals into nanomaterials is important to bear the advantages of metals to nanoscale and also to raise the stability of nanomaterials. In this dissertation, we study two approaches of associating transition metals into nanomaterials. The first approach is via spontaneous self-organization based assembly of small molecule amphiphiles and bulky hydrophilic polymers to produce organic-inorganic hybrid materials that have nanoscale features and can be precisely controlled depending on the experimental conditions used. These hybrid materials can successfully act as templates to design new porous material with interesting architecture. The second approach studied is via electroless reduction of transition metals on the surface of nanocarbons (nanotubes and nanodiamonds) without using any reducing agents or catalysts. The synthesis of these systems is highly efficient and facile resulting in stable and mechanically robust new materials with promising applications in catalysis.

  11. Exciton ionization in multilayer transition-metal dichalcogenides

    Pedersen, Thomas Garm; Latini, Simone; Thygesen, Kristian Sommer

    2016-01-01

    Photodetectors and solar cells based on materials with strongly bound excitons rely crucially on field-assisted exciton ionization. We study the ionization process in multilayer transition-metal dichalcogenides (TMDs) within the Mott-Wannier model incorporating fully the pronounced anisotropy...

  12. Coordination to transition metal surfaces : a theoretical study

    Santen, van R.A.

    1985-01-01

    A theoretical framework is developed that describes the chemisorption of CO to transition metal surfaces analogous to the HOMO-LUMO concept of MO theory. An explanation is given for the exptl. observation that CO adsorbs on top at the (111), face of Pt, but bridge at the (111) face of Ni. One is due

  13. Fullerenes as a new type of ligands for transition metals

    Sokolov, V.I.

    2007-01-01

    Fullerenes are considered as ligands in transition metal π-complexes. The following aspects are discussed: metals able to form π-complexes with fullerenes (Zr, V, Ta, Mo, W, Re, Ru, etc.); haptic numbers; homo- and hetero ligand complexes; ligand compatibility with fullerenes for different metals, including fullerenes with a disturbed structure of conjugation [ru

  14. Vibrational properties of vacancy in bcc transition metals using ...

    The calculated results of the formation entropy of the vacancy compared well with other available ... for Fe, Mo and W transition metals employing a third-neighbour model. ... For the atomic electron density we have chosen a power law: f (r) = fe.

  15. Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

    Chen, Wei-Fu; Iyer, Shweta; Iyer, Shilpa; Sasaki, Kotaro; Muckerman, James T.; Fujita, Etsuko

    2017-02-28

    A catalytic composition from earth-abundant transition metal salts and biomass is disclosed. A calcined catalytic composition formed from soybean powder and ammonium molybdate is specifically exemplified herein. Methods for making the catalytic composition are disclosed as are electrodes for hydrogen evolution reactions comprising the catalytic composition.

  16. Reactivity of monoolefin ligand in transition metal complexes

    Rybinskaya, M.I.

    1978-01-01

    The main tendencies in the coordinated olefin ligand property changes are discussed in the transition metal complexes in comparison with free olefins. The review includes the papers published from 1951 up to 1976. It has been shown that in complexes with transition metal cations olefin π-base acquires the ability to react with nucleophylic reagents. Olefin π-acids in complexes with zero valent metals are easily subjected to electrophylic reagent action. At coordination with transition metal cations the olefin properties are generally preserved, while in the zero-valent metal complexes the nonsaturated ligand acquires the properties of a saturated compounds. The ability of transition metal cations in complexes to intensify reactions of nucleophylic bimolecular substitution of vinyl halogen is clearly detected in contrast to the zero valent metal complexes. It has been shown that investigations of the coordinated olefin ligand reactivity give large possibilities in the further development of the organic synthesis. Some reactions are taken as the basis of important industrial processes

  17. [Non-empirical interatomic potentials for transition metals

    1993-01-01

    The report is divided into the following sections: potential-energy functions for d-band metals, potential-energy functions for aluminides and quasicrystals, electronic structure of complex structures and quasicrystals, potential-energy functions in transition-metal oxides, applications to defect structure and mechanical properties, and basic theory of interatomic potentials

  18. Electronic and thermodynamic properties of transition metal elements and compounds

    Haeglund, J.

    1993-01-01

    This thesis focuses on the use of band-structure calculations for studying thermodynamic properties of solids. We discuss 3d-, 4d- and 5d-transition metal carbides and nitrides. Through a detailed comparison between theoretical and experimental results, we draw conclusions on the character of the atomic bonds in these materials. We show how electronic structure calculations can be used to give accurate predictions for bonding energies. Part of the thesis is devoted to the application of the generalized gradient approximation in electronic structure calculations on transition metals. For structures with vibrational disorder, we present a method for calculating averaged phonon frequencies without using empirical information. For magnetic excitations, we show how a combined use of theoretical results and experimental data can yield information on magnetic fluctuations at high temperatures. The main results in the thesis are: Apart for an almost constant shift, theoretically calculated bonding energies for transition metal carbides and nitrides agree with experimental data or with values from analysis of thermochemical information. The electronic spectrum of transition metal carbides and nitrides can be separated into bonding, antibonding and nonbonding electronic states. The lowest enthalpy of formation for substoichiometric vanadium carbide VC 1-X at zero temperature and pressure occurs for a structure containing vacancies (x not equal to 0). The generalized gradient approximation improves theoretical calculated cohesive energies for 3d-transition metals. Magnetic phase transitions are sensitive to the description of exchange-correlation effects in electronic structure calculations. Trends in Debye temperatures can be successfully analysed in electronic structure calculations on disordered lattices. For the elements, there is a clear dependence on the crystal structure (e.g., bcc, fcc or hcp). Chromium has fluctuating local magnetic moments at temperatures well above

  19. Unraveling the Origin of Magnetism in Mesoporous Cu-Doped SnO₂ Magnetic Semiconductors.

    Fan, Junpeng; Menéndez, Enric; Guerrero, Miguel; Quintana, Alberto; Weschke, Eugen; Pellicer, Eva; Sort, Jordi

    2017-10-25

    The origin of magnetism in wide-gap semiconductors doped with non-ferromagnetic 3d transition metals still remains intriguing. In this article, insights in the magnetic properties of ordered mesoporous Cu-doped SnO₂ powders, prepared by hard-templating, have been unraveled. Whereas, both oxygen vacancies and Fe-based impurity phases could be a plausible explanation for the observed room temperature ferromagnetism, the low temperature magnetism is mainly and unambiguously arising from the nanoscale nature of the formed antiferromagnetic CuO, which results in a net magnetization that is reminiscent of ferromagnetic behavior. This is ascribed to uncompensated spins and shape-mediated spin canting effects. The reduced blocking temperature, which resides between 30 and 5 K, and traces of vertical shifts in the hysteresis loops confirm size effects in CuO. The mesoporous nature of the system with a large surface-to-volume ratio likely promotes the occurrence of uncompensated spins, spin canting, and spin frustration, offering new prospects in the use of magnetic semiconductors for energy-efficient spintronics.

  20. Two-Dimensional Transition Metal Oxide and Chalcogenide-Based Photocatalysts

    Haque, Farjana; Daeneke, Torben; Kalantar-zadeh, Kourosh; Ou, Jian Zhen

    2018-06-01

    Two-dimensional (2D) transition metal oxide and chalcogenide (TMO&C)-based photocatalysts have recently attracted significant attention for addressing the current worldwide challenges of energy shortage and environmental pollution. The ultrahigh surface area and unconventional physiochemical, electronic and optical properties of 2D TMO&Cs have been demonstrated to facilitate photocatalytic applications. This review provides a concise overview of properties, synthesis methods and applications of 2D TMO&C-based photocatalysts. Particular attention is paid on the emerging strategies to improve the abilities of light harvesting and photoinduced charge separation for enhancing photocatalytic performances, which include elemental doping, surface functionalization as well as heterojunctions with semiconducting and conductive materials. The future opportunities regarding the research pathways of 2D TMO&C-based photocatalysts are also presented. [Figure not available: see fulltext.

  1. Observation of large low field magnetoresistance in ramp-edge tunneling junctions based on doped manganite ferromagnetic electrodes and a SrTiO{sub 3} insulator

    Kwon, C.; Jia, Q.X.; Fan, Y.; Hundley, M.F.; Reagor, D.W.; Hawley, M.E.; Peterson, D.E.

    1998-07-01

    The authors report the fabrication of ferromagnet-insulator-ferromagnet junction devices using a ramp-edge geometry based on (La{sub 0.7}Sr{sub 0.3})MnO{sub 3} ferromagnetic electrodes and a SrTiO{sub 3} insulator. The multilayer thin films were deposited using pulsed laser deposition and the devices were patterned using photolithography and ion milling. As expected from the spin-dependent tunneling, the junction magnetoresistance depends on the relative orientation of the magnetization in the electrodes. The maximum junction magnetoresistance (JMR) of 30% is observed below 300 Oe at low temperatures (T < 100 K).

  2. Prediction of two-dimensional diluted magnetic semiconductors: Doped monolayer MoS2 systems

    Cheng, Yingchun; Guo, Z. B.; Mi, W. B.; Schwingenschlö gl, Udo; Zhu, Zhiyong

    2013-01-01

    Using first-principles calculations, we propose a two-dimensional diluted magnetic semiconductor: monolayer MoS2 doped by transition metals. Doping of transition metal atoms from the IIIB to VIB groups results in nonmagnetic states, since the number

  3. Photocatalytic and magnetic properties of anatase doped with V.theoretical study swig DFT

    Cabeza, Gabriela F; Castellani, Norberto J

    2008-01-01

    The electronic properties and the presence of ferromagnetism in TiO 2 (anatase) doped with vanadium are investigated using calculations of first principles based on the theory of functional density. This work has a double purpose. First, to establish a relationship between the chemical nature of the doping element and the catalytic properties of the volume. Many studies state that anatase is an excellent photocatalytic semiconductor with possible applications in environmental purification and in the photodegradation of organic components. Anatase has a band width of ∼ 3eV, which can be excited only in the presence of ultraviolet light. Doping with transition metals will reduce this and facilitate excitation with visible light. Second, the effect of doping with V on the presence of magnetism in the substrate is clarified. The magnetic moment for an atom isolated from V is known to be 3 mB, while a volume of V is paramagnetic. Studies show that anatase doped with V displays ferromagnetism at room temperature, converting it into a potential diluted magnetic semiconductor (DMS) that may be used in spintronic instruments. The results obtained show that the presence of V produces a narrowing of 27% in the width of the gap favoring the adsorption at greater wave longitudes. Based on an analysis of the states density, the Fermi level does not cross any state indicating that it is an insulant. There are 3d states of the V located in the band width. The spin-up states are next to the Fermi level and the spin-down states are close to the conduction band. The imbalance between both states implies the presence of ferromagnetism. The magnetic moment found is ∼ 1 mB according to the experimental results obtained from the literature

  4. Spin relaxation and the Kondo effect in transition metal dichalcogenide monolayers

    Rostami, Habib; Moghaddam, Ali G; Asgari, Reza

    2016-01-01

    We investigate the spin relaxation and Kondo resistivity caused by magnetic impurities in doped transition metal dichalcogenide monolayers. We show that momentum and spin relaxation times, due to the exchange interaction by magnetic impurities, are much longer when the Fermi level is inside the spin-split region of the valence band. In contrast to the spin relaxation, we find that the dependence of Kondo temperature T K on the doping is not strongly affected by the spin–orbit induced splitting, although only one of the spin species are present at each valley. This result, which is obtained using both perturbation theory and the poor man’s scaling methods, originates from the intervalley spin-flip scattering in the spin-split region. We further demonstrate the decline in the conductivity with temperatures close to T K , which can vary with the doping. Our findings reveal the qualitative difference with the Kondo physics in conventional metallic systems and other Dirac materials. (paper)

  5. Co-doping induced coexistence of superconductivity and ferromagnetism in Bi{sub 3.9}Co{sub 0.1}O{sub 4}S{sub 3}

    Yu, Chuan [Department of Physics, Shanghai University, Shanghai 200444 (China); Feng, Zhenjie, E-mail: fengzhenjie@t.shu.edu.cn [Department of Physics, Shanghai University, Shanghai 200444 (China); Shanghai Key Laboratory of High Temperature Superconductors, Shanghai 200444 (China); Yin, Xunqing; Li, Qing; Kang, Baojuan [Department of Physics, Shanghai University, Shanghai 200444 (China); Lu, Bo [Laboratory for Microstructures, Shanghai University, Shanghai 200444 (China); Jing, Chao; Cao, Shixun [Department of Physics, Shanghai University, Shanghai 200444 (China); Shanghai Key Laboratory of High Temperature Superconductors, Shanghai 200444 (China); Zhang, Jincang [Department of Physics, Shanghai University, Shanghai 200444 (China); Materials Genome Institute, Shanghai University, Shanghai 200444 (China)

    2016-09-15

    Highlights: • Bi{sub 4}O{sub 4}S{sub 3} is a new discovered layered superconductor. Some doping effects, such as Ag, Cu, and Pb, are studied, the superconductivity is suppressed in these doping samples. We doped the Ni magnetic ions to the system, it is interesting that the superconductivity is not suppressed in x = 0.1 sample. Meanwhile, the coexistence of the superconductivity and magnetism is observed in the samples from the M-vs. –H loops. - Abstract: The effects of Co doping on the physical properties of the Bi{sub 4}O{sub 4}S{sub 3} system was studied. We discovered that stable Bi{sub 3.9}Co{sub 0.1}O{sub 4}S{sub 3} compound exhibits both long-range ferromagnetism and enhanced superconductivity with thermodynamic evidences for Tc ∼ 5.5 K. We found that there is an anomalous feature which represents superconducting transition in the hysteretic M-vs.-H loops for Bi{sub 3.9}Co{sub 0.1}O{sub 4}S{sub 3} at T = 3 K.

  6. Preparation and characterization of several transition metal oxides

    Wold, A.; Dwight, K.

    1989-01-01

    The structure-property relationships of several conducting transition metal oxides, as well as their preparative methods, are presented in this paper. The importance of preparing homogeneous phases with precisely known stoichiometry is emphasized. A comparison is also made of the various techniques used to prepare both polycrystalline and single crystal samples. For transition metal oxides, the metallic properties are discussed either in terms of metal-metal distances which are short enough to result in metallic behavior, or in terms of the formation of a π* conduction band resulting from covalent metal-oxygen interactions. Metallic behavior is observed when the conduction bands are populated with either electrons or holes. The concentration of these carriers can be affected by either cation or anion substitutions. The discussion in this presentation will be limited to the elements Re, Ti, V, Cr, Mo, and Cu

  7. Control of interlayer physics in 2H transition metal dichalcogenides

    Wang, Kuang-Chung; Stanev, Teodor K.; Valencia, Daniel; Charles, James; Henning, Alex; Sangwan, Vinod K.; Lahiri, Aritra; Mejia, Daniel; Sarangapani, Prasad; Povolotskyi, Michael; Afzalian, Aryan; Maassen, Jesse; Klimeck, Gerhard; Hersam, Mark C.; Lauhon, Lincoln J.; Stern, Nathaniel P.; Kubis, Tillmann

    2017-12-01

    It is assessed in detail both experimentally and theoretically how the interlayer coupling of transition metal dichalcogenides controls the electronic properties of the respective devices. Gated transition metal dichalcogenide structures show electrons and holes to either localize in individual monolayers, or delocalize beyond multiple layers—depending on the balance between spin-orbit interaction and interlayer hopping. This balance depends on the layer thickness, momentum space symmetry points, and applied gate fields. The design range of this balance, the effective Fermi levels, and all relevant effective masses is analyzed in great detail. A good quantitative agreement of predictions and measurements of the quantum confined Stark effect in gated MoS2 systems unveils intralayer excitons as the major source for the observed photoluminescence.

  8. Structural models for amorphous transition metal binary alloys

    Ching, W.Y.; Lin, C.C.

    1976-01-01

    A dense random packing of 445 hard spheres with two different diameters in a concentration ratio of 3 : 1 was hand-built to simulate the structure of amorphous transition metal-metalloid alloys. By introducing appropriate pair potentials of the Lennard-Jones type, the structure is dynamically relaxed by minimizing the total energy. The radial distribution functions (RDF) for amorphous Fe 0 . 75 P 0 . 25 , Ni 0 . 75 P 0 . 25 , Co 0 . 75 P 0 . 25 are obtained and compared with the experimental data. The calculated RDF's are resolved into their partial components. The results indicate that such dynamically constructed models are capable of accounting for some subtle features in the RDF of amorphous transition metal-metalloid alloys

  9. Conductive transition metal oxide nanostructured electrochromic material and optical switching devices constructed thereof

    Mattox, Tracy M.; Koo, Bonil; Garcia, Guillermo; Milliron, Delia J.; Trizio, Luca De; Dahlman, Clayton

    2017-10-10

    An electrochromic device includes a nanostructured transition metal oxide bronze layer that includes one or more transition metal oxide and one or more dopant, a solid state electrolyte, and a counter electrode. The nanostructured transition metal oxide bronze selectively modulates transmittance of near-infrared (NIR) spectrum and visible spectrum radiation as a function of an applied voltage to the device.

  10. Liquid state properties of certain noble and transition metals

    Bhuiyan, G.M.; Rahman, A.; Khaleque, M.A.; Rashid, R.I.M.A.; Mujibur Rahman, S.M.

    1998-07-01

    Certain structural, thermodynamic and atomic transport properties of a number of liquid noble and transition metals are reported. The underlying theory combines together a simple form of the N-body potential and the thermodynamically self-consistent variational modified hypernetted chain (VMHNC) theory of liquid. The static structure factors calculated by using the VMHNC resemble the hard sphere (HS) values. Consequently the HS model is used to calculate the thermodynamic properties viz. specific heat, entropy, isothermal compressibility and atomic transport properties. (author)

  11. Charge transfers in complex transition metal alloys (Ti2Fe)

    Abramovici, G.

    1998-01-01

    We introduce a new non-orthogonal tight-binding model, for complex alloys, in which electronic structure is characterized by charge transfers. We give the analytic calculation of a charge transfer, in which overlapping two-center terms are rigorously taken into account. Then, we apply numerically this result to an approximant phase of a quasicrystal of Ti 2 Fe alloy. This model is more particularly adapted to transition metals, and gives realistic densities of states. (orig.)

  12. Magnetic properties of fcc Ni-based transition metal alloy

    Kudrnovský, Josef; Drchal, Václav

    2009-01-01

    Roč. 100, č. 9 (2009), s. 1193-1196 ISSN 1862-5282 R&D Projects: GA MŠk OC 150; GA AV ČR IAA100100616 Institutional research plan: CEZ:AV0Z10100520 Keywords : transition metal alloys * Ni-based * pair exchange interactions * Curie temperatures * renormalized RPA Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.862, year: 2009

  13. The dynamic behavior of the exohedral transition metal complexes ...

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 7. The dynamic behavior of the exohedral transition metal complexes of B₄₀ : η⁶- and η⁷-B₄₀Cr(CO) ₃ and Cr(CO) ₃η⁷-B₄η₀-Cr(CO) ₃. NAIWRIT KARMODAK ELUVATHINGAL D JEMMIS. REGULAR ARTICLE Volume 129 Issue 7 July 2017 pp ...

  14. Organometallic compounds of the lanthanides, actinides and early transition metals

    Cardin, D J [Trinity Coll., Dublin (Ireland); Cotton, S A [Stanground School, Peterborough (UK); Green, M [Bristol Univ. (UK); Labinger, J A [Atlantic Richfield Co., Los Angeles, CA (USA); eds.

    1985-01-01

    This book provides a reference compilation of physical and biographical data on over 1500 of the most important and useful organometallic compounds of the lanthanides, actinides and early transition metals representing 38 different elements. The compounds are listed in molecular formula order in a series of entries in dictionary format. Details of structure, physical and chemical properties, reactions and key references are clearly set out. All the data is fully indexed and a structural index is provided.

  15. Catalytic olefin polymerization with early transition metal compounds

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and arene oxidation. Traditionally, heterogeneous catalysts have been used for the production of large-scale commodity chemicals such as methanol and ammonia and in the production of high octane gasoline...

  16. Immobilization of transition metal ions on zirconium phosphate monolayers

    Melezhik, A.V.; Brej, V.V.

    1998-01-01

    It is shown that ions of transition metals (copper, iron, vanadyl, titanium) are adsorbed on zirconium phosphate monolayers. The zirconium phosphate threshold capacity corresponds to substitution of all protons of hydroxyphosphate groups by equivalent amounts of copper, iron or vanadyl. Adsorption of polynuclear ions is possible in case of titanium. The layered substance with specific surface up to 300 m 2 /g, wherein ultradispersed titanium dioxide particles are intercalirated between zirconium-phosphate layers, is synthesized

  17. The energetics of ordered intermetallic alloys (of the transition metals)

    Watson, R.E.; Weinert, M.; Davenport, J.W.; Fernando, G.W.; Bennett, L.H.

    1992-01-01

    The atomically ordered phases in ordered transition metal alloys are discussed. This chapter is divided into: physical parameters controlling phase stability (Hume-Rothery, structural maps, Miedema Hamiltonian), wave functions ampersand band theory, comment on entropy terms, cohesive energies (electron promotion energies, Hund's rule on orbital effects), structural energies/stabilities of elemental solids, total energies and atomic positions, charge transfer (Au alloys, charge tailing), heats of formation of ordered compounds

  18. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  19. Hydrogen and dihydrogen bonding of transition metal hydrides

    Jacobsen, Heiko

    2008-01-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2 NO(PH 3 ) 2 and a small proton donor H 2 O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions

  20. Hydrogen and dihydrogen bonding of transition metal hydrides

    Jacobsen, Heiko

    2008-04-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2NO(PH 3) 2 and a small proton donor H 2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H⋯H bond of transition metal hydrides contains both covalent and electrostatic contributions.

  1. Hydrogen and dihydrogen bonding of transition metal hydrides

    Jacobsen, Heiko [KemKom, Libellenweg 2, 25917 Leck, Nordfriesland (Germany)], E-mail: jacobsen@kemkom.com

    2008-04-03

    Intermolecular interactions between a prototypical transition metal hydride WH(CO){sub 2}NO(PH{sub 3}){sub 2} and a small proton donor H{sub 2}O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions.

  2. Transition-metal impurities in semiconductors and heterojunction band lineups

    Langer, Jerzy M.; Delerue, C.; Lannoo, M.; Heinrich, Helmut

    1988-10-01

    The validity of a recent proposal that transition-metal impurity levels in semiconductors may serve as a reference in band alignment in semiconductor heterojunctions is positively verified by using the most recent data on band offsets in the following lattice-matched heterojunctions: Ga1-xAlxAs/GaAs, In1-xGaxAsyP1-y/InP, In1-xGaxP/GaAs, and Cd1-xHgxTe/CdTe. The alignment procedure is justified theoretically by showing that transition-metal energy levels are effectively pinned to the average dangling-bond energy level, which serves as the reference level for the heterojunction band alignment. Experimental and theoretical arguments showing that an increasingly popular notion on transition-metal energy-level pinning to the vacuum level is unjustified and must be abandoned in favor of the internal-reference rule proposed recently [J. M. Langer and H. Heinrich, Phys. Rev. Lett. 55, 1414 (1985)] are presented.

  3. Functionalization of 2D transition metal dichalcogenides for biomedical applications

    Li, Zibiao; Wong, Swee Liang

    2017-01-01

    Recent research has revealed a gamut of interesting properties present in layered two-dimensional (2D) transition metal dichalcogenides (TMDCs) such as photoluminescence, comparatively high electron mobility, flexibility, mechanical strength and relatively low toxicity. The large surface to area ratio inherent in these materials also allows easy functionalization and maximal interaction with the external environment. Due to its unique physical and chemical properties, much work has been done in tailoring TMDCs through chemical functionalization for use in a diverse range of biomedical applications as biosensors, drug delivery carriers or even as therapeutic agents. In this review, current progress on the different types of TMDC functionalization for various biological applications will be presented and its future outlook will be discussed. - Highlights: • The different functionalization strategies and approaches of transition metal dichalcogenides are reviewed. • Properties of transition metal dichalcogenides useful for biomedical usage and their methods of synthesis are introduced. • Functionalization approaches are presented according to material type and their different application purpose is discussed.

  4. Density functional study of ferromagnetism in alkali metal thin films

    thickness uniform jellium model (UJM), and it is argued that within LSDA or GGA, alkali metal thin films cannot be claimed to have an FM ground state. Relevance of these results to the experiments on transition metal-doped alkali metal thin films ...

  5. Tetragonal ternary borides: superconductivity, ferromagnetism and the role of scandium

    Matthias, B.T.; Patel, C.K.N.; Barz, H.; Corenzwit, E.; Vandenberg, J.M.

    1978-01-01

    The authors report and discuss two discoveries made while studying the condensation phenomena of ternary rhodium borides, MRh 4 B 4 . M is generally a trivalent transition metal, usually a rare earth element RE. An exception is scandium which by itself does not form an isomorphous boride, but in combination with many other elements will do just that. A suprising correlation between ferromagnetic and superconducting transition temperatures has been found. (Auth.)

  6. On the sol-gel synthesis and thermal, structural, and magnetic studies of transition metal (Ni, Co, Mn) containing ZnO powders

    Thota, Subhash; Dutta, Titas; Kumar, Jitendra [Materials Science Programme, Indian Institute of Technology Kanpur, Kanpur-208016 (India)

    2006-03-01

    Transition metal containing ZnO powders (Zn{sub 1-x}M{sub x}O, 0{<=}x{<=}0.30; M = Ni, Mn, Co) have been synthesized by a sol-gel process using zinc acetate dihydrate, respective acetate and oxalic acid as precursors with ethanol as a solvent. The process essentially involves gel formation, drying at 80 {sup 0}C for 24 h to provide the oxalate, and calcination at 500 {sup 0}C for 2 h to undergo an exothermic reaction and yield Zn{sub 1-x}M{sub x}O powder. Their XRD patterns correspond to a wurtzite hcp structure similar to that of pure ZnO, but with the lattice parameters varying slightly with type and extent of doping. It is shown that the dissolution of nickel and cobalt in ZnO is less than 10 at.%, whereas that of manganese lies between 10 and 15 at.%. Other phases that emerge include NiO (hexagonal, a = 2.954 A, c = 7.236 A), ZnCo{sub 2}O{sub 4} (cubic, a = 8.094 A) and ZnMnO{sub 3} (cubic, a = 8.35 A) in the Ni, Co and Mn containing ZnO systems, respectively. Observations of hysteresis loops both at 10 and 320 K and the nature of ESR spectra provide evidence for the ferromagnetic state in nickel containing ZnO powder. Besides, the deviation occurs in the magnetization versus temperature curves in zero field cooled (ZFC) and field cooled (FC) conditions (blocking temperature T{sub B} being 32 K for 5 at.% Ni). The magnetic behaviour of manganese and cobalt doped zinc oxide is, however, different, namely (i) no hysteresis loops (ii) decrease in magnetization with increase of Mn or Co content, and (iii) identical M-T curves under ZFC and FC conditions. The inverse susceptibility versus temperature curves of Zn{sub 1-x}Mn{sub x}O compounds reveal ferrimagnetism with Neel temperature T{sub N} of 4 K for x = 0.02, but antiferromagnetism for x = 0.15 and 0.25 with Curie-Weiss temperature of -43 and -30 K, respectively.

  7. Synthesis of Mg2FeH6 containing as additives transition metal and transition metal fluorides or carbon

    Zepon, G.; Leiva, D.R.; Botta, W.J.

    2010-01-01

    The Mg 2 FeH 6 is a promising way of storing hydrogen in solid form, composed by elements that have low cost and, at the same time, high volumetric storage density: 150 kg H 2 /m 3 . However, this complex hydride is not easily synthesized as a single phase material. The hydrogen sorption high temperature and slow kinetics are the major limitations for the practical application of the Mg 2 FeH 6 as a hydrogen storage material. Little is known about the effects of additives in Mg 2 FeH 6 based nanocomposites in this work were synthesized by MAE under hydrogen atmosphere nanocomposites based on Mg 2 FeH 6 containing additives as transition metals, transition metals fluorides of transition metals or carbon, in order to obtain information on the effects of the selected additives. To this end, we used characterization techniques such as XRD, SEM and TEM, thermal analysis by DSC and curves made in apparatus PCT.(author)

  8. First principles calculation of anomalous Hall conductivity in ferromagnetic bcc Fe

    Yao, Y.; Kleinman, L.; MacDonald, A. H.; Sinova, J.; Jungwirth, Tomáš; Wang, D. S.; Wang, E.; Niu, Q.

    2004-01-01

    Roč. 92, č. 3 (2004), 037204/1-037204/4 ISSN 0031-9007 R&D Projects: GA ČR GA202/02/0912 Institutional research plan: CEZ:AV0Z1010914 Keywords : transition metal ferromagnet * anomalous Hall effect Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 7.218, year: 2004

  9. Effects of transition-metal ions on the morphology and electrochemical properties of δ-MnO2 for supercapacitors

    Wang, Jia-Wei; Chen, Ya; Chen, Bai-Zhen

    2014-11-01

    δ-MnO2 materials doped with transition-metal cations (Zn, Co, and Ag) were successfully synthesized using a hydrothermal technique. The structures and morphologies of the obtained oxides were analyzed using X-ray diffraction, scanning electron microscopy and Brunauer-Emmett-Teller measurements. Additionally, the electrochemical properties were evaluated through cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic cycling measurements. The results indicate that the pure and doped samples crystallize in the δ form with a layered structure and that the Mn/Zn, Mn/Co and Mn/Ag molar ratios are all approximately 1:0.09. Both the Zn-doped and pure MnO2 materials exhibit a petal-like morphology; however, the former has a higher specific surface area of up to 98.97m2 g-1. Furthermore, the Zn-doped MnO2 exhibits a near-rectangular cyclic voltammetry (CV) curve with broad quasi-reversible redox peaks and a specific capacitance of 182.9 F g-1 at a CV scan rate of 2 mV s-1. The Co-doped material exhibits a distinct spiny-fiber morphology, and the electrochemical performance of this material is significantly worse than that of pure MnO2. The average attenuation rate of the Ag-doped material is only 0.028% after 1000 cycles, which is lower than that of pure MnO2.

  10. Magnetic engineering in 3d transition metals on phosphorene by strain

    Cai, Xiaolin [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China); School of Physics and Electronic Information Engineering, Henan Polytechnic University, Jiaozuo, 454000 (China); Niu, Chunyao, E-mail: niuchunyao@zzu.edu.cn [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China); Wang, Jianjun [College of Science, Zhongyuan University of Technology, Zhengzhou 450007 (China); Yu, Weiyang [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China); School of Physics and Electronic Information Engineering, Henan Polytechnic University, Jiaozuo, 454000 (China); Ren, XiaoYan; Zhu, Zhili [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China)

    2017-04-11

    Using first-principles density functional theory (DFT) calculations, we systematically investigate the strain effects on the adsorption energies, magnetic ordering and electronic properties of 3d transition metal (TM) atoms (from Sc to Co) adsorbed on phosphorene (P). We find that the adsorption energy of TM can be enhanced by compressive strain whereas weakened by tensile strain. Our results show that strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. Importantly, the transitions from antiferromagnetic (AFM) state to ferromagnetic (FM) state or to another different AFM ordering can be induced by strain effect. In addition, we observe the semiconductor to metal or half-metal transitions in some TM@P systems by applying strain. Our findings shed a new light on precisely engineering the magnetic properties and electronic properties of the TM@P systems, which will have great potential applications in spin electronics and other related fields. - Highlights: • The adsorption of TM atoms on phosphorene can be enhanced by compressive strain whereas weakened by tensile strain. • Strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. • Applying strain can induce the semiconductor to metal or half-metal transitions in some TM@P systems.

  11. Magnetic engineering in 3d transition metals on phosphorene by strain

    Cai, Xiaolin; Niu, Chunyao; Wang, Jianjun; Yu, Weiyang; Ren, XiaoYan; Zhu, Zhili

    2017-01-01

    Using first-principles density functional theory (DFT) calculations, we systematically investigate the strain effects on the adsorption energies, magnetic ordering and electronic properties of 3d transition metal (TM) atoms (from Sc to Co) adsorbed on phosphorene (P). We find that the adsorption energy of TM can be enhanced by compressive strain whereas weakened by tensile strain. Our results show that strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. Importantly, the transitions from antiferromagnetic (AFM) state to ferromagnetic (FM) state or to another different AFM ordering can be induced by strain effect. In addition, we observe the semiconductor to metal or half-metal transitions in some TM@P systems by applying strain. Our findings shed a new light on precisely engineering the magnetic properties and electronic properties of the TM@P systems, which will have great potential applications in spin electronics and other related fields. - Highlights: • The adsorption of TM atoms on phosphorene can be enhanced by compressive strain whereas weakened by tensile strain. • Strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. • Applying strain can induce the semiconductor to metal or half-metal transitions in some TM@P systems.

  12. Light-matter interaction in transition metal dichalcogenides and their heterostructures

    Wurstbauer, Ursula; Miller, Bastian; Parzinger, Eric; Holleitner, Alexander W.

    2017-05-01

    The investigation of two-dimensional (2D) van der Waals materials is a vibrant, fast-moving and still growing interdisciplinary area of research. These materials are truly 2D crystals with strong covalent in-plane bonds and weak van der Waals interaction between the layers, and have a variety of different electronic, optical and mechanical properties. Transition metal dichalcogenides are a very prominent class of 2D materials, particularly the semiconducting subclass. Their properties include bandgaps in the near-infrared to the visible range, decent charge carrier mobility together with high (photo-) catalytic and mechanical stability, and exotic many-body phenomena. These characteristics make the materials highly attractive for both fundamental research as well as innovative device applications. Furthermore, the materials exhibit a strong light-matter interaction, providing a high sunlight absorbance of up to 15% in the monolayer limit, strong scattering cross section in Raman experiments, and access to excitonic phenomena in van der Waals heterostructures. This review focuses on the light-matter interaction in MoS2, WS2, MoSe2 and WSe2, which is dictated by the materials’ complex dielectric functions, and on the multiplicity of studying the first-order phonon modes by Raman spectroscopy to gain access to several material properties such as doping, strain, defects and temperature. 2D materials provide an interesting platform for stacking them into van der Waals heterostructures without the limitation of lattice mismatch, resulting in novel devices for applications but also to enable the study of exotic many-body interaction phenomena such as interlayer excitons. Future perspectives of semiconducting transition metal dichalcogenides and their heterostructures for applications in optoelectronic devices will be examined, and routes to study emergent fundamental problems and many-body quantum phenomena under excitations with photons will be discussed.

  13. Photodetectors based on junctions of two-dimensional transition metal dichalcogenides

    Wei Xia; Yan Fa-Guang; Shen Chao; Lv Quan-Shan; Wang Kai-You

    2017-01-01

    Transition metal dichalcogenides (TMDCs) have gained considerable attention because of their novel properties and great potential applications. The flakes of TMDCs not only have great light absorption from visible to near infrared, but also can be stacked together regardless of lattice mismatch like other two-dimensional (2D) materials. Along with the studies on intrinsic properties of TMDCs, the junctions based on TMDCs become more and more important in applications of photodetection. The junctions have shown many exciting possibilities to fully combine the advantages of TMDCs, other 2D materials, conventional and organic semiconductors together. Early studies have greatly enriched the application of TMDCs in photodetection. In this review, we investigate the efforts in photodetectors based on the junctions of TMDCs and analyze the properties of those photodetectors. Homojunctions based on TMDCs can be made by surface chemical doping, elemental doping and electrostatic gating. Heterojunction formed between TMDCs/2D materials, TMDCs/conventional semiconductors and TMDCs/organic semiconductor also deserve more attentions. We also compare the advantages and disadvantages of different junctions, and then give the prospects for the development of junctions based on TMDCs. (topical reviews)

  14. Thermal properties of zirconium diboride -- transition metal boride solid solutions

    McClane, Devon Lee

    This research focuses on the thermal properties of zirconium diboride (ZrB2) based ceramics. The overall goal was to improve the understanding of how different transition metal (TM) additives influence thermal transport in ZrB2. To achieve this, ZrB2 with 0.5 wt% carbon, and 3 mol% of individual transition metal borides, was densified by hot-press sintering. The transition metals that were investigated were: Y, Ti, Hf, V, Nb, Ta, Cr, Mo, W, and Re. The room temperature thermal diffusivities of the compositions ranged from 0.331 cm2/s for nominally pure ZrB2 to 0.105 cm2/s for (Zr,Cr)B2 and converged around 0.155cm2/s at higher temperatures for all compositions. Thermal conductivities were calculated from the diffusivities, using temperature-dependent values for density and heat capacity. The electron contribution to thermal conductivity was calculated from measured electrical resistivity according to the Wiedemann-Franz law. The phonon contribution to thermal conductivity was calculated by subtracting the electron contribution from the total thermal conductivity. Rietveld refinement of x-ray diffraction data was used to determine the lattice parameters of the compositions. The decrease in thermal conductivity for individual additives correlated directly to the metallic radius of the additive. Additional strain appeared to exist for additives when the stable TM boride for that metal had different crystal symmetries than ZrB2. This research provided insight into how additives and impurities affect thermal transport in ZrB2. The research potentially offers a basis for future modeling of thermal conductivity in ultra-high temperature ceramics based on the correlation between metallic radius and the decrease in thermal conductivity.

  15. Cell complexes of transition metals in biochemistry and medicine

    Voloshin, Ya.Z.; Varzatskij, O.A.; Bubnov, Yu.N.

    2007-01-01

    Basic directions and prospects of use of cell complexes of transition metals in medicine and biochemistry are considered: incapsulation of radioactive metal ions for radiotherapy and diagnostics; preparation of contrast compounds for magnetic resonance tomography, antidotes and pharmaceutical preparation of prolonged effect, preparations for boron-neutron-capture therapy of neoplasms, antioxidants; membrane transport of metal ions; study of interaction of cell metal complexes with nucleic acids; possibility of use of self-assembly of cell complexes for imitation of ligases and use of clathrochelates as linkers; design of inhibitors of viruses for AIDS therapy [ru

  16. Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically...... versatile method to form iminium and oxocarbenium ions. Given the number of reactions involving these highly electrophilic intermediates, this concept provides a sea of opportunities for heterocycle synthesis, (see scheme; Nu=nucleophile). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim....

  17. Compton profiles of some 4d transition-metals

    Sharma, B.K.; Tomak, M.

    1982-08-01

    We have computed Compton profiles for 4d transition-metals using the Renormalized Free Atom (RFA) model for two different electron configurations, namely 4dsup(n-1)5s 1 and 4dsup(n-2)5s 2 . The results for niobium and molybdenum are presented and compared with those obtained for these metals within free atom model. For low values of momenta the RFA profiles are broader than the latter ones. The constancy of J(0) values reported for 3d-metals is shown to be present also in case of 4d-metals. (author)

  18. Correlated electron pseudopotentials for 3d-transition metals

    Trail, J. R.; Needs, R. J.

    2015-01-01

    A recently published correlated electron pseudopotentials (CEPPs) method has been adapted for application to the 3d-transition metals, and to include relativistic effects. New CEPPs are reported for the atoms Sc − Fe, constructed from atomic quantum chemical calculations that include an accurate description of correlated electrons. Dissociation energies, molecular geometries, and zero-point vibrational energies of small molecules are compared with all electron results, with all quantities evaluated using coupled cluster singles doubles and triples calculations. The CEPPs give better results in the correlated-electron calculations than Hartree-Fock-based pseudopotentials available in the literature

  19. Trends on 3d transition metal impurities in diamond

    Assali, L.V.C.; Machado, W.V.M.; Justo, J.F.

    2009-01-01

    We carried out a first principles investigation on the electronic properties and chemical trends of 3d transition metal related impurities in diamond. In terms of formation energy, the interstitial site is considerably more unfavorable than the substitutional or divacancy ones. Going from Ti to Ni, the 3d-related energy levels in the gap become deeper toward the valence band in all three sites. However, in the divacancy one, those levels cross with the divacancy-related ones, such that the electronic property of the center depends on the character of the highest occupied level.

  20. Band engineering in transition metal dichalcogenides: Stacked versus lateral heterostructures

    Guo, Yuzheng; Robertson, John

    2016-01-01

    We calculate a large difference in the band alignments for transition metal dichalcogenide (TMD) heterojunctions when arranged in the stacked layer or lateral (in-plane) geometries, using direct supercell calculations. The stacked case follows the unpinned limit of the electron affinity rule, whereas the lateral geometry follows the strongly pinned limit of alignment of charge neutrality levels. TMDs therefore provide one of the few clear tests of band alignment models, whereas three-dimensional semiconductors give less stringent tests because of accidental chemical trends in their properties.

  1. Transition metal oxide as anode interface buffer for impedance spectroscopy

    Xu, Hui; Tang, Chao; Wang, Xu-Liang; Zhai, Wen-Juan; Liu, Rui-Lan; Rong, Zhou; Pang, Zong-Qiang; Jiang, Bing; Fan, Qu-Li; Huang, Wei

    2015-12-01

    Impedance spectroscopy is a strong method in electric measurement, which also shows powerful function in research of carrier dynamics in organic semiconductors when suitable mathematical physical models are used. Apart from this, another requirement is that the contact interface between the electrode and materials should at least be quasi-ohmic contact. So in this report, three different transitional metal oxides, V2O5, MoO3 and WO3 were used as hole injection buffer for interface of ITO/NPB. Through the impedance spectroscopy and PSO algorithm, the carrier mobilities and I-V characteristics of the NPB in different devices were measured. Then the data curves were compared with the single layer device without the interface layer in order to investigate the influence of transitional metal oxides on the carrier mobility. The careful research showed that when the work function (WF) of the buffer material was just between the work function of anode and the HOMO of the organic material, such interface material could work as a good bridge for carrier injection. Under such condition, the carrier mobility measured through impedance spectroscopy should be close to the intrinsic value. Considering that the HOMO (or LUMO) of most organic semiconductors did not match with the work function of the electrode, this report also provides a method for wide application of impedance spectroscopy to the research of carrier dynamics.

  2. Cohesion and coordination effects on transition metal surface energies

    Ruvireta, Judit; Vega, Lorena; Viñes, Francesc

    2017-10-01

    Here we explore the accuracy of Stefan equation and broken-bond model semiempirical approaches to obtain surface energies on transition metals. Cohesive factors are accounted for either via the vaporization enthalpies, as proposed in Stefan equation, or via cohesive energies, as employed in the broken-bond model. Coordination effects are considered including the saturation degree, as suggested in Stefan equation, employing Coordination Numbers (CN), or as the ratio of broken bonds, according to the bond-cutting model, considering as well the square root dependency of the bond strength on CN. Further, generalized coordination numbers CN bar are contemplated as well, exploring a total number of 12 semiempirical formulations on the three most densely packed surfaces of 3d, 4d, and 5d Transition Metals (TMs) displaying face-centered cubic (fcc), body-centered cubic (bcc), or hexagonal close-packed (hcp) crystallographic structures. Estimates are compared to available experimental surface energies obtained extrapolated to zero temperature. Results reveal that Stefan formula cohesive and coordination dependencies are only qualitative suited, but unadvised for quantitative discussion, as surface energies are highly overestimated, favoring in addition the stability of under-coordinated surfaces. Broken-bond cohesion and coordination dependencies are a suited basis for quantitative comparison, where square-root dependencies on CN to account for bond weakening are sensibly worse. An analysis using Wulff shaped averaged surface energies suggests the employment of broken-bond model using CN to gain surface energies for TMs, likely applicable to other metals.

  3. Transition-metal interactions in aluminum-rich intermetallics

    Al-Lehyani, Ibrahim; Widom, Mike; Wang, Yang; Moghadam, Nassrin; Stocks, G. Malcolm; Moriarty, John A.

    2001-01-01

    The extension of the first-principles generalized pseudopotential theory (GPT) to transition-metal (TM) aluminides produces pair and many-body interactions that allow efficient calculations of total energies. In aluminum-rich systems treated at the pair-potential level, one practical limitation is a transition-metal overbinding that creates an unrealistic TM-TM attraction at short separations in the absence of balancing many-body contributions. Even with this limitation, the GPT pair potentials have been used effectively in total-energy calculations for Al-TM systems with TM atoms at separations greater than 4 Aa. An additional potential term may be added for systems with shorter TM atom separations, formally folding repulsive contributions of the three- and higher-body interactions into the pair potentials, resulting in structure-dependent TM-TM potentials. Towards this end, we have performed numerical ab initio total-energy calculations using the Vienna ab initio simulation package for an Al-Co-Ni compound in a particular quasicrystalline approximant structure. The results allow us to fit a short-ranged, many-body correction of the form a(r 0 /r) b to the GPT pair potentials for Co-Co, Co-Ni, and Ni-Ni interactions

  4. Heterocycles by Transition Metals Catalyzed Intramolecular Cyclization of Acetylene Compounds

    Vizer, S.A.; Yerzhanov, K.B.; Dedeshko, E.C.

    2003-01-01

    Review shows the new strategies in the synthesis of heterocycles, having nitrogen, oxygen and sulfur atoms, via transition metals catalyzed intramolecular cyclization of acetylenic compounds on the data published at the last 30 years, Unsaturated heterocyclic compounds (pyrroles and pyrroline, furans, dihydro furans and benzofurans, indoles and iso-indoles, isoquinolines and isoquinolinones, aurones, iso coumarins and oxazolinone, lactams and lactones with various substitutes in heterocycles) are formed by transition metals, those salts [PdCl 2 , Pd(OAc) 2 , HgCl 2 , Hg(OAc) 2 , Hg(OCOCF 3 ) 2 , AuCl 3 ·2H 2 O, NaAuCl 4 ·2H 2 O, CuI, CuCl], oxides (HgO) and complexes [Pd(OAc) 2 (PPh 3 )2, Pd(PPh 3 ) 4 , PdCl 2 (MeCN) 2 , Pd(OAc ) 2 /TPPTS] catalyzed intramolecular cyclization of acetylenic amines, amides, ethers, alcohols, acids, ketones and βdiketones. More complex hetero polycyclic systems typical for natural alkaloids can to obtain similar. Proposed mechanisms of pyrroles, isoquinolines, iso indoles and indoles, benzofurans and iso coumarins, thiazolopyrimidinones formation are considered. (author)

  5. Mechanical and electronic properties of Janus monolayer transition metal dichalcogenides

    Shi, Wenwu; Wang, Zhiguo

    2018-05-01

    The mechanical and electronic properties of Janus monolayer transition metal dichalcogenides MXY (M  =  Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W; X/Y  =  S, Se, Te) were investigated using density functional theory. Results show that breaking the out-of-plane structural symmetry can be used to tune the electronic and mechanical behavior of monolayer transition metal dichalcogenides. The band gaps of monolayer WXY and MoXY are in the ranges of 0.16–1.91 and 0.94–1.69 eV, respectively. A semiconductor to metallic phase transition occurred in Janus monolayer MXY (M  =  Ti, Zr and Hf). The monolayers MXY (M  =  V, Nb, Ta and Cr) show metallic characteristics, which show no dependence on the structural symmetry breaking. The mechanical properties of MXY depended on the composition. Monolayer MXY (M  =  Mo, Ti, Zr, Hf and W) showed brittle characteristic, whereas monolayer CrXY and VXY are with ductile characteristic. The in-plane stiffness of pristine and Janus monolayer MXY are in the range between 22 and 158 N m‑1. The tunable electronic and mechanical properties of these 2D materials would advance the development of ultra-sensitive detectors, nanogenerators, low-power electronics, and energy harvesting and electromechanical systems.

  6. Colloquium: Excitons in atomically thin transition metal dichalcogenides

    Wang, Gang; Chernikov, Alexey; Glazov, Mikhail M.; Heinz, Tony F.; Marie, Xavier; Amand, Thierry; Urbaszek, Bernhard

    2018-04-01

    Atomically thin materials such as graphene and monolayer transition metal dichalcogenides (TMDs) exhibit remarkable physical properties resulting from their reduced dimensionality and crystal symmetry. The family of semiconducting transition metal dichalcogenides is an especially promising platform for fundamental studies of two-dimensional (2D) systems, with potential applications in optoelectronics and valleytronics due to their direct band gap in the monolayer limit and highly efficient light-matter coupling. A crystal lattice with broken inversion symmetry combined with strong spin-orbit interactions leads to a unique combination of the spin and valley degrees of freedom. In addition, the 2D character of the monolayers and weak dielectric screening from the environment yield a significant enhancement of the Coulomb interaction. The resulting formation of bound electron-hole pairs, or excitons, dominates the optical and spin properties of the material. Here recent progress in understanding of the excitonic properties in monolayer TMDs is reviewed and future challenges are laid out. Discussed are the consequences of the strong direct and exchange Coulomb interaction, exciton light-matter coupling, and influence of finite carrier and electron-hole pair densities on the exciton properties in TMDs. Finally, the impact on valley polarization is described and the tuning of the energies and polarization observed in applied electric and magnetic fields is summarized.

  7. Rare-earth metal transition metal borocarbide and nitridoborate superconductors

    Niewa, Rainer; Shlyk, Larysa; Blaschkowski, Bjoern [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

    2011-07-01

    Few years after the discovery of superconductivity in high-T{sub c} cuprates, borocarbides and shortly after nitridoborates with reasonably high T{sub c}s up to about 23 K attracted considerable attention. Particularly for the rare-earth metal series with composition RNi{sub 2}[B{sub 2}C] it turned out, that several members exhibit superconductivity next to magnetic order with both T{sub c} above or below the magnetic ordering temperature. Therefore, these compounds have been regarded as ideal materials to study the interplay and coexistence of superconductivity and long range magnetic order, due to their comparably high ordering temperatures and similar magnetic and superconducting condensation energies. This review gathers information on the series RNi{sub 2}[B{sub 2}C] and isostructural compounds with different transition metals substituting Ni as well as related series like RM[BC], RM[BN], AM[BN] and R{sub 3}M{sub 2}[BN]{sub 2}N (all with R = rare-earth metal, A = alkaline-earth metal, M = transition metal) with special focus on synthesis, crystal structures and structural trends in correspondence to physical properties. (orig.)

  8. Designer Shape Anisotropy on Transition-Metal-Dichalcogenide Nanosheets.

    Martella, Christian; Mennucci, Carlo; Lamperti, Alessio; Cappelluti, Emmanuele; de Mongeot, Francesco Buatier; Molle, Alessandro

    2018-03-01

    MoS 2 and generally speaking, the wide family of transition-metal dichalcogenides represents a solid nanotechnology platform on which to engineer a wealth of new and outperforming applications involving 2D materials. An even richer flexibility can be gained by extrinsically inducing an in-plane shape anisotropy of the nanosheets. Here, the synthesis of anisotropic MoS 2 nanosheets is proposed as a prototypical example in this respect starting from a highly conformal chemical vapor deposition on prepatterend substrates and aiming at the more general purpose of tailoring anisotropy of 2D nanosheets by design. This is envisioned to be a suitable configuration for strain engineering as far as strain can be spatially redistributed in morphologically different regions. With a similar approach, both the optical and electronic properties of the 2D transition-metal dichalcogenides can be tailored over macroscopic sample areas in a self-organized fashion, thus paving the way for new applications in the field of optical metasurfaces, light harvesting, and catalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. A DFT study of volatile organic compounds adsorption on transition metal deposited graphene

    Kunaseth, Manaschai; Poldorn, Preeyaporn; Junkeaw, Anchalee; Meeprasert, Jittima; Rungnim, Chompoonut; Namuangruk, Supawadee; Kungwan, Nawee; Inntam, Chan; Jungsuttiwong, Siriporn

    2017-01-01

    Highlights: • VOCs removal via modified carbon-based adsorbent using density functional theory. • The single-vacancy defective graphene (SDG) with metal-deposited significantly increase the adsorption efficiency. • TM-doped SDG is a suitable adsorbent material for VOC removal. • Electron in hybridized sp"2-orbitals of heteroatoms has an effect on mode of adsorption. - Abstract: Recently, elevated global emission of volatile organic compounds (VOCs) was associated to the acceleration and increasing severity of climate change worldwide. In this work, we investigated the performance of VOCs removal via modified carbon-based adsorbent using density functional theory. Here, four transition metals (TMs) including Pd, Pt, Ag, and Au were deposited onto single-vacancy defective graphene (SDG) surface to increase the adsorption efficiency. Five prototypical VOCs including benzene, furan, pyrrole, pyridine, and thiophene were used to study the adsorption capability of metal-deposited graphene adsorbent. Calculation results revealed that Pd, Pt, Au, and Ag atoms and nanoclusters bind strongly onto the SDG surface. In this study, benzene, furan and pyrrole bind in the π-interaction mode using delocalized π-electron in aromatic ring, while pyridine and thiophene favor X- interaction mode, donating lone pair electron from heteroatom. In terms of adsorption, pyridine VOC adsorption strengths to the TM-cluster doped SDG surfaces are Pt_4 (−2.11 eV) > Pd_4 (−2.05 eV) > Ag_4 (−1.53 eV) > Au_4 (−1.87 eV). Our findings indicate that TM-doped SDG is a suitable adsorbent material for VOC removal. In addition, partial density of states analysis suggests that benzene, furan, and pyrrole interactions with TM cluster are based on p-orbitals of carbon atoms, while pyridine and thiophene interactions are facilitated by hybridized sp"2-orbitals of heteroatoms. This work provides a key insight into the fundamentals of VOCs adsorption on carbon-based adsorbent.

  10. A Systematic Transport and Thermodynamic Study of Heavy Transition Metal Oxides with Hexagonal Structure

    Butrouna, Kamal

    There is no apparent, dominant interaction in heavy transition metal oxides (TMO), especially in 5d-TMO, where all relevant interactions are of comparable energy scales, and therefore strongly compete. In particular, the spin-orbit interaction (SOI) strongly competes with the electron-lattice and on-site Coulomb interaction (U). Therefore, any tool that allows one to tune the relative strengths of SOI and U is expected to offer an opportunity for the discovery and study of novel materials. BaIrO3 is a magnetic insulator driven by SOI, whereas the isostructural BaRuO3 is a paramagnetic metal. The contrasting ground states have been shown to result from the critical role of SOI in the iridate. This dissertation thoroughly examines a wide array of newly observed novel phenomena induced by adjusting the relative strengths of SOI and U via a systematic chemical substitution of the Ru4+(4d 4) ions for Ir4+(5d5) ions in BaIrO3, i.e., in high quality single crystals of BaIr1--x RuxO3(0.0 ≤ x ≤ 1.0). Our investigation of structural, magnetic, transport and thermal properties reveals that Ru substitution directly rebalances the competing energies so profoundly that it generates a rich phase diagram for BaIr 1--xRuxO 3 featuring two major effects: (1) Light Ru doping (0 ≤ x ≤ 0.15) prompts a simultaneous and precipitous drop in both the magnetic ordering temperature TC and the electrical resistivity, which exhibits metal-insulator transition at around TC. (2) Heavier Ru doping (0.41 ≤ x ≤ 0.82) induces a robust metallic and spin frustration state. For comparison and contrast, we also substituted Rh4+(4d 5) ions for Ir4+(5d5) ions in BaIrO3, i.e. in BaIr1--xRhxO 3(0.0 ≤ x ≤ 0.1), where Rh only reduces the SOI, but without altering the band filling. Hence, this system remains tuned at the Mott instability and is very susceptible to disorder scattering which gives rise to Anderson localization. KEYWORDS: spin-orbit interaction, heavy transition metal oxides

  11. First-principles study on ferromagnetism in double perovskite Sr2AlTaO6 doped with Cu or Zn at B sites

    Li, Y. D.; Wang, C. C.; Guo, Y. M.; Yu, Y.; Lu, Q. L.; Huang, S. G.; Li, Q. J.; Wang, H.; Cheng, R. L.; Liu, C. S.

    2018-05-01

    The possibilities of ferromagnetism induced by nonmagnetic dopants (Cu, Zn) in double perovskite Sr2AlTaO6 at B sites are investigated by density functional theory. Calculations reveal that substitutions at Ta-site tend to form high spin electronic configurations and could induce ferromagnetism which can be attributed to the hole-mediated p- d hybridization between Cu (or Zn) eg states and the neighboring O 2p states. The dopants preferably substitute at Al-site and adopt low spin electronic structures. Due to the smaller hole concentration and weaker covalent intensity, Sr2AlTaO6 with dopants at Al-site exhibits p-type metallic semiconductors without spin polarization.

  12. Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

    Smith, Kjell-Tore

    1996-08-01

    Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

  13. Electrical and Magnetic Properties of Binary Amorphous Transition Metal Alloys.

    Liou, Sy-Hwang

    The electrical, superconductive and magnetic properties of several binary transition metal amorphous and metastable crystalline alloys, Fe(,x)Ti(,100-x) (30 (LESSTHEQ) x (LESSTHEQ) 100), Fe(,x)Zr(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 93), Fe(,x)Hf(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 100), Fe(,x)Nb(,100 -x) (22 (LESSTHEQ) x (LESSTHEQ) 85), Ni(,x)Nb(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 80), Cu(,x)Nb(,100-x) (10 (LESSTHEQ) x (LESSTHEQ) 90) were studied over a wide composition range. Films were made using a magnetron sputtering system, and the structure of the films was investigated by energy dispersive x-ray diffraction. The composition region of each amorphous alloys system was determined and found in good agreement with a model proposed by Egami and Waseda. The magnetic properties and hyperfine interactions in the films were investigated using a conventional Mossbauer spectrometer and a ('57)Co in Rh matrix source. In all Fe-early transition metal binary alloys systems, Fe does not retain its moment in the low iron concentration region and the result is that the critical concentration for magnetic order (x(,c)) is much larger than anticipated from percolation considerations. A direct comparison between crystalline alloys and their amorphous counterparts of the same composition illustrate no clear correlation between crystalline and amorphous states. Pronounced discontinuities in the magnetic properties with variation in Fe content of all Fe-early transition metal alloys at phase boundaries separating amorphous and crystalline states have been observed. This is caused by the differences in the atomic arrangement and the electronic structure between crystalline and amorphous solids. The temperature dependence of resistivity, (rho)(T), of several binary amorphous alloys of Fe-TM (where TM = Ti, Zr, Hf, Nb etc.) has been studied from 2K to 300K. The Fe-poor (x x(,c)) samples have distinctive differences in (rho)(T) at low temperature (below 30K). All the magnetic samples

  14. Transition metal borides. Synthesis, characterization and superconducting properties

    Kayhan, Mehmet

    2013-07-12

    A systematic study was done on the synthesis and superconducting properties of metal rich transition metal borides. Five different binary systems were investigated including the boride systems of niobium, tantalum, molybdenum, tungsten and rhenium. High temperature solid state methods were used in order to synthesize samples of different transition metal borides of the composition M{sub 2}B, MB, M{sub 3}B{sub 2}, MB{sub 2}, and M{sub 2}B{sub 4}. The reactions were carried out in three different furnaces with different sample containers: the electric arc (copper crucible), the high frequency induction furnace (boron nitride, tantalum or glassy carbon crucibles), and the conventional tube furnace (sealed evacuated quartz ampoules). The products obtained were characterized with X-ray powder diffractometry, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Phase analyses and crystal structure refinements using the Rietveld method and based on structure models known from literature were performed. A neutron diffraction measurement was done for W{sub 2}B{sub 4} to allow for a complete crystal structure determination, because of the presence of a heavy element like tungsten and a light element like boron that made it difficult to determine the accurate determination of the boron atom positions and occupancies from X-ray data. A new structure model for W{sub 2}B{sub 4} was proposed. Magnetic measurements in a SQUID magnetometer down to temperatures as low as 1.8 K were performed to several of the products in order to see if the transition metal borides become superconducting at low temperatures, and the results were compared with data from literature. Superconducting properties were found for the following compounds: NbB{sub 2} (T{sub C} = 3.5 K), β-MoB (T{sub C} = 2.4 K), β-WB (T{sub C} = 2.0 K), α-WB (T{sub C} = 4.3 K), W{sub 2}B{sub 4} (T{sub C} = 5.4 K), Re{sub 7}B{sub 3} (T{sub C} = 2.4 K). A relationship between the superconducting properties

  15. Transition metal borides. Synthesis, characterization and superconducting properties

    Kayhan, Mehmet

    2013-01-01

    A systematic study was done on the synthesis and superconducting properties of metal rich transition metal borides. Five different binary systems were investigated including the boride systems of niobium, tantalum, molybdenum, tungsten and rhenium. High temperature solid state methods were used in order to synthesize samples of different transition metal borides of the composition M 2 B, MB, M 3 B 2 , MB 2 , and M 2 B 4 . The reactions were carried out in three different furnaces with different sample containers: the electric arc (copper crucible), the high frequency induction furnace (boron nitride, tantalum or glassy carbon crucibles), and the conventional tube furnace (sealed evacuated quartz ampoules). The products obtained were characterized with X-ray powder diffractometry, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Phase analyses and crystal structure refinements using the Rietveld method and based on structure models known from literature were performed. A neutron diffraction measurement was done for W 2 B 4 to allow for a complete crystal structure determination, because of the presence of a heavy element like tungsten and a light element like boron that made it difficult to determine the accurate determination of the boron atom positions and occupancies from X-ray data. A new structure model for W 2 B 4 was proposed. Magnetic measurements in a SQUID magnetometer down to temperatures as low as 1.8 K were performed to several of the products in order to see if the transition metal borides become superconducting at low temperatures, and the results were compared with data from literature. Superconducting properties were found for the following compounds: NbB 2 (T C = 3.5 K), β-MoB (T C = 2.4 K), β-WB (T C = 2.0 K), α-WB (T C = 4.3 K), W 2 B 4 (T C = 5.4 K), Re 7 B 3 (T C = 2.4 K). A relationship between the superconducting properties and the compositional and structural features was discussed for metal diborides. Also it was

  16. Room temperature ferromagnetism with large magnetic moment at low field in rare-earth-doped BiFeO₃ thin films.

    Kim, Tae-Young; Hong, Nguyen Hoa; Sugawara, T; Raghavender, A T; Kurisu, M

    2013-05-22

    Thin films of rare earth (RE)-doped BiFeO3 (where RE=Sm, Ho, Pr and Nd) were grown on LaAlO3 substrates by using the pulsed laser deposition technique. All the films show a single phase of rhombohedral structure with space group R3c. The saturated magnetization in the Ho- and Sm-doped films is much larger than the values reported in the literature, and is observed at quite a low field of 0.2 T. For Ho and Sm doping, the magnetization increases as the film becomes thinner, suggesting that the observed magnetism is mostly due to a surface effect. In the case of Nd doping, even though the thin film has a large magnetic moment, the mechanism seems to be different.

  17. Revival of ferromagnetic behavior in charge-ordered Pr0.75Na0.25MnO3 manganite by ruthenium doping at Mn site and its MR effect

    Elyana, E.; Mohamed, Z.; Kamil, S. A.; Supardan, S. N.; Chen, S. K.; Yahya, A. K.

    2018-02-01

    Ru doping in charge-ordered Pr0.75Na0.25Mn1-xRuxO3 (x = 0-0.1) manganites was studied to investigate its effect on structure, electrical transport, magnetic properties, and magnetotransport properties. DC electrical resistivity (ρ), magnetic susceptibility, and χ' measurements showed that sample x = 0 exhibits insulating behavior within the entire temperature range and antiferromagnetic (AFM) behavior below the charge-ordering (CO) transition temperature TCO of 221 K. Ru4+ substitution (x>0.01) suppressed the CO state, which resulted in the revival of paramagnetic to ferromagnetic (FM) transition at the Curie temperature Tc, increasing from 120 K (x = 0.01) to 193 K (x = 0.1). Deviation from the Curie-Weiss law above Tc in the 1/χ' versus T plot for x = 0.01 doped samples indicated the existence of Griffiths phase with Griffith temperature at 169 K. Electrical resistivity measurements showed that Ru4+ substitution increased the metallic-to-insulating transition temperature TMI from 144 K (x = 0.01) to 192 K (x = 0.05) due to enhanced double-exchange mechanism, but TMI decreased to 176 K (x = 0.1) probably due to the existence of AFM clusters within the FM domain. The present work also discussed the possible theoretical models at the resistivity curve of Pr0.75Na0.25Mn1-xRuxO3 (x = 0-0.1) for the entire temperature range.

  18. Zeolites as supports for transition-metal complexes

    Le Van Mao, R

    1979-01-01

    The unique structural characteristics of the zeolites, including the presence of molecular-size cages and channels and of an internal electrostatic field, make them promising as supports for converting homogeneous to heterogeneous catalysts. The acidic sites on the zeolites may also contribute to catalysis of reactions, such as hydrocracking; may stabilize metal complexes in a highly disperse state; and may improve activity or selectivity. Recent studies on the synthesis of new types of zeolite-supported complexes of transition metals (TM), such as Co, Cu, Ag, Fe, Mo, Ru, Rh, Re, and Os, suggest the feasibility of the direct introduction of some TM complexes into the zeolitic cages during zeolite synthesis, especially during the crystallization phase. This method may considerably reduce the structural limitations associated with the incorporation of TM complexes into zeolites by conventional methods.

  19. Density functional theory studies of transition metal nanoparticles in catalysis

    Greeley, Jeffrey Philip; Rankin, Rees; Zeng, Zhenhua

    2013-01-01

    Periodic Density Functional Theory calculations are capable of providing powerful insights into the structural, energetics, and electronic phenomena that underlie heterogeneous catalysis on transition metal nanoparticles. Such calculations are now routinely applied to single crystal metal surfaces...... and to subnanometer metal clusters. Descriptions of catalysis on truly nanosized structures, however, are generally not as well developed. In this talk, I will illustrate different approaches to analyzing nanocatalytic phenomena with DFT calculations. I will describe case studies from heterogeneous catalysis...... and electrocatalysis, in which single crystal models are combined with Wulff construction-based ideas to produce descriptions of average nanocatalyst behavior. Then, I will proceed to describe explicitly DFT-based descriptions of catalysis on truly nanosized particles (

  20. Investigation of electronic transport properties of some liquid transition metals

    Patel, H. P.; Sonvane, Y. A.; Thakor, P. B.

    2018-04-01

    We investigated electronic transport properties of some liquid transition metals (V, Cr, Mn, Fe, Co and Pt) using Ziman formalism. Our parameter free model potential which is realized on ionic and atomic radius has been incorporated with the Hard Sphere Yukawa (HSY) reference system to study the electronic transport properties like electrical resistivity (ρ), thermal conductivity (σ) and thermo electrical power (Q). The screening effect on aforesaid properties has been studied by using different screening functions. The correlations of our results and others data with in addition experimental values are profoundly promising to the researchers working in this field. Also, we conclude that our newly constructed parameter free model potential is capable to explain the aforesaid electronic transport properties.

  1. Signatures of exciton condensation in a transition metal dichalcogenide

    Kogar, Anshul; Rak, Melinda S.; Vig, Sean; Husain, Ali A.; Flicker, Felix; Joe, Young Il; Venema, Luc; MacDougall, Greg J.; Chiang, Tai C.; Fradkin, Eduardo; van Wezel, Jasper; Abbamonte, Peter

    2017-12-01

    Bose condensation has shaped our understanding of macroscopic quantum phenomena, having been realized in superconductors, atomic gases, and liquid helium. Excitons are bosons that have been predicted to condense into either a superfluid or an insulating electronic crystal. Using the recently developed technique of momentum-resolved electron energy-loss spectroscopy (M-EELS), we studied electronic collective modes in the transition metal dichalcogenide semimetal 1T-TiSe2. Near the phase-transition temperature (190 kelvin), the energy of the electronic mode fell to zero at nonzero momentum, indicating dynamical slowing of plasma fluctuations and crystallization of the valence electrons into an exciton condensate. Our study provides compelling evidence for exciton condensation in a three-dimensional solid and establishes M-EELS as a versatile technique sensitive to valence band excitations in quantum materials.

  2. New Transition metal assisted complex borohydrides for hydrogen storage

    Sesha Srinivasan; Elias Lee Stefanakos; Yogi Goswami

    2006-01-01

    High capacity hydrogen storage systems are indeed essential for the on-board vehicular application that leads to the pollution free environment. Apart from the various hydrogen storage systems explored in the past, complex hydrides involving light weight alkali/alkaline metals exhibits promising hydrogenation/ dehydrogenation characteristics. New transition metal assisted complex borohydrides [Zn(BH 4 ) 2 ] have been successfully synthesized by an inexpensive mechano-chemical process. These complex hydrides possesses gravimetric hydrogen storage capacity of ∼8.4 wt.% at around 120 C. We have determined the volumetric hydrogen absorption and desorption of these materials for a number of cycles. Another complex borohydride mixture LiBH 4 /MgH 2 catalyzed with ZnCl 2 has been synthesized and characterized using various analytical techniques. (authors)

  3. Induced magnetism in transition metal intercalated graphitic systems

    Kaloni, Thaneshwor P.

    2011-10-26

    We investigate the structure, chemical bonding, electronic properties, and magnetic behavior of a three-dimensional graphitic network in aba and aaa stacking with intercalated transition metal atoms (Mn, Fe, Co, Ni, and Cu). Using density functional theory, we find induced spin-polarization of the C atoms both when the graphene sheets are aba stacked (forming graphite) and aaa stacked (resembling bi-layer graphene). The magnetic moment induced by Mn, Fe, and Co turns out to vary from 1.38 μB to 4.10 μB, whereas intercalation of Ni and Cu does not lead to a magnetic state. The selective induction of spin-polarization can be utilized in spintronic and nanoelectronic applications.

  4. Thermophysical Property Measurements of Silicon-Transition Metal Alloys

    Banish, R. Michael; Erwin, William R.; Sansoucie, Michael P.; Lee, Jonghyun; Gave, Matthew A.

    2014-01-01

    Metals and metallic alloys often have high melting temperatures and highly reactive liquids. Processing reactive liquids in containers can result in significant contamination and limited undercooling. This is particularly true for molten silicon and it alloys. Silicon is commonly termed "the universal solvent". The viscosity, surface tension, and density of several silicon-transition metal alloys were determined using the Electrostatic Levitator system at the Marshall Space Flight Center. The temperature dependence of the viscosity followed an Arrhenius dependence, and the surface tension followed a linear temperature dependence. The density of the melts, including the undercooled region, showed a linear behavior as well. Viscosity and surface tension values were obtain for several of the alloys in the undercooled region.

  5. Induced magnetism in transition metal intercalated graphitic systems

    Kaloni, Thaneshwor P.; Schwingenschlö gl, Udo; Upadhyay Kahaly, M.

    2011-01-01

    We investigate the structure, chemical bonding, electronic properties, and magnetic behavior of a three-dimensional graphitic network in aba and aaa stacking with intercalated transition metal atoms (Mn, Fe, Co, Ni, and Cu). Using density functional theory, we find induced spin-polarization of the C atoms both when the graphene sheets are aba stacked (forming graphite) and aaa stacked (resembling bi-layer graphene). The magnetic moment induced by Mn, Fe, and Co turns out to vary from 1.38 μB to 4.10 μB, whereas intercalation of Ni and Cu does not lead to a magnetic state. The selective induction of spin-polarization can be utilized in spintronic and nanoelectronic applications.

  6. Preparation of transition metal sulfide nanoparticles via hydrothermal route

    Fei-Ling, P.; Chin-Hua, C.; Sarani Zakaria; Tze-Khong, L.; Mohd Ambar Yarmo; Nay-Ming, H.

    2010-01-01

    Nano sized copper sulfide, iron sulfide and molybdenum sulfide were successfully synthesised via a simple hydrothermal method. Sodium thiosulfate pentahydrate (Na 2 S 2 O 3 ·5H 2 O) and hydroxylamine sulfate ((H 3 NO) 2 ·H 2 SO 4 ) were used as the starting materials and reacted with the transition metal source at 200 degree Celsius for 90 min. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and Fourier transform infrared spectroscopy (FTIR). Spherical shape CuS and FeS 2 nanoparticles with high crystallinity were successfully produced. The transmission electron micrographs revealed the well-dispersibility of the produced nanoparticles. Scanning electron micrograph showed the MoS 2 nanoparticles possessed a spherical shape with sheet-like structure covering on the outer surface of the particles. (author)

  7. Laser surface alloying of aluminium-transition metal alloys

    Almeida, A.; Vilar, R.

    1998-01-01

    Laser surface alloying has been used as a tool to produce hard and corrosion resistant Al-transition metal (TM) alloys. Cr and Mo are particularly interesting alloying elements to produce stable high-strength alloys because they present low diffusion coefficients and solid solubility in Al. To produce Al-TM surface alloys a two-step laser process was developed: firstly, the material is alloyed using low scanning speed and secondly, the microstructure is modified by a refinement step. This process was used in the production of Al-Cr, Al-Mo and Al-Mo and Al-Nb surface alloys by alloying Cr, Mo or Nb powder into an Al and 7175 Al alloy substrate using a CO 2 laser . This paper presents a review of the work that has been developed at Instituto Superior Tecnico on laser alloying of Al-TM alloy, over the last years. (Author) 16 refs

  8. Nonequilibrium carrier dynamics in transition metal dichalcogenide semiconductors

    Steinhoff, A.; Florian, M.; Rösner, M.; Lorke, M.; Wehling, T. O.; Gies, C.; Jahnke, F.

    2016-09-01

    When exploring new materials for their potential in (opto)electronic device applications, it is important to understand the role of various carrier interaction and scattering processes. In atomically thin transition metal dichalcogenide semiconductors, the Coulomb interaction is known to be much stronger than in quantum wells of conventional semiconductors like GaAs, as witnessed by the 50 times larger exciton binding energy. The question arises, whether this directly translates into equivalently faster carrier-carrier Coulomb scattering of excited carriers. Here we show that a combination of ab initio band-structure and many-body theory predicts Coulomb-mediated carrier relaxation on a sub-100 fs time scale for a wide range of excitation densities, which is less than an order of magnitude faster than in quantum wells.

  9. Gravimetric determination of beryllium in the presence of transition metals

    Morozova, S.S.; Nikitina, L.V.; Dyatlova, N.M.; Serebryakova, G.V.; Vol'nyagina, A.N.

    1976-01-01

    A new organic reagent, nitrolotrimethylphosphonic acid (H 6 L), is proposed for gravimetric determination of beryllium. This complexone forms with Be hardly soluble complexes in a wide pH range. The separated complex has a composition Be 5 (HL) 2 x10H 2 O. To elucidate the possibility of determining Be in the presence of transition metals, often accompanying beryllium in alloys, interaction of cations of these metals with H 6 L at different pH has been studied potentiometrically. It has been established that at pH=1.1 in the presence of masking reagent (diethylentriaminopentacetic acid) Be can be determined when zinc, copper, chromium, cobalt, nickel, iron, manganese and cadmium are present. Gravimetric method of determining Be with the help of H 6 L has been developed. The weight form is obtained by drying the precipitate which reduces considerably the time of analysis and the error of determination

  10. A review of cobalt adsorption on transition metal oxides

    Walker, S.M.

    1987-04-01

    This report reviews studies of cobalt adsorption on transition metal oxides, in the context of corrosion product and radioactivity transport in PWR primary circuits. In general, uptake of cobalt increases with pH, with temperature and with decreasing ionic strength. Very little data are available under PWR primary circuit conditions, but the limited data available suggest that cobalt uptake by the zirconium oxide corrosion product layer on fuel pins may be significant compared to that deposited on fuel crud. If fuel crud levels can be reduced in future by coolant chemistry control then uptake by the zirconia will assume a greater relative role. It is planned to use an autoclave to study uptake of cobalt on oxidised Zircaloy surfaces at temperatures up to 593K under PWR primary circuit chemistry conditions. (author)

  11. Determination of Surface Properties of Liquid Transition Metals

    Korkmaz, S. D.

    2008-01-01

    Certain surface properties of liquid simple metals are reported. Using the expression derived by Gosh and coworkers we investigated the surface entropy of liquid transition metals namely Fe, Co and Ni. We have also computed surface tensions of the metals concerned. The pair distribution functions are calculated from the solution of Ornstein-Zernike integral equation with Rogers-Young closure using the individual version of the electron-ion potential proposed by Fioalhais and coworkers which was originally developed for solid state. The predicted values of surface tension and surface entropy are in very good agreement with available experimental data. The present study results show that the expression derived by Gosh and coworkers is very useful for the surface entropy by using Fioalhais pseudopotential and Rogers-Young closure

  12. Quantum-based Atomistic Simulation of Transition Metals

    Moriarty, J A; Benedict, L X; Glosli, J N; Hood, R Q; Orlikowski, D A; Patel, M V; Soderlind, P; Streitz, F H; Tang, M; Yang, L H

    2005-01-01

    First-principles generalized pseudopotential theory (GPT) provides a fundamental basis for transferable multi-ion interatomic potentials in d-electron transition metals within density-functional quantum mechanics. In mid-period bcc metals, where multi-ion angular forces are important to structural properties, simplified model GPT or MGPT potentials have been developed based on canonical d bands to allow analytic forms and large-scale atomistic simulations. Robust, advanced-generation MGPT potentials have now been obtained for Ta and Mo and successfully applied to a wide range of structural, thermodynamic, defect and mechanical properties at both ambient and extreme conditions of pressure and temperature. Recent algorithm improvements have also led to a more general matrix representation of MGPT beyond canonical bands allowing increased accuracy and extension to f-electron actinide metals, an order of magnitude increase in computational speed, and the current development of temperature-dependent potentials

  13. Study of transition metal oxides by photoelectron spectroscopy

    Rao, C.N.R.; Sarma, D.D.; Vasudevan, S.; Hegde, M.S.

    1979-01-01

    Systematics in the X-ray photoelectron spectra (X.p.e.s.) of Ti, V, Cr, Mn and Nb oxides with the metal ion in different oxidation states as well as of related series of mono-, sesqui- and di-oxides of the first row of transition metals have been investigated in detail. Core level binding energies, spin-orbit splittings and exchange splittings are found to exhibit interesting variations with the oxidation state of the metal or the nuclear charge. The 3d binding energies of the monoxides show a proportionality to Goodenough's (R - RC). Other aspects of interest in the study are the satellite structure and final state effects in the X.p.e.s. of the oxides, and identification of different valence states in oxides of the general formulae Mn02n-1 and M304. The nature of changes in the 3d bands of oxides undergoing metal-insulator transitions is also indicated. (author)

  14. Phase stability and electronic structure of transition-metal aluminides

    Carlsson, A.E.

    1992-01-01

    This paper will describe the interplay between die electronic structure and structural energetics in simple, complex, and quasicrystalline Al-transition metal (T) intermetallics. The first example is the Ll 2 -DO 22 competition in Al 3 T compounds. Ab-initio electronic total-energy calculations reveal surprisingly large structural-energy differences, and show that the phase stability of both stoichiometric and ternary-substituted compounds correlates closely with a quasigap in the electronic density of states (DOS). Secondly, ab-initio calculations for the structural stability of the icosahedrally based Al 12 W structure reveal similar quasigap effects, and provide a simple physical explanation for the stability of the complex aluminide structures. Finally, parametrized tight-binding model calculations for the Al-Mn quasicrystal reveal a large spread in the local Mn DOS behavior, and support a two-site model for the quasicrystal's magnetic behavior

  15. New technique for producing the alloys based on transition metals

    Dolukhanyan, S.K.; Aleksanyan, A.G.; Shekhtman, V.Sh.; Mantashyan, A.A.; Mayilyan, D.G.; Ter-Galstyan, O.P.

    2007-01-01

    In principle new technique was elaborated for obtaining the alloys of refractory metals by their hydrides compacting and following dehydrogenation. The elaborated technique is described. The conditions of alloys formation from different hydrides of appropriate metals was investigated in detail. The influence of the process parameters such as: chemical peculiarities, composition of source hydrides, phase transformation during dehydrogenation, etc. on the alloys formation were established. The binary and tertiary alloys of α and ω phases: Ti 0 .8Zr 0 .8; Ti 0 .66Zr 0 .33; Ti 0 .3Zr 0 .8; Ti 0 .2Zr 0 .8; Ti 0 .8Hf 0 .2; Ti 0 .6Hf 0 .4Ti 0 .66Zr 0 .23Hf 0 .11; etc were recieved. Using elaborated special hydride cycle, an earlier unknown effective process for formation of alloys of transition metals was realized. The dependence of final alloy structure on the composition of initial mixture and hydrogen content in source hydrides was established

  16. Thermal plasma synthesis of transition metal nitrides and alloys

    Ronsheim, P.; Christensen, A.N.; Mazza, A.

    1981-01-01

    Applications of arc plasma processing to high-temperature chemistry of Group V nitrides and Si and Ge alloys are studied. The transition metal nitrides 4f-VN, 4f-NbN, and 4f-TaN are directly synthesized in a dc argon-nitrogen plasma from powders of the metals. A large excess of N 2 is required to form stoichiometric 4f-VN, while the Nb and Ta can only be synthesized with a substoichiometric N content. In a dc argon plasma the alloys V 3 Si, VSi 2 , NbSi 2 , NbGe 2 , Cr 3 Si, and Mo 3 Si are obtained from powder mixtures of the corresponding elements. The compounds are identified by x-ray diffraction patterns and particle shape and size are studied by electron microscopy

  17. Hot carrier dynamics in plasmonic transition metal nitrides

    Habib, Adela; Florio, Fred; Sundararaman, Ravishankar

    2018-06-01

    Extraction of non-equilibrium hot carriers generated by plasmon decay in metallic nano-structures is an increasingly exciting prospect for utilizing plasmonic losses, but the search for optimum plasmonic materials with long-lived carriers is ongoing. Transition metal nitrides are an exciting class of new plasmonic materials with superior thermal and mechanical properties compared to conventional noble metals, but their suitability for plasmonic hot carrier applications remains unknown. Here, we present fully first principles calculations of the plasmonic response, hot carrier generation and subsequent thermalization of all group IV, V and VI transition metal nitrides, fully accounting for direct and phonon-assisted transitions as well as electron–electron and electron–phonon scattering. We find the largest frequency ranges for plasmonic response in ZrN, HfN and WN, between those of gold and silver, while we predict strongest absorption in the visible spectrum for the VN, NbN and TaN. Hot carrier generation is dominated by direct transitions for most of the relevant energy range in all these nitrides, while phonon-assisted processes dominate only below 1 eV plasmon energies primarily for the group IV nitrides. Finally, we predict the maximum hot carrier lifetimes to be around 10 fs for group IV and VI nitrides, a factor of 3–4 smaller than noble metals, due to strong electron–phonon scattering. However, we find longer carrier lifetimes for group V nitrides, comparable to silver for NbN and TaN, while exceeding 100 fs (twice that of silver) for VN, making them promising candidates for efficient hot carrier extraction.

  18. Comparative study of the synthesis of layered transition metal molybdates

    Mitchell, S.; Gomez-Aviles, A.; Gardner, C.; Jones, W.

    2010-01-01

    Mixed metal oxides (MMOs) prepared by the mild thermal decomposition of layered double hydroxides (LDHs) differ in their reactivity on exposure to aqueous molybdate containing solutions. In this study, we investigate the reactivity of some T-Al containing MMOs (T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates (LTMs) possessing the general formula AT 2 (OH)(MoO 4 ) 2 .H 2 O, where A=NH 4 + , Na + or K + . The phase selectivity of the reaction was studied with respect to the source of molybdate, the ratio of T to Mo and the reaction pH. LTMs were obtained on reaction of Cu-Al and Zn-Al containing MMOs with aqueous solutions of ammonium heptamolybdate. Rehydration of these oxides in the presence of sodium or potassium molybdate yielded a rehydrated LDH phase as the only crystalline product. The LTM products obtained by the rehydration of MMO precursors were compared with LTMs prepared by direct precipitation from the metal salts in order to study the influence of preparative route on their chemical and physical properties. Differences were noted in the composition, morphology and thermal properties of the resulting products. - Graphical abstract: Mixed metal oxides (MMOs) derived from layered double hydroxide precursors differ in their reactivity on exposure to aqueous molybdate containing solutions. We investigate the influence of the molybdate source, the rehydration pH and the ratio of T/Mo on the reactivity of some T-Al containing MMOs (T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates of general formula AT 2 (OH)(MoO 4 ) 2 .H 2 O (where A + =NH 4 + , K + or Na + ).

  19. Structural, electronic and magnetic properties of transition-metal embedded zigzag-edged graphene nanoribbons

    Yu Guodong; Lü Xiaoling; Jiang Liwei; Gao Wenzhu; Zheng Yisong

    2013-01-01

    By means of ab initio calculations within density-functional theory, the structural, electronic and magnetic properties of a zigzag-edged graphene nanoribbon (ZGNR) with 3d transition-metal atoms (TMAs) (Sc–Zn) embedded in the periodically distributed single vacancies are systematically studied. Different from the pristine ZGNR, all of these composite structures show the subband structures with nontrivial spin polarizations, regardless of the type and the embedding position of the TMA. Embedding one kind of these atoms (V, Cr, Ni, Cu or Zn) near one ribbon edge can cause a notable edge distortion. Except for the cases of Sc, Fe and Co doping, other kinds of TMAs embedded near an edge of the ribbon can suppress the inherent magnetism of the zigzag edge. By further analysis, we find that two effects are responsible for the suppression of edge magnetism. One is the variation of the occupied spin-polarized subbands due to the hybridization of the edge state of the ZGNR and 3d atomic states of the dopant. The other is the delocalization of the edge state caused by the exotic TMA. The unilateral magnetism of these TMA-embedded ZGNRs can be utilized to realize the spin-polarized electronic transport, which is the key electronic property in the context of spintronics applications of carbon-based materials. (paper)

  20. Tunnel Field-Effect Transistors in 2-D Transition Metal Dichalcogenide Materials

    Ilatikhameneh, Hesameddin; Tan, Yaohua; Novakovic, Bozidar; Klimeck, Gerhard; Rahman, Rajib; Appenzeller, Joerg

    2015-12-01

    In this work, the performance of Tunnel Field-Effect Transistors (TFETs) based on two-dimensional Transition Metal Dichalcogenide (TMD) materials is investigated by atomistic quantum transport simulations. One of the major challenges of TFETs is their low ON-currents. 2D material based TFETs can have tight gate control and high electric fields at the tunnel junction, and can in principle generate high ON-currents along with a sub-threshold swing smaller than 60 mV/dec. Our simulations reveal that high performance TMD TFETs, not only require good gate control, but also rely on the choice of the right channel material with optimum band gap, effective mass and source/drain doping level. Unlike previous works, a full band atomistic tight binding method is used self-consistently with 3D Poisson equation to simulate ballistic quantum transport in these devices. The effect of the choice of TMD material on the performance of the device and its transfer characteristics are discussed. Moreover, the criteria for high ON-currents are explained with a simple analytic model, showing the related fundamental factors. Finally, the subthreshold swing and energy-delay of these TFETs are compared with conventional CMOS devices.

  1. Layered lithium transition metal nitrides as novel anodes for lithium secondary batteries

    Liu Yu; Horikawa, Kumi; Fujiyosi, Minako; Imanishi, Nobuyuki; Hirano, Atsushi; Takeda, Yasuo

    2004-01-01

    We report the approach to overcome the deterrents of the hexagonal Li 2.6 Co 0.4 N as potential insertion anode for lithium ion batteries: the rapid capacity fading upon long cycles and the fully Li-rich state before cycling. Research reveals that the appropriate amount of Co substituted by Cu can greatly improve the cycling performance of Li 2.6 Co 0.4 N. It is attributed to the enhanced electrochemical stability and interfacial comparability. However, doped Cu leads to a slightly decreased capacity. High energy mechanical milling (HEMM) was found to effectively improve the reversible capacity associated with the electrochemical kinetics by modifying the active hosts' morphology characteristics. Moreover, the composite based on mesocarbon microbead (MCMB) and Li 2.6 Co 0.4 N was developed under HEMM. The composite demonstrates a high first cycle efficiency at 100% and a large reversible capacity of ca. 450 mAh g -1 , as well as a stable cycling performance. This work may contribute to a development of the lithium transition metal nitrides as novel anodes for lithium ion batteries

  2. Investigation of iron adsorption on composite transition metal carbides in steel by first-principles calculation

    Xiong, Hui-Hui; Gan, Lei; Tong, Zhi-Fang; Zhang, Heng-Hua; Zhou, Yang

    2018-05-01

    The nucleation potential of transition metal (TM) carbides formed in steel can be predicted by the behavior of iron adsorption on their surface. Therefore, Fe adsorption on the (001) surface of (A1-xmx)C (A = Nb, Ti, m = Mo, V) was investigated by the first-principles method to reveal the initialization of Fe nucleation. The Mulliken population and partial density of state (PDOS) were also calculated and analyzed in this work. The results show that Fe adsorption depends on the composition and configuration of the composite carbides. The adsorption energy (Wads) of Fe on most of (A1-xmx)C is larger than that of Fe on pure TiC or NbC. The maximum Wads is found for Fe on (Nb0.5Mo0.5)C complex carbide, indicating that this carbide has the high nucleation capacity at early stage. The Fe adsorption could be improved by the segregation of Cr and Mn atoms on the surfaces of (Nb0.5Mo0.5)C and (Ti0.5Mo0.5)C. The PDOS analysis of (Cr, Mn)-doped systems further explains the strong interactions between Fe and Cr or Mn atoms.

  3. Effect of trivalent transition metal ion substitution in Dy2O3 system

    Dhilip, M.; Saravana Kumar, K.; Anbarasu, V.

    2015-01-01

    One of the very promising approaches to create novel materials is to combine different physical properties in one material to achieve rich functionality. Magnetoelectric multiferroics are attracting attention for fundamental physics due to their unique coupling behaviour between ferroelectricity, ferromagnetism and ferroelasticity and also because of their promising applications for devices in spintronics, information storage, sensing and actuation. The existence of spontaneous magnetization in the perovskite like phase (layer of perovskite) has encouraged exploring the possibility of fabrication of a multiferroic material for multifunctional devices using the concept of magnetoelectric effect. The rare earth orthoferrites (LnFeO 3 where, Ln = La, Sm, Gd, Dy, Er and Yb) are a class of materials having potential for various applications. These compounds and metal ion substituted ferrites crystallising in perovskite structure show promise as catalysts gas separators, cathodes in solid oxide fuel cells, sensor materials, magneto-optic materials and as spin valves. In this present work, Fe substituted in Dysprosium Oxide compounds were prepared by standard solid state reaction at a temperature of 1300℃. The structural analysis of the prepared samples was characterized with powder X-Ray Diffraction technique and the lattice parameters were calculated with PodwerX indexing software. The structural analysis reveals that the substitution of Fe in Dy 2 O 3 system leads to change of crystalline structure from Cubic to Tetragonal. Further, decreasing trend of volume of the unit cell confirms the occupation of smaller ionic radii element Fe in the Dy site of Dy 2 O 3 system. Hence the possibilities of incorporation of trivalent transition metal ion in to the host Dy 2 O 3 site were analyzed. (author)

  4. On the effects of magnetic bonding in rare earth transition metal intermetallics

    Kumar, R.; Bentley, J.; Yelon, W.B.

    1990-01-01

    Neutron diffraction experiments on rare-earth transition metal magnetic alloys Er 2 Fe 14 B and Er 2 Fe 17 have been carried out at temperature above and below the ordering temperature (T c ). An anomalously large magnetic moment is observed at the crystallographic j 2 site in Er 2 Fe 14 B which is the intersection point of the major ligand lines in the crystal structure. The interatomic Fe-Fe distances are in the range of strong ferromagnetic bonds (≥ 2.66 angstrom). The analogous f site in Er 2 Fe 17 does not develop as large a magnetic moment. In addition, the same sites show strong preference for Fe atoms in the respective substituted compounds. Due to poor phase stability of Er 2 (Co x Fe 1 -x ) 14 B compounds, iron substitution has been studied in detail in Er 2 (Co x Fe 1 -x ) 17 alloys for site specific order an lattice distortion effects. However, a nonlinear change in the c lattice parameter observed in the neutron diffraction results cannot be explained on the basis of site preference alone. The neutron refinement results indicate iron rich compositions in Er 2 (Co x Fe 1 -x ) 17 materials, which is related to random substitution of Fe dumbbell pairs in the rare earth sites in the lattice. However, extensive electron microscopy (selected area electron diffraction and high resolution imaging) of Er 2 Fe 17 and Er 2 (Co .40 Fe .60 ) 17 failed to reveal any microscopic inhomogeneity. 12 refs., 5 figs., 2 tabs

  5. Drawing the geometry of 3d transition metal-boron pairs in silicon from electron emission channeling experiments

    Silva, Daniel; Wahl, Ulrich; Martins Correia, Joao; Augustyns, Valerie; De Lemos Lima, Tiago Abel; Granadeiro Costa, Angelo Rafael; David Bosne, Eric; Castro Ribeiro Da Silva, Manuel; Esteves De Araujo, Araujo Joao Pedro; Da Costa Pereira, Lino Miguel

    2016-01-01

    Although the formation of transition metal-boron pairs is currently well established in silicon processing, the geometry of these complexes is still not completely understood. We investigated the lattice location of the transition metals manganese, iron, cobalt and nickel in n- and p+-type silicon by means of electron emission channeling. For manganese, iron and cobalt, we observed an increase of sites near the ideal tetrahedral interstitial position by changing the doping from n- to p+-type Si. Such increase was not observed for Ni. We ascribe this increase to the formation of pairs with boron, driven by Coulomb interactions, since the majority of iron, manganese and cobalt is positively charged in p+-type silicon while Ni is neutral. We propose that breathing mode relaxation around the boron ion within the pair causes the observed displacement from the ideal tetrahedral interstitial site. We discuss the application of the emission channeling technique in this system and, in particular, how it provides insi...

  6. Ferromagnetic and twin domains in LCMO manganites

    Jung, G.; Markovich, V.; Mogilyanski, D.; Beek, C. van der; Mukovskii, Y.M.

    2005-01-01

    Ferromagnetic and twin domains in lightly Ca-doped La 1-x Ca x MnO 3 single crystals have been visualized and investigated by means of the magneto-optical technique. Both types of domains became visible below the Curie temperature. The dominant structures seen in applied magnetic field are associated with magneto-crystalline anisotropy and twin domains. In a marked difference to the twin domains which appear only in applied magnetic field, ferromagnetic domains show up in zero applied field and are characterized by oppositely oriented spontaneous magnetization in adjacent domains. Ferromagnetic domains take form of almost periodic, corrugated strip-like structures. The corrugation of the ferromagnetic domain pattern is enforced by the underlying twin domains

  7. High-frequency EPR on high-spin transition-metal sites

    Mathies, Guinevere

    2012-01-01

    The electronic structure of transition-metal sites can be probed by electron-paramagnetic-resonance (EPR) spectroscopy. The study of high-spin transition-metal sites benefits from EPR spectroscopy at frequencies higher than the standard 9.5 GHz. However, high-frequency EPR is a developing field. In

  8. The 1s x-ray absorption pre-edge structures in transition metal oxides

    de Groot, Frank|info:eu-repo/dai/nl/08747610X; Vanko, Gyoergy; Glatzel, Pieter

    2009-01-01

    We develop a general procedure to analyse the pre-edges in 1s x-ray absorption near edge structure (XANES) of transition metal oxides and coordination complexes. Transition metal coordination complexes can be described from a local model with one metal ion. The 1s 3d quadrupole transitions are

  9. Predicted stability, structures, and magnetism of 3d transition metal nitrides: the M4N phases

    Fang, C.M.; Koster, R.S.; Li, W.F.; van Huis, M.A.

    2014-01-01

    The 3d transition metal nitrides M4N (Sc4N, Ti4N, V4N, Cr4N, Mn4N, Fe4N, Co4N, Ni4N, and Cu4N) have unique phase relationships, crystal structures, and electronic and magnetic properties. Here we present a systematic density functional theory (DFT) study on these transition metal nitrides, assessing

  10. Converged G W quasiparticle energies for transition metal oxide perovskites

    Ergönenc, Zeynep; Kim, Bongjae; Liu, Peitao; Kresse, Georg; Franchini, Cesare

    2018-02-01

    The ab initio calculation of quasiparticle (QP) energies is a technically and computationally challenging problem. In condensed matter physics, the most widely used approach to determine QP energies is the G W approximation. Although the G W method has been widely applied to many typical semiconductors and insulators, its application to more complex compounds such as transition metal oxide perovskites has been comparatively rare, and its proper use is not well established from a technical point of view. In this work, we have applied the single-shot G0W0 method to a representative set of transition metal oxide perovskites including 3 d (SrTiO3, LaScO3, SrMnO3, LaTiO3, LaVO3, LaCrO3, LaMnO3, and LaFeO3), 4 d (SrZrO3, SrTcO3, and Ca2RuO4 ), and 5 d (SrHfO3, KTaO3, and NaOsO3) compounds with different electronic configurations, magnetic orderings, structural characteristics, and band gaps ranging from 0.1 to 6.1 eV. We discuss the proper procedure to obtain well-converged QP energies and accurate band gaps within single-shot G0W0 by comparing the conventional approach based on an incremental variation of a specific set of parameters (number of bands, energy cutoff for the plane-wave expansion and number of k points) and the basis-set extrapolation scheme [J. Klimeš et al., Phys. Rev. B 90, 075125 (2014), 10.1103/PhysRevB.90.075125]. Although the conventional scheme is not supported by a formal proof of convergence, for most cases it delivers QP energies in reasonably good agreement with those obtained by the basis-set correction procedure and it is by construction more useful for calculating band structures. In addition, we have inspected the difference between the adoption of norm-conserving and ultrasoft potentials in G W calculations and found that the norm violation for the d shell can lead to less accurate results in particular for charge-transfer systems and late transition metals. A minimal statistical analysis indicates that the correlation of the G W data

  11. Magnetoresistance of magnetically doped ZnO films

    Behan, A J; Mokhtari, A; Blythe, H J; Fox, A M; Gehring, G A [Department of Physics and Astronomy, University of Sheffield, Sheffield S3 7RH (United Kingdom); Ziese, M, E-mail: G.A.Gehring@sheffield.ac.u [Division of Superconductivity and Magnetism, University of Leipzig, D-04103, Leipzig (Germany)

    2009-08-26

    Magnetoresistance measurements have been made at 5 K on doped ZnO thin films grown by pulsed laser deposition. ZnCoO, ZnCoAlO and ZnMnAlO samples have been investigated and compared to similar films containing no transition metal dopants. It is found that the Co-doped samples with a high carrier concentration have a small negative magnetoresistance, irrespective of their magnetic moment. On decreasing the carrier concentration, a positive contribution to the magnetoresistance appears and a further negative contribution. This second, negative contribution, which occurs at very low carrier densities, correlates with the onset of ferromagnetism due to bound magnetic polarons suggesting that the negative magnetoresistance results from the destruction of polarons by a magnetic field. An investigation of the anisotropic magnetoresistance showed that the orientation of the applied magnetic field, relative to the sample, had a large effect. The results for the ZnMnAlO samples showed less consistent trends.

  12. A novel recipe to improve the magnetic properties of Mn doped CeO{sub 2} as a room temperature ferromagnetic diluted metal oxide

    Al-Agel, Faisal A., E-mail: fagel2@yahoo.com [King Abdulaziz University, Faculty of Science, Department of Physics, Jeddah (Saudi Arabia); Al-Arfaj, Esam [Umm Alqura University, Department of Physics, Makkah (Saudi Arabia); Al-Ghamdi, Ahmed A. [King Abdulaziz University, Faculty of Science, Department of Physics, Jeddah (Saudi Arabia); Losovyj, Yaroslav [Indiana University, Department of Chemistry, Bloomington, IN 47405 (United States); Bronstein, Lyudmila M. [King Abdulaziz University, Faculty of Science, Department of Physics, Jeddah (Saudi Arabia); Indiana University, Department of Chemistry, Bloomington, IN 47405 (United States); Mahmoud, Waleed E. [King Abdulaziz University, Faculty of Science, Department of Physics, Jeddah (Saudi Arabia); Suez Canal University, Faculty of Science, Department of Physics, Ismailia (Egypt)

    2014-06-01

    Mn doped ceria nanocrystals have been prepared using hexamethylene triperoxide diamine assisted solvothermal technique for the first time. The impact of this novel recipe on the structure, magnetic and spectroscopic behaviors was discussed. The doped oxides were studied using X-ray powder diffraction (XRD), transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), and magnetic measurements. The XRD analysis revealed that all the powders can be indexed to the pure cubic ceria, revealing complete solubility of Mn atoms in the ceria crystal structure with an interstitial substitution of Mn in the Ce sites. At the percolation concentration x=0.08 (Mn{sub 0.08}Ce{sub 0.92}O{sub 2}), the Mn doped cerium oxide displays a very high saturation magnetization of 4.48 emu/g and coercivity of 175.5 Oe. The enhanced magnetic properties are attributed to the formation of the complex between the Mn ion and an oxygen vacancy which is confirmed by the XPS analysis. According to the obtained results, one can say that this novel synthetic recipe increased the solubility of Mn ions into the CeO{sub 2} crystal structure and improved the magnetization by more than 37 times compared to the Mn doped CeO{sub 2} prepared by conventional methods. - Highlights: • Mn doped ceria was prepared by HMTD assisted solvothermal technique. • Complete solubility of Mn atoms in the ceria structure was achieved up to 10 at%. • High saturation magnetization of 4.48 emu/g was achieved at 8 at%. • The magnetization was improved by more than 37 times compared to conventional methods.

  13. Ferromagnetic nanorings

    Vaz, C A F; Hayward, T J; Llandro, J; Schackert, F; Morecroft, D; Bland, J A C; Klaeui, M; Laufenberg, M; Backes, D; Ruediger, U; Castano, F J; Ross, C A; Heyderman, L J; Nolting, F; Locatelli, A; Faini, G; Cherifi, S; Wernsdorfer, W

    2007-01-01

    Ferromagnetic metal rings of nanometre range widths and thicknesses exhibit fundamentally new spin states, switching behaviour and spin dynamics, which can be precisely controlled via geometry, material composition and applied field. Following the discovery of the 'onion state', which mediates the switching to and between vortex states, a range of fascinating phenomena has been found in these structures. In this overview of our work on ring elements, we first show how the geometric parameters of ring elements determine the exact equilibrium spin configuration of the domain walls of rings in the onion state, and we show how such behaviour can be understood as the result of the competition between the exchange and magnetostatic energy terms. Electron transport provides an extremely sensitive probe of the presence, spatial location and motion of domain walls, which determine the magnetic state in individual rings, while magneto-optical measurements with high spatial resolution can be used to probe the switching behaviour of ring structures with very high sensitivity. We illustrate how the ring geometry has been used for the study of a wide variety of magnetic phenomena, including the displacement of domain walls by electric currents, magnetoresistance, the strength of the pinning potential introduced by nanometre size constrictions, the effect of thermal excitations on the equilibrium state and the stochastic nature of switching events

  14. First-Principles Study on the Adsorption Properties of Transition-Metal Atoms on CaO(001) Surfaces

    Yu, Byung Deok [University of Seoul, Seoul (Korea, Republic of); Jang, Young-Rok [Incheon National University, Incheon (Korea, Republic of)

    2017-03-15

    By using first-principles electronic-structure calculations based on the density functional theory, we systematically investigated the adsorption properties of transition-metal (TM) adatoms on CaO(001) surfaces. Optimized adsorption structures and energetics of TM adatoms on CaO(001) are reported for various adsorption structures. The results are different from those of TM adatoms on MgO(001). Concomitantly, this suggests different dynamical properties of TM adatoms on CaO(001) surfaces as compared with TM adatoms on MgO(001) surfaces. Also performed was an analysis of the electronic structures of the TM adatoms on CaO(001) by using the energy positions of the adsorbate states with respect to the valence band maximum of CaO. The results are discussed in connection with the charge states of the TM adatoms on doped CaO(001).

  15. Impurities in Antiferromagnetic Transition-Metal Oxides - Symmetry and Optical Transitions

    Petersen, John Emil, III

    considered. For example, simple rock-salt transition-metal oxides are quite different from the high temperature superconducting cuprates. A range of materials is studied here, in order to gain a greater understanding of optical transitions in highly-correlated systems. In this work, O vacancies are introduced in NiO, along with Fe impurities, to understand better the band filling in the insulating behavior observed experimentally. These results are compared with those of La2NiO4, La2CuO4, La2-xSr xNiO4, and La2-xSrxCuO4. to elucidate the mechanisms behind the symmetry breaking phenomena in the Sr doped systems. As it turns out, indeed, the x2 - y2 orbital in these materials plays a critical role in spatial charge distribution, magnetic, and spin densities which are coupled to the dopant position in the lattice. The in-depth study of electronic and optical properties of transition-metal oxides presented here provides theoretical characterization of the infamous pseudogap in the cuprates - one of the greatest mysteries of modern solid state physics. In addition, via Density Functional Perturbation Theory, the phonon coupling with charge-density wave is explored in La2-xSr xNiO4 and found to be the dominant contributing factor to the colossal dielectric constant.

  16. Atomic structure of non-stoichiometric transition metal carbides

    Moisy-Maurice, Virginie.

    1981-10-01

    Different kinds of experimental studies of the atomic arrangement in non-stoichiometric transition metal carbides are proposed: the ordering of carbon vacancies and the atomic static displacements are the main subjects studied. Powder neutron diffraction on TiCsub(1-x) allowed us to determine the order-disorder transition critical temperature -Tsub(c) approximately 770 0 C- in the TiCsub(0.52-0.67) range, and to analyze at 300 K the crystal structure of long-range ordered samples. A neutron diffuse scattering quantitative study at 300 K of short-range order in TiCsub(0.76), TiCsub(0.79) and NbCsub(0.73) single crystals is presented: as in Ti 2 Csub(1+x) and Nb 6 C 5 superstructures, vacancies avoid to be on each side of a metal atom. Besides, the mean-square carbon atom displacements from their sites are small, whereas metal atoms move radially about 0.03 A away from vacancies. These results are in qualitative agreement with EXAFS measurements at titanium-K edge of TiCsub(1-x). An interpretation of ordering in term of short-range interaction pair potentials between vacancies is proposed [fr

  17. The prospects of transition metal dichalcogenides for ultimately scaled CMOS

    Thiele, S.; Kinberger, W.; Granzner, R.; Fiori, G.; Schwierz, F.

    2018-05-01

    MOSFET gate length scaling has been a main source of progress in digital electronics for decades. Today, researchers still spend considerable efforts on reducing the gate length and on developing ultimately scaled MOSFETs, thereby exploring both new device architectures and alternative channel materials beyond Silicon such as two-dimensional TMDs (transition metal dichalcogenide). On the other hand, the envisaged scaling scenario for the next 15 years has undergone a significant change recently. While the 2013 ITRS edition required a continuation of aggressive gate length scaling for at least another 15 years, the 2015 edition of the ITRS suggests a deceleration and eventually a levelling off of gate length scaling and puts more emphasis on alternative options such as pitch scaling to keep Moore's Law alive. In the present paper, future CMOS scaling is discussed in the light of emerging two-dimensional MOSFET channel, in particular two-dimensional TMDs. To this end, the scaling scenarios of the 2013 and 2015 ITRS editions are considered and the scaling potential of TMD MOSFETs is investigated by means of quantum-mechanical device simulations. It is shown that for ultimately scaled MOSFETs as required in the 2013 ITRS, the heavy carrier effective masses of the Mo- and W-based TMDs are beneficial for the suppression of direct source-drain tunneling, while to meet the significantly relaxed scaling targets of the 2016 ITRS heavy-effective-mass channels are not needed.

  18. Hierarchically Nanostructured Transition Metal Oxides for Lithium‐Ion Batteries

    Zheng, Mingbo; Tang, Hao; Li, Lulu; Hu, Qin; Zhang, Li; Xue, Huaiguo

    2018-01-01

    Abstract Lithium‐ion batteries (LIBs) have been widely used in the field of portable electric devices because of their high energy density and long cycling life. To further improve the performance of LIBs, it is of great importance to develop new electrode materials. Various transition metal oxides (TMOs) have been extensively investigated as electrode materials for LIBs. According to the reaction mechanism, there are mainly two kinds of TMOs, one is based on conversion reaction and the other is based on intercalation/deintercalation reaction. Recently, hierarchically nanostructured TMOs have become a hot research area in the field of LIBs. Hierarchical architecture can provide numerous accessible electroactive sites for redox reactions, shorten the diffusion distance of Li‐ion during the reaction, and accommodate volume expansion during cycling. With rapid research progress in this field, a timely account of this advanced technology is highly necessary. Here, the research progress on the synthesis methods, morphological characteristics, and electrochemical performances of hierarchically nanostructured TMOs for LIBs is summarized and discussed. Some relevant prospects are also proposed. PMID:29593962

  19. Nano tubular Transition Metal Oxide for Hydrogen Production

    Sreekantan, S.; San, E.P.; Kregvirat, W.; Wei, L.C.

    2011-01-01

    TiO 2 , transition metal oxide nano tubes were successfully grown by anodizing of titanium foil (Ti) in ethylene glycol electrolyte containing 5wt. % hydrogen peroxide and 5wt. % ammonium fluoride for 60 minutes at 60V. It was found such electrochemical condition resulted in the formation of nano tube with average diameter of 90nm and length of 6.6 μm. These samples were used to study the effect of W loading by RF sputtering on TiO 2 nano tubes. Amorphous TiO 2 nano tube substrate leads to enhance incorporation of W instead of anatase. Therefore for the entire study, W was sputtered on amorphous TiO 2 nano tube substrate. TiO 2 nano tube sputtered for 1 minute resulted in the formation of W-O-Ti while beyond this point (10 minutes); it accumulates to form a self independent structure of WO 3 on the surface of the nano tubes. TiO 2 nano tube sputtered for 1 minute at 150 W and annealed at 450 degree Celsius exhibited best photocurrent density (1.4 mA/ cm 2 ) with photo conversion efficiency of 2.5 %. The reason for such behavior is attributed to W 6+ ions allows for electron traps that suppress electron hole recombination and exploit the lower band gap of material to produce a water splitting process by increasing the charge separation and extending the energy range of photoexcitation for the system. (author)

  20. Magnesium nanoparticles with transition metal decoration for hydrogen storage

    Pasquini, Luca; Callini, Elsa; Brighi, Matteo; Boscherini, Federico; Montone, Amelia; Jensen, Torben R.; Maurizio, Chiara; Vittori Antisari, Marco; Bonetti, Ennio

    2011-01-01

    We report on the hydrogen storage behaviour of Mg nanoparticles (NPs) (size range 100 nm–1 μm) with metal-oxide core–shell morphology synthesized by inert gas condensation and decorated by transition metal (TM) (Pd or Ti) clusters via in situ vacuum deposition. The structure and morphology of the as-prepared and hydrogenated NPs is studied by electron microscopy, X-ray diffraction including in situ experiments and X-ray absorption spectroscopy, in order to investigate the relationships with the hydrogen storage kinetics measured by the volumetric Sieverts method. With both Pd and Ti, the decoration deeply improves the hydrogen sorption properties: previously inert NPs exhibit complete hydrogenation with fast transformation kinetics, good stability and reversible gravimetric capacity that can attain 6 wt%. In the case of Pd-decoration, the occurrence of Mg–Pd alloying is observed at high temperatures and in dependence of the hydrogen pressure conditions. These structural transformations modify both the kinetics and thermodynamics of hydride formation, while Ti-decoration has an effect only on the kinetics. The experimental results are discussed in relation with key issues such as the amount of decoration, the heat of mixing between TM and Mg and the binding energy between TM and hydrogen.