The Effect of Acceptor and Donor Doping on Oxygen Vacancy Concentrations in Lead Zirconate Titanate (PZT).

Science.gov (United States)

Slouka, Christoph; Kainz, Theresa; Navickas, Edvinas; Walch, Gregor; Hutter, Herbert; Reichmann, Klaus; Fleig, Jürgen

2016-11-22

The different properties of acceptor-doped (hard) and donor-doped (soft) lead zirconate titanate (PZT) ceramics are often attributed to different amounts of oxygen vacancies introduced by the dopant. Acceptor doping is believed to cause high oxygen vacancy concentrations, while donors are expected to strongly suppress their amount. In this study, La 3+ donor-doped, Fe 3+ acceptor-doped and La 3+ /Fe 3+ -co-doped PZT samples were investigated by oxygen tracer exchange and electrochemical impedance spectroscopy in order to analyse the effect of doping on oxygen vacancy concentrations. Relative changes in the tracer diffusion coefficients for different doping and quantitative relations between defect concentrations allowed estimates of oxygen vacancy concentrations. Donor doping does not completely suppress the formation of oxygen vacancies; rather, it concentrates them in the grain boundary region. Acceptor doping enhances the amount of oxygen vacancies but estimates suggest that bulk concentrations are still in the ppm range, even for 1% acceptor doping. Trapped holes might thus considerably contribute to the charge balancing of the acceptor dopants. This could also be of relevance in understanding the properties of hard and soft PZT.

The Effect of Acceptor and Donor Doping on Oxygen Vacancy Concentrations in Lead Zirconate Titanate (PZT

Directory of Open Access Journals (Sweden)

Christoph Slouka

2016-11-01

Full Text Available The different properties of acceptor-doped (hard and donor-doped (soft lead zirconate titanate (PZT ceramics are often attributed to different amounts of oxygen vacancies introduced by the dopant. Acceptor doping is believed to cause high oxygen vacancy concentrations, while donors are expected to strongly suppress their amount. In this study, La3+ donor-doped, Fe3+ acceptor-doped and La3+/Fe3+-co-doped PZT samples were investigated by oxygen tracer exchange and electrochemical impedance spectroscopy in order to analyse the effect of doping on oxygen vacancy concentrations. Relative changes in the tracer diffusion coefficients for different doping and quantitative relations between defect concentrations allowed estimates of oxygen vacancy concentrations. Donor doping does not completely suppress the formation of oxygen vacancies; rather, it concentrates them in the grain boundary region. Acceptor doping enhances the amount of oxygen vacancies but estimates suggest that bulk concentrations are still in the ppm range, even for 1% acceptor doping. Trapped holes might thus considerably contribute to the charge balancing of the acceptor dopants. This could also be of relevance in understanding the properties of hard and soft PZT.

High-throughput DFT calculations of formation energy, stability and oxygen vacancy formation energy of ABO3 perovskites

Science.gov (United States)

Emery, Antoine A.; Wolverton, Chris

2017-10-01

ABO3 perovskites are oxide materials that are used for a variety of applications such as solid oxide fuel cells, piezo-, ferro-electricity and water splitting. Due to their remarkable stability with respect to cation substitution, new compounds for such applications potentially await discovery. In this work, we present an exhaustive dataset of formation energies of 5,329 cubic and distorted perovskites that were calculated using first-principles density functional theory. In addition to formation energies, several additional properties such as oxidation states, band gap, oxygen vacancy formation energy, and thermodynamic stability with respect to all phases in the Open Quantum Materials Database are also made publicly available. This large dataset for this ubiquitous crystal structure type contains 395 perovskites that are predicted to be thermodynamically stable, of which many have not yet been experimentally reported, and therefore represent theoretical predictions. The dataset thus opens avenues for future use, including materials discovery in many research-active areas.

Oxygen vacancy defects in Ta{sub 2}O{sub 5} showing long-range atomic re-arrangements

Energy Technology Data Exchange (ETDEWEB)

Guo, Yuzheng; Robertson, John [Engineering Department, Cambridge University, Cambridge CB2 1PZ (United Kingdom)

2014-03-17

The structure, formation energy, and energy levels of the various oxygen vacancies in Ta{sub 2}O{sub 5} have been calculated using the λ phase model. The intra-layer vacancies give rise to unusual, long-range bonding rearrangements, which are different for each defect charge state. The 2-fold coordinated intra-layer vacancy is the lowest cost vacancy and forms a deep level 1.5 eV below the conduction band edge. The 3-fold intra-layer vacancy and the 2-fold inter-layer vacancy are higher cost defects, and form shallower levels. The unusual bonding rearrangements lead to low oxygen migration barriers, which are useful for resistive random access memory applications.

Effects of oxygen vacancies on the structural and optical properties of β-Ga2O3.

Science.gov (United States)

Dong, Linpeng; Jia, Renxu; Xin, Bin; Peng, Bo; Zhang, Yuming

2017-01-09

The structural, electronic, and optical properties of β-Ga 2 O 3 with oxygen vacancies are studied by employing first-principles calculations based on density function theory. Based on the defects formation energies, we conclude the oxygen vacancies are most stable in their fully charge states. The electronic structures and optical properties of β-Ga 2 O 3 are calculated by Generalized Gradient Approximation + U formalisms with the Hubbard U parameters set 7.0 eV and 8.5 eV for Ga and O ions, respectively. The calculated bandgap is 4.92 eV, which is consistent with the experimental value. The static real dielectric constants of the defective structures are increased compared with the intrinsic one, which is attributed to the level caused by the Ga-4s states in the bandgap. Extra peaks are introduced in the absorption spectra, which are related to Ga-4s and O-2p states. Experimentally, β-Ga 2 O 3 films are deposited under different O 2 volume percentage with ratio-frequency magnetron sputtering method. The measured results indicate that oxygen vacancies can induce extra emission peaks in the photoluminescence spectrum, the location of these peaks are close to the calculated results. Extra O 2 can increase the formation energies of oxygen vacancies and thus reduce oxygen vacancies in β-Ga 2 O 3 .

High-temperature equilibrium vacancy formation in ceramic materials studied by positron annihilation

International Nuclear Information System (INIS)

Forster, M.; Claudy, W.; Hermes, H.; Major, J.; Schaefer, H.E.; Koch, M.; Maier, K.; Stoll, H.

1992-01-01

Positron lifetime measurements were used in order to study thermal vacancy formation in NiO, YBa 2 Cu 3 O 7-δ , α-Al 2 O 3 , MgO and 6H-SiC at high temperatures. In NiO two increases of the positron trapping rate at 450K and 1200K (po 2 =10 5 Pa) are attributed to the change of charge of neutral extrinsic Ni-vacancies (c ≅ 10 -4 ) into a negative charge state and to the nonstochiometric formation of charged Ni-vacancies at high temperatures. In YBa 2 Cu 3 O 7-δ the oxygen loss or uptake at T > 680K with an activation enthalpy of 1.03eV can be studied by the variation of the positron lifetime with temperature and oxygen partial pressure. In α-Al 2 O 3 the positrons are annihilated from the delocalized free state between 1000K and 2250K and no positron trapping of thermally formed vacancies was detected which may be understood in terms of the theoretically predicted low concentrations of thermal vacancies. In MgO and 6H-SiC positron lifetime measurements were performed up to temperatures of about 2000K

Tracking Oxygen Vacancies in Thin Film SOFC Cathodes

Science.gov (United States)

Leonard, Donovan; Kumar, Amit; Jesse, Stephen; Kalinin, Sergei; Shao-Horn, Yang; Crumlin, Ethan; Mutoro, Eva; Biegalski, Michael; Christen, Hans; Pennycook, Stephen; Borisevich, Albina

2011-03-01

Oxygen vacancies have been proposed to control the rate of the oxygen reduction reaction and ionic transport in complex oxides used as solid oxide fuel cell (SOFC) cathodes [1,2]. In this study oxygen vacancies were tracked, both dynamically and statically, with the combined use of scanned probe microscopy (SPM) and scanning transmission electron microscopy (STEM). Epitaxial films of La 0.8 Sr 0.2 Co O3 (L SC113) and L SC113 / LaSrCo O4 (L SC214) on a GDC/YSZ substrate were studied, where the latter showed increased electrocatalytic activity at moderate temperature. At atomic resolution, high angle annular dark field STEM micrographs revealed vacancy ordering in L SC113 as evidenced by lattice parameter modulation and EELS studies. The evolution of oxygen vacancy concentration and ordering with applied bias and the effects of bias cycling on the SOFC cathode performance will be discussed. Research is sponsored by the of Materials Sciences and Engineering Division, U.S. DOE.

Ferromagnetism and half metallicity induced by oxygen vacancies in the double perovskite BaSrNiWO{sub 6}: DFT study

Energy Technology Data Exchange (ETDEWEB)

Aharbil, Y. [Laboratoire de Chimie Physique des Matériaux LCPM, Faculté des Sciences Ben M' Sik, Casablanca (Morocco); Labrim, H. [Unité Science de la Matière/DERS/Centre National de l’Energie, des Sciences et des Techniques Nucléaires (CNESTEN), Rabat (Morocco); Benmokhtar, S.; Haddouch, M. Ait [Laboratoire de Chimie Physique des Matériaux LCPM, Faculté des Sciences Ben M' Sik, Casablanca (Morocco); Bahmad, L., E-mail: bahmad@fsr.ac.ma [Mohammed V University in Rabat, Laboratoire de Magnétisme et Physique des Hautes Energies L.M.P.H.E. URAC-12, B.P. 1014, Rabat (Morocco); Belhaj, A. [LIRST, Département de Physique, Faculté Poly-disciplinaire, Université Sultan Moulay Slimane, Béni Mellal (Morocco); Ez-Zahraouy, H.; Benyoussef, A. [Mohammed V University in Rabat, Laboratoire de Magnétisme et Physique des Hautes Energies L.M.P.H.E. URAC-12, B.P. 1014, Rabat (Morocco)

2016-11-01

Using the spin polarized density functional theory (DFT) and exploring the Plane-Wave Self-Consistent Field (PWscf) code implemented in Quantum-ESPRESSO package, we investigate the effect of the Oxygen vacancies (V{sub O}) and the Oxygen interstitial (O{sub i}) on the double perovskite BaSrNiWO{sub 6}. This deals with the magnetic ordering and the electronic structure in such a pure sample exhibiting the insulating anti-ferromagnetic (AFM) state. This study shows that the presence of oxygen deficient defects converts the insulating to half metal with ferromagnetic or anti-ferromagnetic states. The magnetic ordering in BaSrNiWO{sub 6−δ} depends on the position of the Oxygen vacancy in the unit cell. However, it has been shown that the Oxygen interstitial preserves the anti-ferromagnetic propriety. We have computed the formation energies of different positions of the Oxygen vacancy (V{sub O}) and the Oxygen interstitial (O{sub i}) in the BaSrNiWO{sub 6} compound. We showed that the formation of V{sub O} is easier and vice versa for the O{sub i} formation. The obtained results reveal(V{sub O}) and the Oxygen interstitial (O{sub i}) that the anti-ferromagnetic can be converted to ferromagnetic in the double perovskite BaSrNiWO{sub 6} induced by Oxygen vacancies V{sub O}. - Highlights: • We have studied the ferromagnetism and Half Metallicity in Double Perovskite BaSrNiWO{sub 6}. • We have applied the Ab-inito calculations using the DFT approach. • We showed the effects induced by Oxygen Vacancies and Oxygen interstitial. • We found that the magnetic ordering in BaSrNiWO{sub 6−δ} depends on the position of the Oxygen vacancy in the unit cell.

Oxygen vacancy effects in HfO2-based resistive switching memory: First principle study

Directory of Open Access Journals (Sweden)

Yuehua Dai

2016-08-01

Full Text Available The work investigated the shape and orientation of oxygen vacancy clusters in HfO2-base resistive random access memory (ReRAM by using the first-principle method based on the density functional theory. Firstly, the formation energy of different local Vo clusters was calculated in four established orientation systems. Then, the optimized orientation and charger conductor shape were identified by comparing the isosurface plots of partial charge density, formation energy, and the highest isosurface value of oxygen vacancy. The calculated results revealed that the [010] orientation was the optimal migration path of Vo, and the shape of system D4 was the best charge conductor in HfO2, which effectively influenced the SET voltage, formation voltage and the ON/OFF ratio of the device. Afterwards, the PDOS of Hf near Vo and total density of states of the system D4_010 were obtained, revealing the composition of charge conductor was oxygen vacancy instead of metal Hf. Furthermore, the migration barriers of the Vo hopping between neighboring unit cells were calculated along four different orientations. The motion was proved along [010] orientation. The optimal circulation path for Vo migration in the HfO2 super-cell was obtained.

A theoretical study of stability and vacancy replenishing of MoO{sub 3}(0 1 0) surfaces in oxygen atmosphere

Energy Technology Data Exchange (ETDEWEB)

Lei, Yan-Hua; Chen, Zhao-Xu, E-mail: zxchen@nju.edu.cn

2016-01-15

Graphical abstract: - Highlights: • Under normal experimental conditions perfect surface of MoO{sub 3}(0 1 0) is favorable. • Line defects along asymmetric oxygen direction in lean oxygen condition are favored. • Vacancy replenishing occurs on vacancies formed by terminal and asymmetrical oxygen. - Abstract: Oxygen vacancies on transition metal oxide surfaces are catalytically very important. The stability, shape and replenishing process of the vacancies are critical to understanding reactions happening on the surfaces. In this paper we investigate the stability of various defective MoO{sub 3}(0 1 0) surfaces and examine the influence of environmental oxygen on the stability as well as the active sites for the replenishing process. Our calculations reveal that the line oxygen defect along a (asymmetric oxygen) direction is thermodynamically most favorable at higher defect concentration whereas point defect surfaces are unfavorable. Under normal experimental conditions the perfect surface dominates the MoO{sub 3}(0 1 0). We show that for stoichiometric surfaces of any oxides (A{sub x}O{sub y}) the formation energy per vacancy controls the favorable defect shape (line or point defects). Calculations indicate that O{sub 2} can dissociate readily on the surfaces that double vacancies share one Mo atom. The replenishing process of the oxygen vacancies through O{sub 2} dissociation most likely occurs on the double-vacancy containing one terminal and one asymmetrical oxygen vacancies.

Zinc Vacancy Formation and its Effect on the Conductivity of ZnO

Science.gov (United States)

Khan, Enamul; Weber, Marc; Langford, Steve; Dickinson, Tom

2010-03-01

Exposing single crystal ZnO to 193-nm ArF excimer laser radiation can produce metallic zinc nanoparticles along the surface. The particle production mechanism appears to involve interstitial-vacancy pair formation in the near-surface bulk. Conductivity measurements made with one probe inside the laser spot and the other outside show evidence for rectifying behavior. Positron annihilation spectroscopy confirms the presence of Zn vacancies. We suggest that Zn vacancies are a possible source of p-type behavior in irradiated ZnO. Quadrupole mass spectroscopy shows that both oxygen and zinc are emitted during irradiation. Electron-hole pair production has previously been invoked to account for particle desorption from ZnO during UV illumination. Our results suggest that preexisting and laser-generated defects play a critical role in particle desorption and Zn vacancy formation.

Experimental evidence for fast cluster formation of chain oxygen vacancies in YBa2Cu3O7-d being at the origin of the fishtail anomaly

OpenAIRE

Erb, Andreas; Manuel, Alfred A.; Dhalle, Marc; Marti, Frank; Genoud, Jean-Yves; Revaz, Bernard; Junod, Alain; Vasumathi, Dharmavaram; Ishibashi, Shoji; Shukla, Abhay; Walker, Eric; Fischer, Oystein; Fluekiger, Rene; Pozzi, Riccardo; Mali, Mihael

1998-01-01

We report on three different and complementary measurements, namely magnetisation measurements, positron annihilation spectroscopy and NMR measurements, which give evidence that the formation of oxygen vacancy clusters is on the origin of the fishtail anomaly in YBa2Cu3O7-d. While in the case of YBa2Cu3O7.0 the anomaly is intrinsically absent, it can be suppressed in the optimally doped state where vacancies are present. We therefore conclude that the single vacancies or point defects can not...

First principle simulations on the effects of oxygen vacancy in HfO2-based RRAM

Directory of Open Access Journals (Sweden)

Yuehua Dai

2015-01-01

Full Text Available HfO2-based resistive random access memory (RRAM takes advantage of oxygen vacancy (V o defects in its principle of operation. Since the change in resistivity of the material is controlled by the level of oxygen deficiency in the material, it is significantly important to study the performance of oxygen vacancies in formation of conductive filament. Excluding effects of the applied voltage, the Vienna ab initio simulation package (VASP is used to investigate the orientation and concentration mechanism of the oxygen vacancies based on the first principle. The optimal value of crystal orientation [010] is identified by means of the calculated isosurface plots of partial charge density, formation energy, highest isosurface value, migration barrier, and energy band of oxygen vacancy in ten established orientation systems. It will effectively influence the SET voltage, forming voltage, and the ON/OFF ratio of the device. Based on the results of orientation dependence, different concentration models are established along crystal orientation [010]. The performance of proposed concentration models is evaluated and analyzed in this paper. The film is weakly conductive for the samples deposited in a mixture with less than 4.167at.% of V o contents, and the resistive switching (RS phenomenon cannot be observed in this case. The RS behavior improves with an increase in the V o contents from 4.167at.% to 6.25at.%; nonetheless, it is found difficult to switch to a stable state. However, a higher V o concentration shows a more favorable uniformity and stability for HfO2-based RRAM.

Molecular dynamics simulations of oxygen vacancy diffusion in SrTiO3

International Nuclear Information System (INIS)

Schie, Marcel; Marchewka, Astrid; Waser, Rainer; Müller, Thomas; De Souza, Roger A

2012-01-01

A classical force-field model with partial ionic charges was applied to study the behaviour of oxygen vacancies in the perovskite oxide strontium titanate (SrTiO 3 ). The dynamical behaviour of these point defects was investigated as a function of temperature and defect concentration by means of molecular dynamics (MD) simulations. The interaction between oxygen vacancies and an extended defect, here a Σ3(111) grain boundary, was also examined by means of MD simulations. Analysis of the vacancy distribution revealed considerable accumulation of vacancies in the envelope of the grain boundary. The possible clustering of oxygen vacancies in bulk SrTiO 3 was studied by means of static lattice calculations within the Mott-Littleton approach. All binary vacancy-vacancy configurations were found to be energetically unfavourable.

Molecular dynamics simulations of oxygen vacancy diffusion in SrTiO3.

Science.gov (United States)

Schie, Marcel; Marchewka, Astrid; Müller, Thomas; De Souza, Roger A; Waser, Rainer

2012-12-05

A classical force-field model with partial ionic charges was applied to study the behaviour of oxygen vacancies in the perovskite oxide strontium titanate (SrTiO(3)). The dynamical behaviour of these point defects was investigated as a function of temperature and defect concentration by means of molecular dynamics (MD) simulations. The interaction between oxygen vacancies and an extended defect, here a Σ3(111) grain boundary, was also examined by means of MD simulations. Analysis of the vacancy distribution revealed considerable accumulation of vacancies in the envelope of the grain boundary. The possible clustering of oxygen vacancies in bulk SrTiO(3) was studied by means of static lattice calculations within the Mott-Littleton approach. All binary vacancy-vacancy configurations were found to be energetically unfavourable.

Interaction of oxygen vacancies in yttrium germanates

KAUST Repository

Wang, Hao

2012-01-01

Forming a good Ge/dielectric interface is important to improve the electron mobility of a Ge metal oxide semiconductor field-effect transistor. A thin yttrium germanate capping layer can improve the properties of the Ge/GeO 2 system. We employ electronic structure calculations to investigate the effect of oxygen vacancies in yttrium-doped GeO 2 and the yttrium germanates Y 2Ge 2O 7 and Y 2GeO 5. The calculated densities of states indicate that dangling bonds from oxygen vacancies introduce in-gap states, but the system remains insulating. However, yttrium-doped GeO 2 becomes metallic under oxygen deficiency. Y-doped GeO 2, Y 2Ge 2O 7 and Y 2GeO 5 are calculated to be oxygen substoichiometric under low Fermi energy conditions. The use of yttrium germanates is proposed as a way to effectively passivate the Ge/dielectric interface. This journal is © 2012 the Owner Societies.

Correlated lifetimes of free paraexcitons and excitons trapped at oxygen vacancies in cuprous oxide

International Nuclear Information System (INIS)

Koirala, Sandhaya; Naka, Nobuko; Tanaka, Koichiro

2013-01-01

We have studied transients of luminescence due to free excitons and excitons trapped at oxygen vacancies in cuprous oxide. We find that both trapped and free paraexcitons have lifetime dependent on temperature and on the oxygen concentration. By using samples containing much less copper vacancies relative to oxygen vacancies, we find out the direct correlation between the free paraexciton lifetime and trapped exciton lifetime. - Highlights: ► We have investigated trapping of free excitons at oxygen vacancies in cuprous oxide. ► Lifetimes of free and trapped excitons exhibit correlative temperature dependence. ► Four-level model with the activation energy of 33 meV well explains the observation. ► Comparison is made using the four samples with different vacancy concentrations. ► We clarified the crucial role of the oxygen vacancy in shortening the lifetimes.

Deep vs shallow nature of oxygen vacancies and consequent n -type carrier concentrations in transparent conducting oxides

Science.gov (United States)

Buckeridge, J.; Catlow, C. R. A.; Farrow, M. R.; Logsdail, A. J.; Scanlon, D. O.; Keal, T. W.; Sherwood, P.; Woodley, S. M.; Sokol, A. A.; Walsh, A.

2018-05-01

The source of n -type conductivity in undoped transparent conducting oxides has been a topic of debate for several decades. The point defect of most interest in this respect is the oxygen vacancy, but there are many conflicting reports on the shallow versus deep nature of its related electronic states. Here, using a hybrid quantum mechanical/molecular mechanical embedded cluster approach, we have computed formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides: In2O3 ,SnO2, and ZnO. We find that, in all three systems, oxygen vacancies form well-localized, compact donors. We demonstrate, however, that such compactness does not preclude the possibility of these states being shallow in nature, by considering the energetic balance between the vacancy binding electrons that are in localized orbitals or in effective-mass-like diffuse orbitals. Our results show that, thermodynamically, oxygen vacancies in bulk In2O3 introduce states above the conduction band minimum that contribute significantly to the observed conductivity properties of undoped samples. For ZnO and SnO2, the states are deep, and our calculated ionization energies agree well with thermochemical and optical experiments. Our computed equilibrium defect and carrier concentrations, however, demonstrate that these deep states may nevertheless lead to significant intrinsic n -type conductivity under reducing conditions at elevated temperatures. Our study indicates the importance of oxygen vacancies in relation to intrinsic carrier concentrations not only in In2O3 , but also in SnO2 and ZnO.

Spin-dependent recombination involving oxygen-vacancy complexes in silicon

OpenAIRE

Franke, David P.; Hoehne, Felix; Vlasenko, Leonid S.; Itoh, Kohei M.; Brandt, Martin S.

2014-01-01

Spin-dependent relaxation and recombination processes in $\\gamma$-irradiated $n$-type Czochralski-grown silicon are studied using continuous wave (cw) and pulsed electrically detected magnetic resonance (EDMR). Two processes involving the SL1 center, the neutral excited triplet state of the oxygen-vacancy complex, are observed which can be separated by their different dynamics. One of the processes is the relaxation of the excited SL1 state to the ground state of the oxygen-vacancy complex, t...

The interplay between dopants and oxygen vacancies in the magnetism of V-doped TiO2

KAUST Repository

Grau-Crespo, Ricardo

2011-08-03

Density functional theory calculations indicate that the incorporation of V into Ti lattice positions of rutile TiO2 leads to magnetic V 4 + species, but the extension and sign of the coupling between dopant moments confirm that ferromagnetic order cannot be reached via low-concentration doping in the non-defective oxide. Oxygen vacancies can introduce additional magnetic centres, and we show here that one of the effects of vanadium doping is to reduce the formation energies of these defects. In the presence of both V dopants and O vacancies all the spins tend to align with the same orientation. We conclude that V doping favours the ferromagnetic behaviour of TiO2 not only by introducing spins associated with the dopant centres but also by increasing the concentration of oxygen vacancies with respect to the pure oxide. © 2001 IOP Publishing Ltd.

The interplay between dopants and oxygen vacancies in the magnetism of V-doped TiO2

KAUST Repository

Grau-Crespo, Ricardo; Schwingenschlö gl, Udo

2011-01-01

Density functional theory calculations indicate that the incorporation of V into Ti lattice positions of rutile TiO2 leads to magnetic V 4 + species, but the extension and sign of the coupling between dopant moments confirm that ferromagnetic order cannot be reached via low-concentration doping in the non-defective oxide. Oxygen vacancies can introduce additional magnetic centres, and we show here that one of the effects of vanadium doping is to reduce the formation energies of these defects. In the presence of both V dopants and O vacancies all the spins tend to align with the same orientation. We conclude that V doping favours the ferromagnetic behaviour of TiO2 not only by introducing spins associated with the dopant centres but also by increasing the concentration of oxygen vacancies with respect to the pure oxide. © 2001 IOP Publishing Ltd.

Understanding cation ordering and oxygen vacancy site preference in Ba3CaNb2O9 from first-principles

Science.gov (United States)

Ding, Hepeng; Virkar, Anil; Liu, Feng

2014-03-01

We investigate the physical mechanism underlying the formation of the B-site cation ordering and the oxygen vacancy site selection in Ba3CaNb2O9 using density functional theory calculations. We found that either cation site exchange or oxygen vacancy formation induces negligible lattice strain. This implies that the ionic radius plays an insignificant role in governing these two processes. Furthermore, the electrostatic interactions are found dominant in the ordering of mixed valence species on one or more sites, the ionic bond strength is identified as the dominant force in governing both the 1:2 B-site cation ordering along the direction and the oxygen vacancy site preference in Ba3CaNb2O9. Specifically, the cation ordering can be rationalized by the increased mixing bonding energy of the Ca-O-Nb bonds over the Ca-O-Ca and Nb-O-Nb bonds, i.e., 1/2(Ca-O-Ca + Nb-O-Nb) Grant Number DE-SC0001061 as a flow through from the University of South Carolina.

The effect of carbon and boron on the accumulation of vacancy-oxygen complexes in silicon

International Nuclear Information System (INIS)

Akhmetov, V.D.; Bolotov, V.V.

1980-01-01

By means of IR-absorption measurements the dose dependencies of the concentrations of vacancy-oxygen complexes (VO), interstitial oxygen atoms (Osub(I)), substitutional carbon atoms (Csub(S)) and interstitial carbon-oxygen complexes (Csub(I)Osub(I)) in n- and p-type silicon irradiated with 1.1 MeV electrons have been investigated. The observed increase of the production rate of VO-complexes with the rise of carbon and boron atoms concentrations (these impurities act as sinks for silicon interstitial atoms) has been explained in terms of annihilation of the vacancies and interstitials on the oxygen atoms. The results obtained show that boron atoms are more effective sinks than carbon atoms for the interstitial silicon atoms. That seems to be connected not only with the higher probability of boron injection into interstitial position but also with the further capture of interstitial silicon atoms on the interstitial boron, i.e. with the interstitial cluster formation. (author)

Oxygen vacancies in oxides studied by annihilation of mono-energetic positrons

Energy Technology Data Exchange (ETDEWEB)

Hugenschmidt, Christoph; Pikart, Philip [ZWE FRM II, Technische Universitaet Muenchen, Lichtenbergstrasse 1, 85747 Garching (Germany); Physik-Department E21, Technische Universitaet Muenchen, James-Franck-Strasse, 85748 Garching (Germany); Schreckenbach, Klaus [Physik-Department E21, Technische Universitaet Muenchen, James-Franck-Strasse, 85748 Garching (Germany)

2009-07-01

Oxygen vacancies play a fundamental role for the material properties of various oxides, e.g. charge carrier density in high-Tc superconductors, magnetic properties of diluted magnetic semiconductors or paramagnetic properties of SiO{sub 2}. In this study, open volume defects in (metal) oxides are investigated by Doppler-broadening spectroscopy (DBS) of the positron annihilation. More detailed information about the chemical surrounding at the positron annihilation site is gained by additional coincident DBS experiments, where a signature of positrons annihilating with electrons from oxygen is observed. The mono-energetic positron beam at NEPOMUC was used which allows depth dependent measurements, and hence the investigation of thin oxide layers. Recent results for metallic oxides such as ZnO are presented and compared with various non-metallic oxides such as amorphous and crystalline SiO{sub 2}, oxygen terminated Si-surface, and ice. The role of neutral and charged oxygen vacancies and the application of the positron annihilation technique to study oxygen vacancies will be discussed.

Evidence of oxygen vacancy and possible intermediate gap state in layered α-MoO{sub 3} single-crystal nanobelts

Energy Technology Data Exchange (ETDEWEB)

Chen, C.Z., E-mail: tcccz@shu.edu.cn; Li, Y.; Tang, X.D.

2016-01-15

Multilayered meso-structured MoO{sub 3} nanobelts have been synthesized by thermally oxidizing a molybdenum chip in a reduced oxygen atmosphere, with a view to disclosing the existence of oxygen vacancy and understanding the mechanism behind the influence of oxygen vacancy on the electronic structure of molybdenum oxides. Based on the measurements from X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM) and transmission electron microscope (TEM), it is found that the as-grown sample is single-crystal α-MoO{sub 3} with a (001) preferred orientation, which shows an irregular belt-like morphology being composed of some ~20 nm single-crystal thin layers. The present sample includes a lot of oxygen vacancies in the lattice, as evidenced by the considerably reduced coordination number of the central Mo atoms from X-ray absorption spectra (XAS) as well as the red shift of the main Raman peaks. The existence of the oxygen vacancies are further tested by the photoluminescence (PL) results as the main emission peak shows an obvious red shift with the corresponding optical band gap reduced to 2.3 eV. Very importantly, an extra emission positioned at 738 nm (1.68 eV) is believed to originate from the recombination of the electrons from the intermediate band (IB) to the valence band (VB), and the formation of the IB in the gap is also caused by oxygen-ion vacancies.

Oxygen Vacancy-Mediated ZnO Nanoparticle Photocatalyst for Degradation of Methylene Blue

Directory of Open Access Journals (Sweden)

Qiuping Zhang

2018-02-01

Full Text Available ZnO nanoparticles (NPs are synthesized by deoxidizing ZnO powder in a vacuum drying process. This process reduces the size of the NPs and increases the concentration of oxygen vacancies on their surfaces. ZnO NPs with sufficient oxygen vacancies are highly effective for the photodecomposition of methylene blue (MB dye in water under ultraviolet irradiation. The MB degradation efficiency exceeds 99 percent after 50 min of light irradiation, and the catalytic property of the NPs remains stable over several complete degradation cycles. It is revealed that the concentration of oxygen vacancies on the surface, and the photocatalytic activity, are both higher for smaller NPs. Oxygen vacancies reduce the recombination rate of photo-generated charge carriers by capturing the electrons and hence, improve the efficiency of redox reactions. In addition, a smaller particle size leads to a larger specific surface area and a higher photonic efficiency for the ZnO NPs.

Effects of hydration and oxygen vacancy on CO2 adsorption and activation on beta-Ga2O3(100).

Science.gov (United States)

Pan, Yun-xiang; Liu, Chang-jun; Mei, Donghai; Ge, Qingfeng

2010-04-20

The effects of hydration and oxygen vacancy on CO(2) adsorption on the beta-Ga(2)O(3)(100) surface have been studied using density functional theory slab calculations. Adsorbed CO(2) is activated on the dry perfect beta-Ga(2)O(3)(100) surface, resulting in a carbonate species. This adsorption is slightly endothermic, with an adsorption energy of 0.07 eV. Water is preferably adsorbed molecularly on the dry perfect beta-Ga(2)O(3)(100) surface with an adsorption energy of -0.56 eV, producing a hydrated perfect beta-Ga(2)O(3)(100) surface. Adsorption of CO(2) on the hydrated surface as a carbonate species is also endothermic, with an adsorption energy of 0.14 eV, indicating a slightly repulsive interaction when H(2)O and CO(2) are coadsorbed. The carbonate species on the hydrated perfect surface can be protonated by the coadsorbed H(2)O to a bicarbonate species, making the CO(2) adsorption exothermic, with an adsorption energy of -0.13 eV. The effect of defects on CO(2) adsorption and activation has been examined by creating an oxygen vacancy on the dry beta-Ga(2)O(3)(100) surface. The formation of an oxygen vacancy is endothermic, by 0.34 eV, with respect to a free O(2) molecule in the gas phase. Presence of the oxygen vacancy promoted the adsorption and activation of CO(2). In the most stable CO(2) adsorption configuration on the dry defective beta-Ga(2)O(3)(100) surface with an oxygen vacancy, one of the oxygen atoms of the adsorbed CO(2) occupies the oxygen vacancy site, and the CO(2) adsorption energy is -0.31 eV. Water favors dissociative adsorption at the oxygen vacancy site on the defective surface. This process is spontaneous, with a reaction energy of -0.62 eV. These results indicate that, when water and CO(2) are present in the adsorption system simultaneously, water will compete with CO(2) for the oxygen vacancy sites and impact CO(2) adsorption and conversion negatively.

Enhanced Photocatalytic Activity of Vacuum-activated TiO2 Induced by Oxygen Vacancies.

Science.gov (United States)

Dong, Guoyan; Wang, Xin; Chen, Zhiwu; Lu, Zhenya

2018-05-01

TiO 2 (Degussa P25) photocatalysts harboring abundant oxygen vacancies (Vacuum P25) were manufactured using a simple and economic Vacuum deoxidation process. Control experiments showed that temperature and time of vacuum deoxidation had a significant effect on Vacuum P25 photocatalytic activity. After 240 min of visible light illumination, the optimal Vacuum P25 photocatalysts (vacuum deoxidation treated at 330 °C for 3 h) reach as high as 94% and 88% of photodegradation efficiency for rhodamine B (RhB) and tetracycline, respectively, which are around 4.5 and 4.9 times as that of pristine P25. The XPS, PL and EPR analyses indicated that the oxygen vacancies were produced in the Vacuum P25 during the vacuum deoxidation process. The oxygen vacancy states can produce vacancy energy level located below the conduction band minimum, which resulting in the bandgap narrowing, thus extending the photoresponse wavelength range of Vacuum P25. The positron annihilation analysis indicated that the concentrations ratio of bulk and surface oxygen vacancies could be adjusted by changing the vacuum deoxidation temperature and time. Decreasing the ratio of bulk and surface oxygen vacancies was shown to improve photogenerated electron-hole pair separation efficiency, which leads to an obvious enhancement of the visible photocatalytic activities of Vacuum P25. © 2017 The American Society of Photobiology.

Unraveling the oxygen vacancy structures at the reduced Ce O2(111 ) surface

Science.gov (United States)

Han, Zhong-Kang; Yang, Yi-Zhou; Zhu, Beien; Ganduglia-Pirovano, M. Verónica; Gao, Yi

2018-03-01

Oxygen vacancies at ceria (Ce O2 ) surfaces play an essential role in catalytic applications. However, during the past decade, the near-surface vacancy structures at Ce O2(111 ) have been questioned due to the contradictory results from experiments and theoretical simulations. Whether surface vacancies agglomerate, and which is the most stable vacancy structure for varying vacancy concentration and temperature, are being heatedly debated. By combining density functional theory calculations and Monte Carlo simulations, we proposed a unified model to explain all conflicting experimental observations and theoretical results. We find a novel trimeric vacancy structure which is more stable than any other one previously reported, which perfectly reproduces the characteristics of the double linear surface oxygen vacancy clusters observed by STM. Monte Carlo simulations show that at low temperature and low vacancy concentrations, vacancies prefer subsurface sites with a local (2 × 2) ordering, whereas mostly linear surface vacancy clusters do form with increased temperature and degree of reduction. These results well explain the disputes about the stable vacancy structure and surface vacancy clustering at Ce O2(111 ) , and provide a foundation for the understanding of the redox and catalytic chemistry of metal oxides.

Hydroxyl-dependent Evolution of Oxygen Vacancies Enables the Regeneration of BiOCl photocatalyst

KAUST Repository

Wu, Sujuan

2017-05-02

Photoinduced oxygen vacancies (OVs) are widely investigated as a vital point defect in wide-band-gap semiconductors. Still, the formation mechanism of OVs remains unclear in various materials. To elucidate the formation mechanism of photoinduced OVs in bismuth oxychloride (BiOCl), we synthesized two surface hydroxyl discrete samples in light of the discovery of the significant variance of hydroxyl groups before and after UV light exposure. It is noted that OVs can be obtained easily after UV light irradiation in the sample with surface hydroxyl groups, while variable changes were observed in samples without surface hydroxyls. Density functional theory (DFT) calculations reveal that the binding energy of Bi-O is drastically influenced by surficial hydroxyl groups, which is intensely correlated to the formation of photoinduced OVs. Moreover, DFT calculations reveal that the adsorbed water molecules are energetically favored to dissociate into separate hydroxyl groups at the OV sites via proton transfer to a neighboring bridging oxygen atom, forming two bridging hydroxyl groups per initial oxygen vacancy. This result is consistent with the experimental observation that the disappearance of photoinduced OVs and the recovery of hydroxyl groups on the surface of BiOCl after exposed to a H2O(g)-rich atmosphere, and finally enables the regeneration of BiOCl photocatalyst. Here, we introduce new insights that the evolution of photoinduced OVs is dependent on surface hydroxyl groups, which will lead to the regeneration of active sites in semiconductors. This work is useful for controllable designs of defective semiconductors for applications in photocatalysis and photovoltaics.

Significant room-temperature ferromagnetism in porous ZnO films: The role of oxygen vacancies

Energy Technology Data Exchange (ETDEWEB)

Hou, Xue; Liu, Huiyuan [College of Physics Science & Information Engineering, Hebei Normal University, Shijiazhuang 050024 (China); Key Laboratory of Advanced Films of Hebei Province, Shijiazhuang 050024 (China); Sun, Huiyuan, E-mail: huiyuansun@126.com [College of Physics Science & Information Engineering, Hebei Normal University, Shijiazhuang 050024 (China); Key Laboratory of Advanced Films of Hebei Province, Shijiazhuang 050024 (China); Liu, Lihu; Jia, Xiaoxuan [College of Physics Science & Information Engineering, Hebei Normal University, Shijiazhuang 050024 (China); Key Laboratory of Advanced Films of Hebei Province, Shijiazhuang 050024 (China)

2015-10-15

Graphical abstract: - Highlights: • Porous ZnO films were deposited on porous anodic alumina substrates. • Significant ferromagnetism (FM) has been observed in porous ZnO films (110 emu/cm{sup 3}). • The strong magnetic anisotropy was observed in the porous ZnO films. • The origin of FM is attributed to the oxygen vacancy with a local magnetic moment. - Abstract: Pure porous ZnO films were prepared by direct current reactive magnetron sputtering on porous anodic alumina substrates. Remarkably large room-temperature ferromagnetism was observed in the films. The highest saturation moment along the out-of-plane direction was about 110 emu/cm{sup 3}. Experimental and theoretical results suggested that the oxygen vacancies and the unique porous structure of the films are responsible for the large ferromagnetism. There are two modes of coupling between oxygen vacancies in the porous ZnO films: (i) exchange interactions directly between the oxygen vacancies and (ii) with the mediation of conduction electrons. In addition, it was found that the magnetic moment of ZnO films can be changed by tuning the concentration of oxygen vacancies. These observations may be useful in the development of ZnO-based spintronics devices.

Anisotropic chemical strain in cubic ceria due to oxygen-vacancy-induced elastic dipoles.

Science.gov (United States)

Das, Tridip; Nicholas, Jason D; Sheldon, Brian W; Qi, Yue

2018-06-06

Accurate characterization of chemical strain is required to study a broad range of chemical-mechanical coupling phenomena. One of the most studied mechano-chemically active oxides, nonstoichiometric ceria (CeO2-δ), has only been described by a scalar chemical strain assuming isotropic deformation. However, combined density functional theory (DFT) calculations and elastic dipole tensor theory reveal that both the short-range bond distortions surrounding an oxygen-vacancy and the long-range chemical strain are anisotropic in cubic CeO2-δ. The origin of this anisotropy is the charge disproportionation between the four cerium atoms around each oxygen-vacancy (two become Ce3+ and two become Ce4+) when a neutral oxygen-vacancy is formed. Around the oxygen-vacancy, six of the Ce3+-O bonds elongate, one of the Ce3+-O bond shorten, and all seven of the Ce4+-O bonds shorten. Further, the average and maximum chemical strain values obtained through tensor analysis successfully bound the various experimental data. Lastly, the anisotropic, oxygen-vacancy-elastic-dipole induced chemical strain is polarizable, which provides a physical model for the giant electrostriction recently discovered in doped and non-doped CeO2-δ. Together, this work highlights the need to consider anisotropic tensors when calculating the chemical strain induced by dilute point defects in all materials, regardless of their symmetry.

Enhanced oxygen vacancy diffusion in Ta2O5 resistive memory devices due to infinitely adaptive crystal structure

Science.gov (United States)

Jiang, Hao; Stewart, Derek A.

2016-04-01

Metal oxide resistive memory devices based on Ta2O5 have demonstrated high switching speed, long endurance, and low set voltage. However, the physical origin of this improved performance is still unclear. Ta2O5 is an important archetype of a class of materials that possess an adaptive crystal structure that can respond easily to the presence of defects. Using first principles nudged elastic band calculations, we show that this adaptive crystal structure leads to low energy barriers for in-plane diffusion of oxygen vacancies in λ phase Ta2O5. Identified diffusion paths are associated with collective motion of neighboring atoms. The overall vacancy diffusion is anisotropic with higher diffusion barriers found for oxygen vacancy movement between Ta-O planes. Coupled with the fact that oxygen vacancy formation energy in Ta2O5 is relatively small, our calculated low diffusion barriers can help explain the low set voltage in Ta2O5 based resistive memory devices. Our work shows that other oxides with adaptive crystal structures could serve as potential candidates for resistive random access memory devices. We also discuss some general characteristics for ideal resistive RAM oxides that could be used in future computational material searches.

A Unifying Perspective on Oxygen Vacancies in Wide Band Gap Oxides.

Science.gov (United States)

Linderälv, Christopher; Lindman, Anders; Erhart, Paul

2018-01-04

Wide band gap oxides are versatile materials with numerous applications in research and technology. Many properties of these materials are intimately related to defects, with the most important defect being the oxygen vacancy. Here, using electronic structure calculations, we show that the charge transition level (CTL) and eigenstates associated with oxygen vacancies, which to a large extent determine their electronic properties, are confined to a rather narrow energy range, even while band gap and the electronic structure of the conduction band vary substantially. Vacancies are classified according to their character (deep versus shallow), which shows that the alignment of electronic eigenenergies and CTL can be understood in terms of the transition between cavity-like localized levels in the large band gap limit and strong coupling between conduction band and vacancy states for small to medium band gaps. We consider both conventional and hybrid functionals and demonstrate that the former yields results in very good agreement with the latter provided that band edge alignment is taken into account.

Simulation of the Atomic and Electronic Structure of Oxygen Vacancies and Polyvacancies in ZrO2

Science.gov (United States)

Perevalov, T. V.

2018-03-01

Cubic, tetragonal, and monoclinic phases of zirconium oxide with oxygen vacancies and polyvacancies are studied by quantum chemical modeling of the atomic and electronic structure. It is demonstrated that an oxygen vacancy in ZrO2 may act as both an electron trap and a hole one. An electron added to the ZrO2 structure with an oxygen vacancy is distributed between two neighboring Zr atoms and is a bonding orbital by nature. It is advantageous for each subsequent O vacancy to form close to the already existing ones; notably, one Zr atom has no more than two removed O atoms related to it. Defect levels from oxygen polyvacancies are distributed in the bandgap with preferential localization in the vicinity of the oxygen monovacancy level.

Formation of vacancy clusters in tungsten crystals under hydrogen-rich condition

Energy Technology Data Exchange (ETDEWEB)

Kato, Daiji, E-mail: kato.daiji@nifs.ac.jp [National Institute for Fusion Science, 322-6 Oroshi-cho, Toki, Gifu 509-5292 (Japan); Iwakiri, Hirotomo, E-mail: iwakiri@edu.u-ryukyu.ac.jp [University of the Ryukyus, Okinawa 903-0213 (Japan); Morishita, Kazunori, E-mail: morishita@iae.kyoto-u.ac.jp [Institute of Advanced Energy, Kyoto University, Kyoto 611-0011 (Japan)

2011-10-01

Di-vacancy formation assisted by hydrogen trapping is studied in terms of nucleation free-energies evaluated with density functional theory. Calculations give binding energies for single hydrogen atom as first- and second-nearest-neighbor of di-vacancies of 1.80 and 2.15 eV, respectively, which are significantly larger than that for mono-vacancies. At elevated atomic concentrations of interstitial hydrogen atoms, evaluated nucleation free-energies indicate that the hydrogen assisted di-vacancy formation becomes more favorable. It is suggested that the formation would be preceded by VH cluster formation.

Formation of vacancy clusters in tungsten crystals under hydrogen-rich condition

International Nuclear Information System (INIS)

Kato, Daiji; Iwakiri, Hirotomo; Morishita, Kazunori

2011-01-01

Di-vacancy formation assisted by hydrogen trapping is studied in terms of nucleation free-energies evaluated with density functional theory. Calculations give binding energies for single hydrogen atom as first- and second-nearest-neighbor of di-vacancies of 1.80 and 2.15 eV, respectively, which are significantly larger than that for mono-vacancies. At elevated atomic concentrations of interstitial hydrogen atoms, evaluated nucleation free-energies indicate that the hydrogen assisted di-vacancy formation becomes more favorable. It is suggested that the formation would be preceded by VH cluster formation.

Pinning by oxygen vacancies in high-Tc superconductors

International Nuclear Information System (INIS)

Chudnovsky, E.M.

1990-01-01

It is shown that recent data of Murray et al. on spatial correlations in flux lattices of Bi-Sr-Ca-Cu-O (BSCCO) may be explained if one assumes that 1% of oxygen atoms in CuO 2 layers are missing. This estimate, being in remarkable agreement with that deduced by Kes and van der Beek from ac-susceptibility measurements, provides strong confidence that oxygen vacancies are the major source of pinning in BSCCO

Mechanism of vacancy formation induced by hydrogen in tungsten

Directory of Open Access Journals (Sweden)

Yi-Nan Liu

2013-12-01

Full Text Available We report a hydrogen induced vacancy formation mechanism in tungsten based on classical molecular dynamics simulations. We demonstrate the vacancy formation in tungsten due to the presence of hydrogen associated directly with a stable hexagonal self-interstitial cluster as well as a linear crowdion. The stability of different self-interstitial structures has been further studied and it is particularly shown that hydrogen plays a crucial role in determining the configuration of SIAs, in which the hexagonal cluster structure is preferred. Energetic analysis has been carried out to prove that the formation of SIA clusters facilitates the formation of vacancies. Such a mechanism contributes to the understanding of the early stage of the hydrogen blistering in tungsten under a fusion reactor environment.

Oxygen vacancies: The origin of n -type conductivity in ZnO

Science.gov (United States)

Liu, Lishu; Mei, Zengxia; Tang, Aihua; Azarov, Alexander; Kuznetsov, Andrej; Xue, Qi-Kun; Du, Xiaolong

2016-06-01

Oxygen vacancy (VO) is a common native point defect that plays crucial roles in determining the physical and chemical properties of metal oxides such as ZnO. However, fundamental understanding of VO is still very sparse. Specifically, whether VO is mainly responsible for the n -type conductivity in ZnO has been still unsettled in the past 50 years. Here, we report on a study of oxygen self-diffusion by conceiving and growing oxygen-isotope ZnO heterostructures with delicately controlled chemical potential and Fermi level. The diffusion process is found to be predominantly mediated by VO. We further demonstrate that, in contrast to the general belief of their neutral attribute, the oxygen vacancies in ZnO are actually +2 charged and thus responsible for the unintentional n -type conductivity as well as the nonstoichiometry of ZnO. The methodology can be extended to study oxygen-related point defects and their energetics in other technologically important oxide materials.

Segregation and Migration of the Oxygen Vacancies in the 3 (111) Tilt Grain Boundaries of Ceria

Energy Technology Data Exchange (ETDEWEB)

Yuan, Fenglin [Univ. of Tennessee, Knoxville, TN (United States); Liu, Bin [Univ. of Tennessee, Knoxville, TN (United States); Zhang, Yanwen [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Weber, William J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2016-03-01

In nanocrystalline materials, defect-grain boundary (GB) interaction plays a key role in determining the structure stability, as well as size-dependent ionic, electronic, magnetic and chemical properties. In this study, we systematically investigated using density functional theory segregation and migration of oxygen vacancies at the Σ3 [110] / (111) grain boundary of ceria. Three oxygen layers near the GB are predicted to be segregation sites for oxygen vacancies. Moreover, the presence of oxygen vacancies stabilizes this tilt GB at a low Fermi level and/or oxygen poor conditions. An atomic strain model was proposed to rationalize layer dependency of the relaxation energy for +2 charged oxygen vacancy. The structural origin of large relaxation energies at layers 1 and 2 was determined to be free-volume space that induces ion relaxation towards the GB. Our results not only pave the way for improving the oxygen transport near GBs of ceria, but also provide important insights into engineering the GB structure for better ionic, magnetic and chemical properties of nanocrystalline ceria.

Strain-induced oxygen vacancies in ultrathin epitaxial CaMnO3 films

Science.gov (United States)

Chandrasena, Ravini; Yang, Weibing; Lei, Qingyu; Delgado-Jaime, Mario; de Groot, Frank; Arenholz, Elke; Kobayashi, Keisuke; Aschauer, Ulrich; Spaldin, Nicola; Xi, Xiaoxing; Gray, Alexander

Dynamic control of strain-induced ionic defects in transition-metal oxides is considered to be an exciting new avenue towards creating materials with novel electronic, magnetic and structural properties. Here we use atomic layer-by-layer laser molecular beam epitaxy to synthesize high-quality ultrathin single-crystalline CaMnO3 films with systematically varying coherent tensile strain. We then utilize a combination of high-resolution soft x-ray absorption spectroscopy and bulk-sensitive hard x-ray photoemission spectroscopy in conjunction with first-principles theory and core-hole multiplet calculations to establish a direct link between the coherent in-plane strain and the oxygen-vacancy content. We show that the oxygen vacancies are highly mobile, which necessitates an in-situ-grown capping layer in order to preserve the original strain-induced oxygen-vacancy content. Our findings open the door for designing and controlling new ionically active properties in strongly-correlated transition-metal oxides.

Oxygen vacancies induced enhancement of photoconductivity of La0.5Sr0.5CoO3 - δ thin film

Science.gov (United States)

Gao, R. L.; Fu, C. L.; Cai, W.; Chen, G.; Deng, X. L.; Yang, H. W.; Sun, J. R.; Zhao, Y. G.; Shen, B. G.

2014-09-01

Effects of light and electrical current on the electrical transport properties and photovoltaic properties of oxygen-stoichiometric La0.5Sr0.5CoO3 and oxygen-deficient La0.5Sr0.5CoO3 - δ films prepared by pulsed laser deposition have been investigated. Oxygen-deficient films annealed in a vacuum show an obvious increase of resistance and lattice parameter. Besides, a direct correlation between the magnitude of the photoconductivity and oxygen vacancies in La0.5Sr0.5CoO3 - δ films has been observed. The light illumination causes a resistance drop to show the photoconductivity effect. Moreover, the photoconductivity can be remarkably enhanced by increasing the electrical current, that is, it exhibits current-enhanced photoconductivity (CEPC) effect. Oxygen deficiency in the annealed film leads to the formation of a structural disorder in the Co-O-Co conduction channel due to the accumulated oxygen vacancies and hence is believed to be responsible for the increase in higher photoconductivity. These results may be important for practical applications in photoelectric devices.

Electronic structure and formation energy of a vacancy in aluminum

International Nuclear Information System (INIS)

Chakraborty, B.; Siegel, R.W.

1981-11-01

The electronic structure of a vacancy in Al was calculated self-consistently using norm-conserving ionic pseudopotentials obtained from ab initio atomic calculations. A 27-atom-site supercell containing 1 vacancy and 26 atoms was used to simulate the environment of the vacancy. A vacancy formation energy of 1.5 eV was also calculated (cf. the experimental value of 0.66 eV). The effects of the supercell and the nature of the ionic potential on the resulting electronic structure and formation energy are discussed. Results for the electronic structure of a divacancy are also presented. 3 figures

Electro-oxidation of water on hematite: Effects of surface termination and oxygen vacancies investigated by first-principles

DEFF Research Database (Denmark)

Hellman, Anders; Iandolo, Beniamino; Wickman, Bjorn

2015-01-01

The oxygen evolution reaction on hydroxyl- and oxygen-terminated hematite was investigated using first-principle calculations within a theoretical electrochemical framework. Both pristine hematite and hematite containing oxygen vacancies were considered. The onset potential was determined to be 1...... on hematite occurs on the oxygen-terminated hematite, containing oxygen vacancies. (C) 2015 Elsevier B.V. All rights reserved....

Controlled oxygen vacancy induced p-type conductivity in HfO{sub 2-x} thin films

Energy Technology Data Exchange (ETDEWEB)

Hildebrandt, Erwin; Kurian, Jose; Mueller, Mathis M.; Kleebe, Hans-Joachim; Alff, Lambert [Institute of Materials Science, Technische Universitaet Darmstadt, 64287 Darmstadt (Germany); Schroeder, Thomas [IHP, 15236 Frankfurt/Oder (Germany)

2011-09-12

We have synthesized highly oxygen deficient HfO{sub 2-x} thin films by controlled oxygen engineering using reactive molecular beam epitaxy. Above a threshold value of oxygen vacancies, p-type conductivity sets in with up to 6 times 10{sup 21} charge carriers per cm{sup 3}. At the same time, the band-gap is reduced continuously by more than 1 eV. We suggest an oxygen vacancy induced p-type defect band as origin of the observed behavior.

Spin-dependent recombination involving oxygen-vacancy complexes in silicon

Science.gov (United States)

Franke, David P.; Hoehne, Felix; Vlasenko, Leonid S.; Itoh, Kohei M.; Brandt, Martin S.

2014-05-01

Spin-dependent relaxation and recombination processes in γ-irradiated n-type Czochralski-grown silicon are studied using continuous wave (cw) and pulsed electrically detected magnetic resonance (EDMR). Two processes involving the SL1 center, the neutral excited triplet state of the oxygen-vacancy complex, are observed which can be separated by their different dynamics. One of the processes is the relaxation of the excited SL1 state to the ground state of the oxygen-vacancy complex, the other a charge transfer between 31P donors and SL1 centers forming close pairs, as indicated by electrically detected electron double resonance. For both processes, the recombination dynamics is studied with pulsed EDMR techniques. We demonstrate the feasibility of true zero-field cw and pulsed EDMR for spin-1 systems and use this to measure the lifetimes of the different spin states of SL1 also at vanishing external magnetic field.

Hydrogen peroxide reduction in the oxygen vacancies of ZnO nanotubes

International Nuclear Information System (INIS)

Peyghan, Ali Ahmadi; Laeen, Shima Parizad; Aslanzadeh, Saeed Amir; Moradi, Morteza

2014-01-01

The adsorption of a H 2 O 2 molecule on the pristine and O-vacancy defected ZnO nanotubes was investigated by means of density functional calculations. It was found that the molecule prefers to attach to two zinc atoms of the tube from its two oxygen atoms with the adsorption energy of 254.1 kJ/mol. Attachment of the H 2 O 2 to the wall of the tube does not have any significant influence on its highest occupied molecular orbital/lowest unoccupied molecular orbital gap (E g ). The presence of oxygen vacancy defect causes a decrease in the E g of the tube and, as a consequence, may cause an increase in the conductivity of the tube. The zinc atoms of the defect are more reactive toward H 2 O 2 reduction to H 2 O than perfect ones with the adsorption energy of 617.4 kJ/mol. During the adsorption process, the H 2 O 2 was reoriented in such a way that its O atom has diffused into vacancy site, so that O-O and O-H bonds of the molecule were dissociated and an H 2 O is formed. Thus, we think that ZnO-NTs may be a candidate for electrochemical reduction and detection of H 2 O 2 . - Highlights: • H 2 O 2 adsorption on pristine and O-vacancy defected ZnO nanotubes was studied by DFT. • H 2 O 2 does not have any significant influence on the gap of the tube. • Presence of oxygen vacancy defect causes a decrease in the gap of the tube. • ZnO nanotubes may be a candidate for electrochemical reduction and detection of H 2 O 2

Control of oxygen vacancies and Ce+3 concentrations in doped ceria nanoparticles via the selection of lanthanide element

International Nuclear Information System (INIS)

Shehata, N.; Meehan, K.; Hudait, M.; Jain, N.

2012-01-01

The effect of lanthanides that have positive association energies with oxygen vacancies, such as samarium and neodymium, and the elements with negative association energies, such as holmium and erbium, on ionization state of cerium and, consequentially, the oxygen vacancy concentration in doped ceria nanoparticles are investigated in this article. Structural and optical characterizations of the doped and undoped ceria nanoparticles, synthesized using chemical precipitation, are carried out using transmission electron microscopy, X-ray diffractometry, optical absorption spectroscopy, and fluorescence spectroscopy. It is deduced that the negative association energy dopants decrease the conversion of Ce +4 into Ce +3 and, hence, scavenge the oxygen vacancies, evidenced by the observed increase in the allowed direct bandgap, decrease in the integrated fluorescence intensity, and increased the size of doped nanoparticles. The opposite trends are obtained when the positive association dopants are used. It is concluded that the determining factor as to whether a lanthanide dopant in ceria acts as a generator or scavenger of oxygen vacancies in ceria nanoparticles is the sign of the association energy between the element and the oxygen vacancies. The ability to tailor the ionization state of cerium and the oxygen vacancy concentration in ceria has applications in a broad range of fields, which include catalysis, biomedicine, electronics, and environmental sensing.

First-principles studies on vacancy-modified interstitial diffusion mechanism of oxygen in nickel, associated with large-scale atomic simulation techniques

International Nuclear Information System (INIS)

Fang, H. Z.; Shang, S. L.; Wang, Y.; Liu, Z. K.; Alfonso, D.; Alman, D. E.; Shin, Y. K.; Zou, C. Y.; Duin, A. C. T. van; Lei, Y. K.; Wang, G. F.

2014-01-01

This paper is concerned with the prediction of oxygen diffusivities in fcc nickel from first-principles calculations and large-scale atomic simulations. Considering only the interstitial octahedral to tetrahedral to octahedral minimum energy pathway for oxygen diffusion in fcc lattice, greatly underestimates the migration barrier and overestimates the diffusivities by several orders of magnitude. The results indicate that vacancies in the Ni-lattice significantly impact the migration barrier of oxygen in nickel. Incorporation of the effect of vacancies results in predicted diffusivities consistent with available experimental data. First-principles calculations show that at high temperatures the vacancy concentration is comparable to the oxygen solubility, and there is a strong binding energy and a redistribution of charge density between the oxygen atom and vacancy. Consequently, there is a strong attraction between the oxygen and vacancy in the Ni lattice, which impacts diffusion

Periodic density functional theory study of ethylene hydrogenation over Co3O4 (1 1 1) surface: The critical role of oxygen vacancies

Science.gov (United States)

Lu, Jinhui; Song, JiaJia; Niu, Hongling; Pan, Lun; Zhang, Xiangwen; Wang, Li; Zou, Ji-Jun

2016-05-01

Recently, metal oxides are attracting increasing interests as hydrogenation catalyst. Herein we studied the hydrogenation of ethylene on perfect and oxygen defective Co3O4 (1 1 1) using periodic density functional theory. The energetics and pathways of ethylene hydrogenation to ethane were determined. We have demonstrated that (i) H2 dissociation on Co3O4 is a complicated two-step process through a heterolytic cleavage, followed by the migration of H atom and finally yields the homolytic product on both perfect and oxygen defective Co3O4 (1 1 1) surfaces easily. (ii) After introducing the surface oxygen vacancy, the stepwise hydrogenation of ethylene by atomic hydrogen is much easier than that on perfect surface due to the weaker bond strength of OH group. The strength of Osbnd H bond is a crucial factor for the hydrogenation reaction which involves the breakage of Osbnd H bond. The formation of oxygen vacancy increases the electronic charges at the adjacent surface O, which reduces its capability of further gaining electrons from adsorbed atomic hydrogen and then weakens the strength of Osbnd H bond. These results emphasize the importance of the oxygen vacancies for hydrogenation on metal oxides.

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

Science.gov (United States)

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.

Evidence for oxygen vacancy or ferroelectric polarization induced switchable diode and photovoltaic effects in BiFeO3 based thin films

International Nuclear Information System (INIS)

Guo Yiping; Guo Bing; Dong Wen; Li Hua; Liu Hezhou

2013-01-01

The diode and photovoltaic effects of BiFeO 3 and Bi 0.9 Sr 0.1 FeO 3−δ polycrystalline thin films were investigated by poling the films with increased magnitude and alternating direction. It was found that both electromigration of oxygen vacancies and polarization flipping are able to induce switchable diode and photovoltaic effects. For the Bi 0.9 Sr 0.1 FeO 3−δ thin films with high oxygen vacancy concentration, reversibly switchable diode and photovoltaic effects can be observed due to the electromigration of oxygen vacancies under an electric field much lower than its coercive field. However, for the pure BiFeO 3 thin films with lower oxygen vacancy concentration, the reversibly switchable diode and photovoltaic effect is hard to detect until the occurrence of polarization flipping. The switchable diode and photovoltaic effects can be explained well using the concepts of Schottky-like barrier-to-Ohmic contacts resulting from the combination of oxygen vacancies and polarization. The sign of photocurrent could be independent of the direction of polarization when the modulation of the energy band induced by oxygen vacancies is large enough to offset that induced by polarization. The photovoltaic effect induced by the electromigration of oxygen vacancies is unstable due to the diffusion of oxygen vacancies or the recombination of oxygen vacancies with hopping electrons. Our work provides deep insights into the nature of diode and photovoltaic effects in ferroelectric films, and will facilitate the advanced design of switchable devices combining spintronic, electronic, and optical functionalities. (paper)

Stability enhancement of Cu2S against Cu vacancy formation by Ag alloying

Science.gov (United States)

Barman, Sajib K.; Huda, Muhammad N.

2018-04-01

As a potential solar absorber material, Cu2S has proved its importance in the field of renewable energy. However, almost all the known minerals of Cu2S suffer from spontaneous Cu vacancy formation in the structure. The Cu vacancy formation causes the structure to possess very high p-type doping that leads the material to behave as a degenerate semiconductor. This vacancy formation tendency is a major obstacle for this material in this regard. A relatively new predicted phase of Cu2S which has an acanthite-like structure was found to be preferable than the well-known low chalcocite Cu2S. However, the Cu-vacancy formation tendency in this phase remained similar. We have found that alloying silver with this structure can help to reduce Cu vacancy formation tendency without altering its electronic property. The band gap of silver alloyed structure is higher than pristine acanthite Cu2S. In addition, Cu diffusion in the structure can be reduced with Ag doped in Cu sites. In this study, a systematic approach is presented within the density functional theory framework to study Cu vacancy formation tendency and diffusion in silver alloyed acanthite Cu2S, and proposed a possible route to stabilize Cu2S against Cu vacancy formations by alloying it with Ag.

Oxygen vacancies as active sites for water dissociation on rutile TiO₂(110)

DEFF Research Database (Denmark)

Schaub, R.; Thostrup, P.; Lopez, Nuria

2001-01-01

to dissociate H2O through the transfer of one proton to a nearby oxygen atom, forming two hydroxyl groups for every vacancy. The amount of water dissociation is limited by the density of oxygen vacancies present on the clean surface exclusively. The dissociation process sets in as soon as molecular water...

Introduction of oxygen vacancies and fluorine into TiO2 nanoparticles by co-milling with PTFE

International Nuclear Information System (INIS)

Senna, Mamoru; Šepelák, Vladimir; Shi, Jianmin; Bauer, Benjamin; Feldhoff, Armin; Laporte, Vincent; Becker, Klaus-Dieter

2012-01-01

Solid-state processes of introducing oxygen vacancies and transference of fluorine to n-TiO 2 nanoparticles by co-milling with poly(tetrafluoroethylene) (PTFE) powder were examined by diffuse reflectance spectroscopy (DRS) of UV, visual, near- and mid-IR regions, thermal analyses (TG-DTA), energy-dispersive X-ray spectroscopy (EDXS), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The broad absorption peak at around 8800 cm −1 (1140 nm) was attributed to the change in the electronic states, viz. electrons trapped at the oxygen vacancies (Vo) and d–d transitions of titanium ions. Incorporation of fluorine into n-TiO 2 was concentrated at the near surface region and amounted to ca. 40 at% of the total fluorine in PTFE, after co-milling for 3 h, as confirmed by the F1s XPS spectrum. The overall atomic ratio, F/Ti, determined by EDXS was 0.294. By combining these analytical results, a mechanism of the present solid state processes at the boundary between PTFE and n-TiO 2 was proposed. The entire process is triggered by the partial oxidative decomposition of PTFE. This is accompanied by the abstraction of oxygen atoms from the n-TiO 2 lattices. Loss of the oxygen atoms results in the formation of the diverse states of locally distorted coordination units of titania, i.e. TiO 6−n Vo n , located at the near surface region. This leads subsequent partial ligand exchange between F and O, to incorporate fluorine preferentially to the near surface region of n-TiO 2 particles, where local non-crystalline states predominate. - Graphical abstract: Scheme of the reaction processes: (a) pristine mixture, (b) oxygen abstraction from TiO 2 and (c) fluorine migration from PTFE to TiO 2 . Highlights: Transfer of fluorine from PTFE to n-TiO 2 in a dry solid state process was confirmed. ► 40% of F in PTFE was incorporated to the near surface region of n-TiO 2 nanoparticles. ► The transfer process is

High temperature thermoelectric properties of strontium titanate thin films with oxygen vacancy and niobium doping

KAUST Repository

Sarath Kumar, S. R.; Barasheed, Abeer Z.; Alshareef, Husam N.

2013-01-01

We report the evolution of high temperature thermoelectric properties of SrTiO3 thin films doped with Nb and oxygen vacancies. Structure-property relations in this important thermoelectric oxide are elucidated and the variation of transport properties with dopant concentrations is discussed. Oxygen vacancies are incorporated during growth or annealing in Ar/H2 above 800 K. An increase in lattice constant due to the inclusion of Nb and oxygen vacancies is found to result in an increase in carrier density and electrical conductivity with simultaneous decrease in carrier effective mass and Seebeck coefficient. The lattice thermal conductivity at 300 K is found to be 2.22 W m-1 K-1, and the estimated figure of merit is 0.29 at 1000 K. © 2013 American Chemical Society.

High temperature thermoelectric properties of strontium titanate thin films with oxygen vacancy and niobium doping

KAUST Repository

Sarath Kumar, S. R.

2013-08-14

We report the evolution of high temperature thermoelectric properties of SrTiO3 thin films doped with Nb and oxygen vacancies. Structure-property relations in this important thermoelectric oxide are elucidated and the variation of transport properties with dopant concentrations is discussed. Oxygen vacancies are incorporated during growth or annealing in Ar/H2 above 800 K. An increase in lattice constant due to the inclusion of Nb and oxygen vacancies is found to result in an increase in carrier density and electrical conductivity with simultaneous decrease in carrier effective mass and Seebeck coefficient. The lattice thermal conductivity at 300 K is found to be 2.22 W m-1 K-1, and the estimated figure of merit is 0.29 at 1000 K. © 2013 American Chemical Society.

Periodic density functional theory study of ethylene hydrogenation over Co3O4 (1 1 1) surface: The critical role of oxygen vacancies

International Nuclear Information System (INIS)

Lu, Jinhui; Song, JiaJia; Niu, Hongling; Pan, Lun; Zhang, Xiangwen; Wang, Li; Zou, Ji-Jun

2016-01-01

Highlights: • H 2 dissociates in heterolytic way following H atoms migration to form O−H bond. • H 2 dissociation occurs at low temperature on perfect and oxygen defective Co 3 O 4 . • Oxygen vacancy promotes hydrogenation thermodynamically and kinetically. • O−H bond is weakened on oxygen defective surface. • Hydrogenation requires compromise between H−H activation and O−H breakage. - Abstract: Recently, metal oxides are attracting increasing interests as hydrogenation catalyst. Herein we studied the hydrogenation of ethylene on perfect and oxygen defective Co 3 O 4 (1 1 1) using periodic density functional theory. The energetics and pathways of ethylene hydrogenation to ethane were determined. We have demonstrated that (i) H 2 dissociation on Co 3 O 4 is a complicated two-step process through a heterolytic cleavage, followed by the migration of H atom and finally yields the homolytic product on both perfect and oxygen defective Co 3 O 4 (1 1 1) surfaces easily. (ii) After introducing the surface oxygen vacancy, the stepwise hydrogenation of ethylene by atomic hydrogen is much easier than that on perfect surface due to the weaker bond strength of OH group. The strength of O−H bond is a crucial factor for the hydrogenation reaction which involves the breakage of O−H bond. The formation of oxygen vacancy increases the electronic charges at the adjacent surface O, which reduces its capability of further gaining electrons from adsorbed atomic hydrogen and then weakens the strength of O−H bond. These results emphasize the importance of the oxygen vacancies for hydrogenation on metal oxides.

Oxygen-vacancy defects on BaTiO3 (001) surface: a quantum chemical study

International Nuclear Information System (INIS)

Duque, Carlos; Stashans, Arvids

2003-01-01

A quantum-chemical study of technologically important BaTiO 3 crystal and oxygen-vacancy defects on its (001) surface is reported in the present work. The computations are made using a quantum-chemical method developed for periodic systems (crystals), which is based on the Hartree-Fock theory. The atomic rearrangement due to the surface creation is obtained for a pure BaTiO 3 by means of the periodic large unit cell (LUC) model and using an automated geometry optimisation procedure. The same technique is employed to study the electronic and structural properties of the material due to the presence of an O vacancy and F centre (two electrons trapped in an oxygen vacancy). The computations are carried out for both cubic and tetragonal lattices

Determination of the vacancy formation enthalpy for high purity Ni

International Nuclear Information System (INIS)

Lynn, K.G.; Snead, C.L. Jr.; Hurst, J.J.; Farrell, K.

1979-01-01

Positron-annihilation lifetime measurements have been made on Ni over a temperature range of 4.2 to 1700 K. We find a small change in the lifetime from 4.2 to 900 K indicating a very small thermal-expansion effect. A small precursor effect is observed before the onset of significant vacancy trapping. A monovacancy formation enthalpy of 1.54/sub +0.2//sup -0.1/ eV is extracted without taking divacancies into consideration in the analysis. No detrapping from mono-vacancies is observed even at the higher temperatures. The vacancy formation enthalpy extracted from the lifetime data is compared to values obtained by Doppler-broadening and angular-correlation techniques

Determination of the vacancy formation enthalpy for high purity Ni

International Nuclear Information System (INIS)

Lynn, K.G.; Snead, C.L. Jr.; Hurst, J.J.; Farrell, K.

1979-01-01

Positron-annihilation lifetime measurements have been made on Ni over a temperature range of 4.2 to 1700 K. We find a small change in the lifetime from 4.2 - 900 K indicating a very small thermal-expansion effect. A small precursor effect is observed before the onset of significant vacancy trapping. A monovacancy formation enthalpy of 1.54sub(+0.2)sup(-0.1) eV is extracted without taking divacancies into consideration in the analysis. No detrapping from mono-vacancies is observed even at the higher temperatures. The vacancy formation enthalpy extracted from the lifetime data is compared to values obtained by Doppler-broadening and angular-correlation techniques. (author)

Oxygen vacancy doping of hematite analyzed by electrical conductivity and thermoelectric power measurements

Science.gov (United States)

Mock, Jan; Klingebiel, Benjamin; Köhler, Florian; Nuys, Maurice; Flohre, Jan; Muthmann, Stefan; Kirchartz, Thomas; Carius, Reinhard

2017-11-01

Hematite (α -F e2O3 ) is known for poor electronic transport properties, which are the main drawback of this material for optoelectronic applications. In this study, we investigate the concept of enhancing electrical conductivity by the introduction of oxygen vacancies during temperature treatment under low oxygen partial pressure. We demonstrate the possibility of tuning the conductivity continuously by more than five orders of magnitude during stepwise annealing in a moderate temperature range between 300 and 620 K. With thermoelectric power measurements, we are able to attribute the improvement of the electrical conductivity to an enhanced charge-carrier density by more than three orders of magnitude. We compare the oxygen vacancy doping of hematite thin films with hematite nanoparticle layers. Thereby we show that the dominant potential barrier that limits charge transport is either due to grain boundaries in hematite thin films or due to potential barriers that occur at the contact area between the nanoparticles, rather than the potential barrier within the small polaron hopping model, which is usually applied for hematite. Furthermore, we discuss the transition from oxygen-deficient hematite α -F e2O3 -x towards the magnetite F e3O4 phase of iron oxide at high density of vacancies.

Trapping of oxygen vacancies on twin walls of CaTiO3: a computer simulation study

International Nuclear Information System (INIS)

Calleja, Mark; Dove, Martin T; Salje, Ekhard K H

2003-01-01

We have studied the atomic structure of [001] 90 deg. rotation twin walls in orthorhombic CaTiO 3 (symmetry Pbnm) at low temperature (10 K) and their effects on oxygen vacancies. The wall thickness was found to be 2.3 nm at T || T c and it was found that it is energetically favourable for such vacancies to reside in the wall, particularly when bridging titania ions in the (001) plane. The binding energy of an oxygen vacancy in the wall with respect to the bulk is calculated to be ≤ 1.2 eV

The dynamics of ultraviolet-induced oxygen vacancy at the surface of insulating SrTiO_3(0 0 1)

International Nuclear Information System (INIS)

Suwanwong, S.; Eknapakul, T.; Rattanachai, Y.; Masingboon, C.; Rattanasuporn, S.; Phatthanakun, R.; Nakajima, H.; King, P.D.C.; Hodak, S.K.; Meevasana, W.

2015-01-01

Highlights: • The dynamics of UV-induced oxygen vacancy is studied from the change of surface resistance. • The formation of 2DEG at the insulating surface of SrTiO_3 is confirmed by ARPES. • The UV-induced change in resistance responds differently to oxygen/gas exposure. • The behavior of resistance recovery suggests an alternative method of low-pressure sensing. - Abstract: The effect of ultra-violet (UV) irradiation on the electronic structure and the surface resistance of an insulating SrTiO_3(0 0 1) crystal is studied in this work. Upon UV irradiation, we show that the two-dimensional electron gas (2DEG) emerges at the insulating SrTiO_3 surface and there is a pronounced change in the surface resistance. By combining the observations of the change in valance band and the resistance change under different environments of gas pressure and gas species, we find that UV-induced oxygen vacancies at the surface plays a major role in the resistance change. The dynamic of the resistance change at different oxygen pressures also suggests an alternative method of low-pressure sensing.

Direct observation of oxygen-vacancy-enhanced polarization in a SrTiO{sub 3}-buffered ferroelectric BaTiO{sub 3} film on GaAs

Energy Technology Data Exchange (ETDEWEB)

Qiao, Qiao [Department of Physics, University of Illinois at Chicago, Chicago, Illinois 60607 (United States); Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37240 (United States); Materials Science and Technology Department, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States); Zhang, Yuyang [Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37240 (United States); Materials Science and Technology Department, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States); Contreras-Guerrero, Rocio; Droopad, Ravi [Ingram School of Engineering, Texas State University, San Marcos, Texas 78666 (United States); Pantelides, Sokrates T. [Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37240 (United States); Materials Science and Technology Department, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States); Department of Electrical Engineering and Computer Science, Vanderbilt University, Nashville, Tennessee 37240 (United States); Pennycook, Stephen J. [Department of Materials Science and Engineering, National University of Singapore, Singapore 117575 (Singapore); Ogut, Serdar; Klie, Robert F. [Department of Physics, University of Illinois at Chicago, Chicago, Illinois 60607 (United States)

2015-11-16

The integration of functional oxide thin-films on compound semiconductors can lead to a class of reconfigurable spin-based optoelectronic devices if defect-free, fully reversible active layers are stabilized. However, previous first-principles calculations predicted that SrTiO{sub 3} thin films grown on Si exhibit pinned ferroelectric behavior that is not switchable, due to the presence of interfacial vacancies. Meanwhile, piezoresponse force microscopy measurements have demonstrated ferroelectricity in BaTiO{sub 3} grown on semiconductor substrates. The presence of interfacial oxygen vacancies in such complex-oxide/semiconductor systems remains unexplored, and their effect on ferroelectricity is controversial. Here, we use a combination of aberration-corrected scanning transmission electron microscopy and first-principles density functional theory modeling to examine the role of interfacial oxygen vacancies on the ferroelectric polarization of a BaTiO{sub 3} thin film grown on GaAs. We demonstrate that interfacial oxygen vacancies enhance the polar discontinuity (and thus the single domain, out-of-plane polarization pinning in BaTiO{sub 3}), and propose that the presence of surface charge screening allows the formation of switchable domains.

First-principles calculations of vacancy formation in In-free photovoltaic semiconductor Cu2ZnSnSe4

International Nuclear Information System (INIS)

Maeda, Tsuyoshi; Nakamura, Satoshi; Wada, Takahiro

2011-01-01

To quantitatively evaluate the formation energies of Cu, Zn, Sn, and Se vacancies in kesterite-type Cu 2 ZnSnSe 4 (CZTSe), first-principles pseudopotential calculations using plane-wave basis functions were performed. The formation energies of neutral Cu, Zn, Sn and Se vacancies were calculated as a function of the atomic chemical potentials of constituent elements. The obtained results were as follows: (1) the formation energy of Cu vacancy was generally smaller than those of the other Zn, Sn and Se vacancies, (2) under the Cu-poor and Zn-rich condition, the formation energy of Cu vacancy was particularly low, (3) the formation energy of Zn vacancy greatly depended on the chemical potentials of the constituent elements and under the Zn-poor and Se-rich condition, the formation energy of Zn vacancy was smaller than that of Cu vacancy, and (4) the formation energy of Sn vacancy did not greatly depend on the chemical potentials of the constituent elements and was much larger than those of Cu, Zn, and Se vacancies. These results indicate that Cu vacancy is easily formed under Cu-poor and Zn-rich conditions, but Zn vacancy is easily formed under the Zn-poor and Se-rich conditions.

Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

Energy Technology Data Exchange (ETDEWEB)

Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com [Department of Physics, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur 440033 (India); Yadav, A. K. [Atomic and molecular Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

2016-04-04

This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It is a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.

First-principles study of vacancy formation and migration in clean and Re-doped γ'-Ni3Al

International Nuclear Information System (INIS)

Zhang Xu; Wang Chongyu

2009-01-01

Using density functional theory calculations in conjunction with the climbing images nudged elastic band method, we studied the vacancy formation and migration in clean and Re-doped Ni 3 Al. Both the chemical potential of the species and the magnetic effect are considered to determine the vacancy formation energy. We also simulated the vacancy migration in a complete set of migration paths. The evaluated vacancy formation energy and activation energy for the motion of vacancy compared well with the experimental results. Also, the obtained migration ways for the diffusion of Ni and Al atoms are consistent with previous theoretical predictions and experimental observations. Magnetism is found to influence both the vacancy formation and migration. Our results reveal that Re doping can inhibit the formation of Ni vacancies but facilitate the formation of Al vacancies, and can also inhibit the migration of neighboring vacancies. While the doped Re atom on the Al site is stable, the Re atom on the Ni site can diffuse within the Ni-sublattice mediated by Ni vacancies

Hafnium carbide formation in oxygen deficient hafnium oxide thin films

Energy Technology Data Exchange (ETDEWEB)

Rodenbücher, C. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); Hildebrandt, E.; Sharath, S. U.; Kurian, J.; Komissinskiy, P.; Alff, L. [Technische Universität Darmstadt, Institute of Materials Science, 64287 Darmstadt (Germany); Szot, K. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); University of Silesia, A. Chełkowski Institute of Physics, 40-007 Katowice (Poland); Breuer, U. [Forschungszentrum Jülich GmbH, Central Institute for Engineering, Electronics and Analytics (ZEA-3), 52425 Jülich (Germany); Waser, R. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); RWTH Aachen, Institute of Electronic Materials (IWE 2), 52056 Aachen (Germany)

2016-06-20

On highly oxygen deficient thin films of hafnium oxide (hafnia, HfO{sub 2−x}) contaminated with adsorbates of carbon oxides, the formation of hafnium carbide (HfC{sub x}) at the surface during vacuum annealing at temperatures as low as 600 °C is reported. Using X-ray photoelectron spectroscopy the evolution of the HfC{sub x} surface layer related to a transformation from insulating into metallic state is monitored in situ. In contrast, for fully stoichiometric HfO{sub 2} thin films prepared and measured under identical conditions, the formation of HfC{sub x} was not detectable suggesting that the enhanced adsorption of carbon oxides on oxygen deficient films provides a carbon source for the carbide formation. This shows that a high concentration of oxygen vacancies in carbon contaminated hafnia lowers considerably the formation energy of hafnium carbide. Thus, the presence of a sufficient amount of residual carbon in resistive random access memory devices might lead to a similar carbide formation within the conducting filaments due to Joule heating.

Unraveling the facet-dependent and oxygen vacancy role for ethylene hydrogenation on Co_3O_4 (110) surface: A DFT+U study

International Nuclear Information System (INIS)

Zhang, Yong-Chao; Pan, Lun; Lu, Jinhui; Song, Jiajia; Li, Zheng; Zhang, Xiangwen; Wang, Li; Zou, Ji-Jun

2017-01-01

Highlights: • The mechanism of ethylene hydrogenation on perfect and oxygen defective Co_3O_4(110) is investigated by using DFT + U. • Oxygen vacancy promotes ethylene hydrogenation thermodynamically and kinetically. • The Co3O4 (110) facet is more active than the (111) one for ethylene hydrogenation. - Abstract: Crystal facet engineering and defect engineering are both critical strategies to improve the catalytic hydrogenation performance of catalyst. Herein, ethylene hydrogenation on the perfect and oxygen defective Co_3O_4(110) surfaces has been studied by using periodic density functional theory calculations. The results are compared with that on Co_3O_4(111) surface to clarify the problem of which facet for Co_3O_4 is more reactive, and to illuminate the role of oxygen vacancy. The low oxygen vacancy formation energy suggests that Co_3O_4(110) surface with defective site is easily formed. The whole mechanism of H_2 dissociation and stepwise hydrogenation of ethylene to ethane is examined, and the most favorable pathway is heterolytic dissociation of H_2 follows two stepwise hydrogenation of ethylene process. The results show that ethyl hydrogenation to ethane on perfect Co_3O_4(110) surface is the rate limiting step with an activation energy of 1.19 eV, and the presence of oxygen vacancy strongly reduces the activation energies of main elementary steps, and the activation energy of rate limiting step is only 0.47 eV. Compared with that on Co_3O_4(111), ethylene hydrogenation is preferred on Co_3O_4(110) surface. Therefore, Co_3O_4 with exposed (110) facet is predicted as an excellent catalyst for ethylene hydrogenation.

Effects of internal hydrogen on the vacancy loop formation probability in Al

International Nuclear Information System (INIS)

Bui, T.X.; Sirois, E.; Robertson, I.M.

1990-04-01

The effect of internal hydrogen on the formation of vacancy dislocation loops from heavy-ion generated displacement cascades in Al has been investigated. Samples of high-purity aluminum and aluminum containing 900 and 1300 appM of hydrogen were irradiated at room temperature with 50 keV Kr+ ions. The ion dose rate was typically 2 x 10 10 ions cm -2 sec -1 and the ion dose was between 10 11 and 10 13 ion cm -2 . Under these irradiation conditions, dislocation loops were observed in all compositions, although the formation probability was relatively low (less than 10 percent of the displacement cascades produced a vacancy loop). The loop formation probability was further reduced by the presence of hydrogen. No difference in the geometry or the size of the loops created in the hydrogen free and hydrogen charged samples was found. These results are difficult to interpret, and the explanation may lie in the distribution and form of the hydrogen. To account for the large hydrogen concentrations and from calculations of the energy associated with hydrogen entry into aluminum, it has been suggested that the hydrogen enters the aluminum lattice with an accompanying vacancy. This will create hydrogen-vacancy complexes in the material; two dimensional complexes have been detected in the hydrogen-charged, but unirradiated, samples by the small-angle x-ray scattering technique. The possibility of these complexes trapping the vacancies produced by the cascade process exists thus lowering the formation probability. However, such a mechanism must occur within the lifetime of the cascade. Alternatively, if a displacement cascade overlaps with the hydrogen-vacancy complexes, the lower atomic density of the region will result in an increase in the cascade volume (decrease in the local vacancy concentration) which will also reduce the loop formation probability

First-principles calculations of the vacancy formation energy in transition and noble metals

DEFF Research Database (Denmark)

Korzhavyi, P.A.; Abrikosov, Igor A.; Johansson, Börje

1999-01-01

approach and include electrostatic multipole corrections to the atomic sphere approximation. The results are in excellent agreement with available full-potential calculations and with the vacancy formation energies obtained in positron annihilation measurements. The variation of the vacancy formation...

The dynamics of ultraviolet-induced oxygen vacancy at the surface of insulating SrTiO{sub 3}(0 0 1)

Energy Technology Data Exchange (ETDEWEB)

Suwanwong, S. [School of Physics, Suranaree University of Technology, Nakhon Ratchasima 30000 (Thailand); Program in General Science Teaching, Faculty of Education, Vongchavalitkul University, Nakhon Ratchasima 30000 (Thailand); Eknapakul, T. [School of Physics, Suranaree University of Technology, Nakhon Ratchasima 30000 (Thailand); Rattanachai, Y. [Department of Applied Physics, Faculty of Sciences and Liberal Arts, Rajamangala University of Technology Isan, Nakhon Ratchasima 30000 (Thailand); Masingboon, C. [School of Physics, Suranaree University of Technology, Nakhon Ratchasima 30000 (Thailand); Faculty of Science and Engineering, Kasetsart University, Chalermphrakiat Sakon Nakhon Province Campus, Sakon Nakhon 47000 (Thailand); Rattanasuporn, S.; Phatthanakun, R.; Nakajima, H. [Synchrotron Light Research Institute, Nakhon Ratchasima 30000 (Thailand); King, P.D.C. [SUPA, School of Physics and Astronomy, University of St. Andrews, St. Andrews, Fife KY16 9SS (United Kingdom); Hodak, S.K. [Department of Physics, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand); Meevasana, W., E-mail: worawat@g.sut.ac.th [School of Physics, Suranaree University of Technology, Nakhon Ratchasima 30000 (Thailand); NANOTEC-SUT Center of Excellence on Advanced Functional Nanomaterials, Suranaree University of Technology, Nakhon Ratchasima 30000 (Thailand); Thailand Center of Excellence in Physics, CHE, Bangkok 10400 (Thailand)

2015-11-15

Highlights: • The dynamics of UV-induced oxygen vacancy is studied from the change of surface resistance. • The formation of 2DEG at the insulating surface of SrTiO{sub 3} is confirmed by ARPES. • The UV-induced change in resistance responds differently to oxygen/gas exposure. • The behavior of resistance recovery suggests an alternative method of low-pressure sensing. - Abstract: The effect of ultra-violet (UV) irradiation on the electronic structure and the surface resistance of an insulating SrTiO{sub 3}(0 0 1) crystal is studied in this work. Upon UV irradiation, we show that the two-dimensional electron gas (2DEG) emerges at the insulating SrTiO{sub 3} surface and there is a pronounced change in the surface resistance. By combining the observations of the change in valance band and the resistance change under different environments of gas pressure and gas species, we find that UV-induced oxygen vacancies at the surface plays a major role in the resistance change. The dynamic of the resistance change at different oxygen pressures also suggests an alternative method of low-pressure sensing.

Identification of the gallium vacancy-oxygen pair defect in GaN

International Nuclear Information System (INIS)

Son, N. T.; Hemmingsson, C. G.; Janzen, E.; Paskova, T.; Evans, K. R.; Usui, A.; Morishita, N.; Ohshima, T.; Isoya, J.; Monemar, B.

2009-01-01

Cation vacancies like V Ga , V Al and their complexes with oxygen are predicted to be abundant in III-nitrides and to play an important role in nonradiative recombination. Appearing in triple or double negatively charged states, they are not paramagnetic and have not so far been detected by magnetic resonance even under illumination. In this Brief Report, we demonstrate an efficient way to make cation vacancy defects in GaN detectable by electron paramagnetic resonance and present our identification of the V Ga O N pair in GaN which is the model material for the III-nitrides and their alloys.

Microstructure evolution characteristics induced by oxygen vacancy generation in anatase TiO2 based resistive switching devices

Science.gov (United States)

Liu, Chen; Gao, Bin; Huang, Peng; Kang, Jinfeng

2017-03-01

In this work, first principle calculations are employed to study the microstructure characteristics of the anatase TiO2 resistive switching material associated with the generation of oxygen vacancy (V o) based nanofilaments during the switching process. The calculations indicate that both the magnéli phase Ti4O7 and V o-defect phase of anatase TiO2 may be formed with the generation of oxygen vacancies during the forming and SET processes. Based on the calculations, a new physical insight is proposed to clarify the microstructure evolution characteristics of the anatase TiO2 resistive switching material and the correlation with resistive switching behaviors. During the forming or SET process, the anatase TiO2 is first excited to a transition state with the generation of oxygen vacancies, then fully relaxes to a stable V o-defect state. This V o-defect state may either recover to the original state with the recombination of the oxygen vacancies, which causes the reversible resistive switching behavior, or further transform to a much more stable state—the magnéli phase Ti4O7, through a phase transition process with the generation of many more oxygen vacancies. The phase transition from V o- defective anatase phase to magnéli phase Ti4O7 causes the failure of the resistive switching due to the significantly reduced possibility of the reversible phase transition from the magnéli phase to the anatase phase, compared with the possibility of the recombination from the V o-defective anatase.

Ab initio study of vacancy formation in cubic LaMnO{sub 3} and SmCoO{sub 3} as cathode materials in solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Olsson, Emilia; Aparicio-Anglès, Xavier [Department of Chemistry, University College London, London WC1H 0AJ (United Kingdom); Leeuw, Nora H. de, E-mail: deleeuwn@cardiff.ac.uk [Department of Chemistry, University College London, London WC1H 0AJ (United Kingdom); School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT (United Kingdom)

2016-07-07

Doped LaMnO{sub 3} and SmCoO{sub 3} are important solid oxide fuel cell cathode materials. The main difference between these two perovskites is that SmCoO{sub 3} has proven to be a more efficient cathode material than LaMnO{sub 3} at lower temperatures. In order to explain the difference in efficiency, we need to gain insight into the materials’ properties at the atomic level. However, while LaMnO{sub 3} has been widely studied, ab initio studies on SmCoO{sub 3} are rare. Hence, in this paper, we perform a comparative DFT + U study of the structural, electronic, and magnetic properties of these two perovskites. To that end, we first determined a suitable Hubbard parameter for the Co d–electrons to obtain a proper description of SmCoO{sub 3} that fully agrees with the available experimental data. We next evaluated the impact of oxygen and cation vacancies on the geometry, electronic, and magnetic properties. Oxygen vacancies strongly alter the electronic and magnetic structures of SmCoO{sub 3}, but barely affect LaMnO{sub 3}. However, due to their high formation energy, their concentrations in the material are very low and need to be induced by doping. Studying the cation vacancy concentration showed that the formation of cation vacancies is less energetically favorable than oxygen vacancies and would thus not markedly influence the performance of the cathode.

Effect of oxygen vacancies on the electronic and optical properties of tungsten oxide from first principles calculations

Science.gov (United States)

Mehmood, Faisal; Pachter, Ruth; Murphy, Neil R.; Johnson, Walter E.; Ramana, Chintalapalle V.

2016-12-01

In this work, we investigated theoretically the role of oxygen vacancies on the electronic and optical properties of cubic, γ-monoclinic, and tetragonal phases of tungsten oxide (WO3) thin films. Following the examination of structural properties and stability of the bulk tungsten oxide polymorphs, we analyzed band structures and optical properties, applying density functional theory (DFT) and GW (Green's (G) function approximation with screened Coulomb interaction (W)) methods. Careful benchmarking of calculated band gaps demonstrated the importance of using a range-separated functional, where results for the pristine room temperature γ-monoclinic structure indicated agreement with experiment. Further, modulation of the band gap for WO3 structures with oxygen vacancies was quantified. Dielectric functions for cubic WO3, calculated at both the single-particle, essentially time-dependent DFT, as well as many-body GW-Bethe-Salpeter equation levels, indicated agreement with experimental data for pristine WO3. Interestingly, we found that introducing oxygen vacancies caused appearance of lower energy absorptions. A smaller refractive index was indicated in the defective WO3 structures. These predictions could lead to further experiments aimed at tuning the optical properties of WO3 by introducing oxygen vacancies, particularly for the lower energy spectral region.

Ultrafast atomic layer-by-layer oxygen vacancy-exchange diffusion in double-perovskite LnBaCo2O5.5+δ thin films.

Science.gov (United States)

Bao, Shanyong; Ma, Chunrui; Chen, Garry; Xu, Xing; Enriquez, Erik; Chen, Chonglin; Zhang, Yamei; Bettis, Jerry L; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qingyu

2014-04-22

Surface exchange and oxygen vacancy diffusion dynamics were studied in double-perovskites LnBaCo2O5.5+δ (LnBCO) single-crystalline thin films (Ln = Er, Pr; -0.5 atoms in the LnBCO thin films is taking the layer by layer oxygen-vacancy-exchange mechanism. The first principles density functional theory calculations indicate that hydrogen atoms are present in LnBCO as bound to oxygen forming O-H bonds. This unprecedented oscillation phenomenon provides the first direct experimental evidence of the layer by layer oxygen vacancy exchange diffusion mechanism.

Unraveling the facet-dependent and oxygen vacancy role for ethylene hydrogenation on Co{sub 3}O{sub 4} (110) surface: A DFT+U study

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yong-Chao; Pan, Lun; Lu, Jinhui; Song, Jiajia; Li, Zheng; Zhang, Xiangwen; Wang, Li [Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University (China); Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Zou, Ji-Jun, E-mail: jj_zou@tju.edu.cn [Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University (China); Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China)

2017-04-15

Highlights: • The mechanism of ethylene hydrogenation on perfect and oxygen defective Co{sub 3}O{sub 4}(110) is investigated by using DFT + U. • Oxygen vacancy promotes ethylene hydrogenation thermodynamically and kinetically. • The Co3O4 (110) facet is more active than the (111) one for ethylene hydrogenation. - Abstract: Crystal facet engineering and defect engineering are both critical strategies to improve the catalytic hydrogenation performance of catalyst. Herein, ethylene hydrogenation on the perfect and oxygen defective Co{sub 3}O{sub 4}(110) surfaces has been studied by using periodic density functional theory calculations. The results are compared with that on Co{sub 3}O{sub 4}(111) surface to clarify the problem of which facet for Co{sub 3}O{sub 4} is more reactive, and to illuminate the role of oxygen vacancy. The low oxygen vacancy formation energy suggests that Co{sub 3}O{sub 4}(110) surface with defective site is easily formed. The whole mechanism of H{sub 2} dissociation and stepwise hydrogenation of ethylene to ethane is examined, and the most favorable pathway is heterolytic dissociation of H{sub 2} follows two stepwise hydrogenation of ethylene process. The results show that ethyl hydrogenation to ethane on perfect Co{sub 3}O{sub 4}(110) surface is the rate limiting step with an activation energy of 1.19 eV, and the presence of oxygen vacancy strongly reduces the activation energies of main elementary steps, and the activation energy of rate limiting step is only 0.47 eV. Compared with that on Co{sub 3}O{sub 4}(111), ethylene hydrogenation is preferred on Co{sub 3}O{sub 4}(110) surface. Therefore, Co{sub 3}O{sub 4} with exposed (110) facet is predicted as an excellent catalyst for ethylene hydrogenation.

Switchable diode effect in oxygen vacancy-modulated SrTiO{sub 3} single crystal

Energy Technology Data Exchange (ETDEWEB)

Pan, Xinqiang; Shuai, Yao; Wu, Chuangui; Luo, Wenbo; Sun, Xiangyu; Zeng, Huizhong; Bai, Xiaoyuan; Gong, Chaoguan; Jian, Ke; Zhang, Wanli [University of Electronic Science and Technology of China, State Key Laboratory of Electronic Thin Films and Integrated Devices, Chengdu (China); Zhang, Lu; Guo, Hongliang [University of Electronic Science and Technology of China, The Center for Robotics, Chengdu (China); Tian, Benlang [26th Institute of China Electronics Technology Group Corporation, Chongqing (China)

2017-09-15

SrTiO{sub 3} (STO) single crystal wafer was annealed in vacuum, and co-planar metal-insulator-metal structure of Pt/Ti/STO/Ti/Pt were formed by sputtering Pt/Ti electrodes onto the surface of STO after annealing. The forming-free resistive switching behavior with self-compliance property was observed in the sample. The sample showed switchable diode effect, which is explained by a simple model that redistribution of oxygen vacancies (OVs) under the external electric field results in the formation of n-n{sup +} junction or n{sup +}-n junction (n donated n-type semiconductor; n{sup +} donated heavily doped n-type semiconductor). The self-compliance property is also interpreted by the formation of n-n{sup +}/n{sup +}-n junction caused by the migration of the OVs under the electric field. (orig.)

First-Principles Study on the Structural and Electronic Properties of N Atoms Doped-Rutile TiO2 of Oxygen Vacancies

Directory of Open Access Journals (Sweden)

Zhong-Liang Zeng

2015-01-01

Full Text Available For the propose of considering the actual situation of electronic neutral, a simulation has been down on the basis of choosing the position of dual N and researching the oxygen vacancy. It is found that the reason why crystal material gets smaller is due to the emergence of impurity levels. By introducing the oxygen vacancy to the structure, the results show that while the oxygen vacancy is near the two nitrogen atoms which have a back to back position, its energy gets the lowest level and its structure gets the most stable state. From its energy band structure and density, the author finds that the impurity elements do not affect the migration of Fermi level while the oxygen vacancy has been increased. Instead of that, the conduction band of metal atoms moves to the Fermi level and then forms the N-type semiconductor material, but the photocatalytic activity is not as good as the dual N-doping state.

Zinc vacancy and oxygen interstitial in ZnO revealed by sequential annealing and electron irradiation

Science.gov (United States)

Knutsen, K. E.; Galeckas, A.; Zubiaga, A.; Tuomisto, F.; Farlow, G. C.; Svensson, B. G.; Kuznetsov, A. Yu.

2012-09-01

By combining results from positron annihilation and photoluminescence spectroscopy with data from Hall effect measurements, the characteristic deep level emission centered at ˜1.75 eV and exhibiting an activation energy of thermal quenching of 11.5 meV is associated with the zinc vacancy. Further, a strong indication that oxygen interstitials act as a dominating acceptor is derived from the analysis of charge carrier losses induced by electron irradiation with variable energy below and above the threshold for Zn-atom displacement. We also demonstrate that the commonly observed green emission is related to an extrinsic acceptorlike impurity, which may be readily passivated by oxygen vacancies.

The role of Ar plasma treatment in generating oxygen vacancies in indium tin oxide thin films prepared by the sol-gel process

Energy Technology Data Exchange (ETDEWEB)

Hwang, Deuk-Kyu [Department of Materials Science and Engineering, Yonsei University, 50 Yonsei-ro, Seoul, 03722 (Korea, Republic of); Misra, Mirnmoy; Lee, Ye-Eun [Department of BioNano Technology, Gachon University, 1342 Seong-nam dae-ro, Seong-nam si, Gyeonggi-do, 13120 (Korea, Republic of); Baek, Sung-Doo [Department of Materials Science and Engineering, Yonsei University, 50 Yonsei-ro, Seoul, 03722 (Korea, Republic of); Myoung, Jae-Min, E-mail: jmmyoung@yonsei.ac.kr [Department of Materials Science and Engineering, Yonsei University, 50 Yonsei-ro, Seoul, 03722 (Korea, Republic of); Lee, Tae Il, E-mail: t2.lee77@gachon.ac.kr [Department of BioNano Technology, Gachon University, 1342 Seong-nam dae-ro, Seong-nam si, Gyeonggi-do, 13120 (Korea, Republic of)

2017-05-31

Highlights: • Indium tin oxide thin film with about 41 nm thickness was obtained by the sol-gel process. • Thin film exhibited low resistivity. • Sheet resistance of thin film decreases with Ar plasma treatment time. • Ar plasma treatment on thin film does not alter the crystal structure and optical properties of the ITO thin-film. • There is no significant change in oxygen vacancies after 20 min of plasma treatment. - Abstract: Argon (Ar) plasma treatment was carried out to reduce the sheet resistance of indium tin oxide (ITO) thin films. The Ar plasma treatment did not cause any significant changes to the crystal structure, surface morphology, or optical properties of the ITO thin films. However, an X-ray photoelectron spectroscopy study confirmed that the concentration of oxygen vacancies in the film dramatically increased with the plasma treatment time. Thus, we concluded that the decrease in the sheet resistance was caused by the increase in the oxygen vacancy concentration in the film. Furthermore, to verify how the concentration of oxygen vacancies in the film increased with the Ar plasma treatment time, cumulative and continuous plasma treatments were conducted. The oxygen vacancies were found to be created by surface heating via the outward thermal diffusion of oxygen atoms from inside the film.

Effect of oxygen vacancy distribution on the thermoelectric properties of La-doped SrTiO3 epitaxial thin films

KAUST Repository

Sarath Kumar, S. R.; Abutaha, Anas I.; Hedhili, Mohamed N.; Alshareef, Husam N.

2012-01-01

A detailed study of the role of oxygen vacancies in determining the effective mass and high temperature (300–1000 K) thermoelectricproperties of La-doped epitaxial SrTiO3 thin films is presented. It is observed that at intermediate temperatures, a transition from degenerate to non-degenerate behavior is observed in the Seebeck coefficient, but not electrical conductivity, which is attributed to heterogeneous oxygen non-stoichiometry. Heikes formula is found to be invalid for the films with oxygen vacancies. By fitting the spectroscopic ellipsometry (SE) data, obtained in the range 300–2100 nm, using a Drude-Lorentz dispersion relation with two Lorentz oscillators, the electrical and optical properties of the films are extracted. Using the excellent agreement between the transport properties extracted from SE modeling and direct electrical measurements, we demonstrate that an increase in concentration of oxygen vacancies results in a simultaneous increase of both carrier concentration and electron effective mass, resulting in a higher power factor.

Effect of oxygen vacancy distribution on the thermoelectric properties of La-doped SrTiO3 epitaxial thin films

KAUST Repository

Sarath Kumar, S. R.

2012-12-03

A detailed study of the role of oxygen vacancies in determining the effective mass and high temperature (300–1000 K) thermoelectricproperties of La-doped epitaxial SrTiO3 thin films is presented. It is observed that at intermediate temperatures, a transition from degenerate to non-degenerate behavior is observed in the Seebeck coefficient, but not electrical conductivity, which is attributed to heterogeneous oxygen non-stoichiometry. Heikes formula is found to be invalid for the films with oxygen vacancies. By fitting the spectroscopic ellipsometry (SE) data, obtained in the range 300–2100 nm, using a Drude-Lorentz dispersion relation with two Lorentz oscillators, the electrical and optical properties of the films are extracted. Using the excellent agreement between the transport properties extracted from SE modeling and direct electrical measurements, we demonstrate that an increase in concentration of oxygen vacancies results in a simultaneous increase of both carrier concentration and electron effective mass, resulting in a higher power factor.

Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Elimelech, Orian [The Institute of Chemistry and The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904 Israel; Liu, Jing [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Plonka, Anna M. [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Frenkel, Anatoly I. [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Banin, Uri [The Institute of Chemistry and The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904 Israel

2017-07-19

Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sized NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.

Contributions of oxygen vacancies and titanium interstitials to band-gap states of reduced titania

Science.gov (United States)

Li, Jingfeng; Lazzari, Rémi; Chenot, Stéphane; Jupille, Jacques

2018-01-01

The spectroscopic fingerprints of the point defects of titanium dioxide remain highly controversial. Seemingly indisputable experiments lead to conflicting conclusions in which oxygen vacancies and titanium interstitials are alternately referred to as the primary origin of the Ti 3 d band-gap states. We report on experiments performed by electron energy loss spectroscopy whose key is the direct annealing of only the very surface of rutile TiO2(110 ) crystals and the simultaneous measurement of its temperature via the Bose-Einstein loss/gain ratio. By surface preparations involving reactions with oxygen and water vapor, in particular, under electron irradiation, vacancy- and interstitial-related band-gap states are singled out. Off-specular measurements reveal that both types of defects contribute to a unique charge distribution that peaks in subsurface layers with a common dispersive behavior.

Roles of grain boundary and oxygen vacancies in Ba{sub 0.6}Sr{sub 0.4}TiO{sub 3} films for resistive switching device application

Energy Technology Data Exchange (ETDEWEB)

Yan, Xiaobing, E-mail: xiaobing-yan@126.com, E-mail: mseyanx@nus.edu.sg [Key Laboratory of Digital Medical Engineering of Hebei Province, College of Electron and Information Engineering, Hebei University, Baoding 071002 (China); Department of Materials Science and Engineering, National University of Singapore, Singapore, Singapore 117576 (Singapore); Li, Yucheng; Zhao, Jianhui; Li, Yan [Key Laboratory of Digital Medical Engineering of Hebei Province, College of Electron and Information Engineering, Hebei University, Baoding 071002 (China); Bai, Gang [College of Electronic Science and Engineering, Nanjing University of Posts and Telecommunications, Nanjing 210023 (China); Zhu, Siqi [Key Laboratory of Optoelectronic Information and Sensing Technologies of Guangdong Higher Education Institutes, Jinan University, Guangzhou 510632 (China)

2016-01-18

Oxygen vacancies are widely thought to be responsible for resistive switching (RS) effects based on polycrystalline oxides films. It is also well known that grain boundaries (GB) serve as reservoirs for accumulating oxygen vacancies. Here, Ar gas was introduced to enlarge the size of GB and increase the quantity of oxygen vacancies when the Ba{sub 0.6}Sr{sub 0.4}TiO{sub 3} (BST) films were deposited by pulse laser deposition technique. The experimental results indicate that the RS properties of the device exhibits better in the Ar-introduced BST films than in the O{sub 2}-grown BST films. High resolution transmission electron microscopy images show that an amorphous region GB with large size appears between two lattice planes corresponding to oxygen vacancies defects in the Ar-introduced BST. Fourier-transform infrared reflectivity spectroscopy results also reveal highly accumulated oxygen vacancies in the Ar-introduced BST films. And we propose that the conduction transport of the cell was dominantly contributed from not ions migration of oxygen vacancies but the electrons in our case according to the value of activation energies of two kinds of films.

Bonding of gold nanoclusters to oxygen vacancies on rutile TiO2(110)

DEFF Research Database (Denmark)

Lopez, Nuria; schaub, R.; Thostrup, P.

2003-01-01

Through an interplay between scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we show that bridging oxygen vacancies are the active nucleation sites for Au clusters on the rutile TiO2(110) surface. We find that a direct correlation exists between a decrease in...

Defective TiO2 with oxygen vacancies: synthesis, properties and photocatalytic applications

Science.gov (United States)

Pan, Xiaoyang; Yang, Min-Quan; Fu, Xianzhi; Zhang, Nan; Xu, Yi-Jun

2013-04-01

Titanium dioxide (TiO2), as an important semiconductor metal oxide, has been widely investigated in the field of photocatalysis. The properties of TiO2, including its light absorption, charge transport and surface adsorption, are closely related to its defect disorder, which in turn plays a significant role in the photocatalytic performance of TiO2. Among all the defects identified in TiO2, oxygen vacancy is one of the most important and is supposed to be the prevalent defect in many metal oxides, which has been widely investigated both by theoretical calculations and experimental characterizations. Here, we give a short review on the existing strategies for the synthesis of defective TiO2 with oxygen vacancies, and the defect related properties of TiO2 including structural, electronic, optical, dissociative adsorption and reductive properties, which are intimately related to the photocatalytic performance of TiO2. In particular, photocatalytic applications with regard to defective TiO2 are outlined. In addition, we offer some perspectives on the challenge and new direction for future research in this field. We hope that this tutorial minireview would provide some useful contribution to the future design and fabrication of defective semiconductor-based nanomaterials for diverse photocatalytic applications.Titanium dioxide (TiO2), as an important semiconductor metal oxide, has been widely investigated in the field of photocatalysis. The properties of TiO2, including its light absorption, charge transport and surface adsorption, are closely related to its defect disorder, which in turn plays a significant role in the photocatalytic performance of TiO2. Among all the defects identified in TiO2, oxygen vacancy is one of the most important and is supposed to be the prevalent defect in many metal oxides, which has been widely investigated both by theoretical calculations and experimental characterizations. Here, we give a short review on the existing strategies for the

Atomic geometry and STM simulations of a TiO.sub.2./sub.(110) surface upon formation of an oxygen vacancy and hydroxyl group

Czech Academy of Sciences Publication Activity Database

Mutombo, Pingo; Kiss, A.M.; Berkó, A.; Cháb, Vladimír

2008-01-01

Roč. 16, - (2008), 025007/1-025007/9 ISSN 0965-0393 R&D Projects: GA AV ČR IAA1010413 Grant - others:MŠMT(CZ) 9/2004 KONTAKT Institutional research plan: CEZ:AV0Z10100521 Source of funding: V - iné verejné zdroje Keywords : vacance * Oxygen * OH group * STM Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.388, year: 2008

Quantum-Size Dependence of the Energy for Vacancy Formation in Charged Small Metal Clusters. Drop Model

Science.gov (United States)

Pogosov, V. V.; Reva, V. I.

2018-04-01

Self-consistent computations of the monovacancy formation energy are performed for Na N , Mg N , and Al N (12 < N ≤ 168) spherical clusters in the drop model for stable jelly. Scenarios of the Schottky vacancy formation and "bubble vacancy blowing" are considered. It is shown that the asymptotic behavior of the size dependences of the energy for the vacancy formation by these two mechanisms is different and the difference between the characteristics of a charged and neutral cluster is entirely determined by the difference between the ionization potentials of clusters and the energies of electron attachment to them.

First-principles simulations of the leakage current in metal-oxide-semiconductor structures caused by oxygen vacancies in HfO2 high-K gate dielectric

International Nuclear Information System (INIS)

Mao, L.F.; Wang, Z.O.

2008-01-01

HfO 2 high-K gate dielectric has been used as a new gate dielectric in metal-oxide-semiconductor structures. First-principles simulations are used to study the effects of oxygen vacancies on the tunneling current through the oxide. A level which is nearly 1.25 eV from the bottom of the conduction band is introduced into the bandgap due to the oxygen vacancies. The tunneling current calculations show that the tunneling currents through the gate oxide with different defect density possess the typical characteristic of stress-induced leakage current. Further analysis shows that the location of oxygen vacancies will have a marked effect on the tunneling current. The largest increase in the tunneling current caused by oxygen vacancies comes about at the middle oxide field when defects are located at the middle of the oxide. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Ab-initio calculation for cation vacancy formation energy in anti-fluorite structure

Science.gov (United States)

Saleel, V. P. Saleel Ahammad; Chitra, D.; Veluraja, K.; Eithiraj, R. D.

2018-04-01

Lithium oxide (Li2O) has been suggested as a suitable breeder blanket material for fusion reactors. Li+ vacancies are created by neutron irradiation, forming bulk defect complex whose extra character is experimentally unclear. We present a theoretical study of Li2O using density functional theory (DFT) with a plane-wave basis set. The generalized gradient approximation (GGA) and local-density approximation (LDA) were used for exchange and correlation. Here we address the total energy for defect free, cation defect, cation vacancy and vacancy formation energy in Li2O crystal in anti-fluorite structure.

Positron annihilation study of vacancy-type defects in fast-neutron-irradiated MgO·nAl2O3

Science.gov (United States)

Rahman, Abu Zayed Mohammad Saliqur; Li, Zhuoxin; Cao, Xingzhong; Wang, Baoyi; Wei, Long; Xu, Qiu; Atobe, Kozo

2014-09-01

The positron lifetimes of fast-neutron-irradiated MgO·nAl2O3 single crystals were measured to investigate the formation of cation vacancies. Al monovacancy was possibly observed in samples irradiated by fast neutrons at ultra-low temperatures. Additionally, vacancy-oxygen complex centers were possibly observed in samples irradiated at higher temperatures and fast neutron fluences. Coincidence Doppler broadening (CDB) spectra were measured to obtain information regarding the vicinity of vacancy-type defects. A peak at approximately 11 × 10-3 m0c was observed, which may be due to the presence of oxygen atoms in the neighborhood of the vacancies.

Study of the movement of oxygen vacancies in the orthorhombic phase of YBa2Cu3O7-x by positron Doppler broadening spectroscopy

International Nuclear Information System (INIS)

Hong Zhang; Xiao-Gan Wang; Yao-Xian Fu

1988-01-01

The positron annihilation Doppler spectroscopy is used to monitor the movement of oxygen vacancy of YBa 2 Cu 3 O 7-x and an activation energy of (0.80 ± 0.10) eV for migration of oxygen vacancy in orthorhombic phase is obtained. (author)

Defect chemistry modelling of oxygen-stoichiometry, vacancy concentrations, and conductivity of (La1-xSrx)(y)MnO3 +/-delta

DEFF Research Database (Denmark)

Poulsen, F.W.

2000-01-01

model, based on delocalised electrons, electron holes and all B-ions being trivalent is given in Appendix A. The sequential mathematical method allows us to calculate the high temperature oxygen partial pressure dependent properties of (La1-xSrx)(y)MnO3+/-delta in a unified manner irrespective...... are calculated by the small polaron model containing only ionic species - the B-ion may be Mn-B' (Mn2+), Mn-B(x) (Mn3+), and Mn-B(Mn4+). The A/B-ratio = y greatly influences the oxygen stoichiometry, oxygen ion vacancy- and cation vacancy concentrations and the total conductivity. Calculations are given...

Oxygen vacancy and Moessbauer parameters of Fe doped tin oxides

International Nuclear Information System (INIS)

Nomura, K.; Mudarra Navarro, A.M.; Errico, L.; Rodriguez Torres, C.E.

2013-01-01

It is not clear what the local environment of Fe ions included in rutile structure is. In order to clarify this point, Moessbauer parameters of 57 Fe doped SnO 2 are compared with the results of ab initio calculation taking into account different configurations of iron and oxygen vacancy in the rutile structure of SnO 2 . Calculations were performed using the LAPW+lo method (Wien2k); RMT x Kmax = 7, A mesh of 50 k-points at IBZ, 2x2x2 super cell of SnO 2 . (J.P.N.)

Anisotropic O vacancy formation and diffusion in LaMnO3

KAUST Repository

Gan, Liyong; Salawu, Omotayo Akande; Schwingenschlö gl, Udo

2014-01-01

Anisotropy effects in solid oxide fuel cells are typically not considered because of high operating temperatures. Focusing on the prototypical perovskite LaMnO3, we apply first-principles calculations to demonstrate that this approximation is no longer valid when the operating temperature is reduced and discuss the consequences for the material properties. In addition, we show that strain and Sr doping can be used to further increase the anisotropy. Tensile strain promotes both the O vacancy formation and diffusion in pristine and Sr doped LaMnO3, while Sr doping enhances the O vacancy formation. Both in LaMnO3 and La0.75Sr0.25MnO3 the O diffusion is found to be favorable in the [011] and [011] directions.

Vacancy enhanced formation and phase transition of Cu-rich precipitates in α - iron under neutron irradiation

Energy Technology Data Exchange (ETDEWEB)

Lv, G. C. [Basic Experimental Center of Natural Science, University of Science and Technology Beijing, Beijing, 100083 (China); Corrosion and Protection Center, Key Laboratory of Environmental Fracture (MOE), University of Science and Technology Beijing, Beijing, 100083 (China); Zhang, H. [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Canada, T6G2V4 (Canada); He, X. F.; Yang, W. [China Institute of Atomic Energy, Beijing, 102413 (China); Su, Y. J., E-mail: yjsu@ustb.edu.cn [Corrosion and Protection Center, Key Laboratory of Environmental Fracture (MOE), University of Science and Technology Beijing, Beijing, 100083 (China)

2016-04-15

In this paper, we employed both molecular statics and molecular dynamics simulation methods to investigate the role of vacancies in the formation and phase transition of Cu-rich precipitates in α-iron. The results indicated that vacancies promoted the diffusion of Cu atoms to form Cu-rich precipitates. After Cu-rich precipitates formed, they further trapped vacancies. The supersaturated vacancy concentration in the Cu-rich precipitate induced a shear strain, which triggered the phase transition from bcc to fcc structure by transforming the initial bcc (110) plane into fcc (111) plane. In addition, the formation of the fcc-twin structure and the stacking fault structure in the Cu-rich precipitates was observed in dynamics simulations.

Sc and Nb Dopants in SrCoO3 Modulate Electronic and Vacancy Structures for Improved Water Splitting and SOFC Cathodes

KAUST Repository

Tahini, Hassan A.; Tan, Xin; Zhou, Wei; Zhu, Zhonghua; Schwingenschlö gl, Udo; Smith, Sean C.

2017-01-01

SrCoO3 is a promising material in the field of electrocatalysis. Difficulties in synthesising the material in its cubic phase have been overcome by doping it with Sc and Nb ions [Mater. Horiz.2015, 2, 495–501]. Using ab initio calculations and special quasi random structures we undertake a systematic study of these dopants in order to elucidate the effect of doping on electronic structure of the SrCoO3 host and the formation of oxygen vacancies. We find that while the overall electronic structure of SrCoO3 is preserved, increasing the Sc fraction leads to a decrease of electrical conductivity, in agreement with earlier experimental work. For low Sc and Nb doping fractions we find that the oxygen vacancy formation increases relative to undoped SrCoO3. However, as the dopants concentration is increased the vacancy formation energy drops significantly, indicating a strong tendency to accommodate high concentration of oxygen vacancies and hence non-stoichiometry. This is explained based on the electronic instabilities caused by the presence of Sc ions which weakens the B-O interactions as well as the increased degree of electron delocalization on the oxygen sublattice. Sc dopants also shift the p-band centre closer to the Fermi level, which can be associated with experimentally reported improvements in oxygen evolution reactions. These findings provide crucial baseline information for the design of better electrocatalysts for oxygen evolution reactions as well as fuel-cell cathode materials.

Sc and Nb Dopants in SrCoO3 Modulate Electronic and Vacancy Structures for Improved Water Splitting and SOFC Cathodes

KAUST Repository

Tahini, Hassan A.

2017-01-12

SrCoO3 is a promising material in the field of electrocatalysis. Difficulties in synthesising the material in its cubic phase have been overcome by doping it with Sc and Nb ions [Mater. Horiz.2015, 2, 495–501]. Using ab initio calculations and special quasi random structures we undertake a systematic study of these dopants in order to elucidate the effect of doping on electronic structure of the SrCoO3 host and the formation of oxygen vacancies. We find that while the overall electronic structure of SrCoO3 is preserved, increasing the Sc fraction leads to a decrease of electrical conductivity, in agreement with earlier experimental work. For low Sc and Nb doping fractions we find that the oxygen vacancy formation increases relative to undoped SrCoO3. However, as the dopants concentration is increased the vacancy formation energy drops significantly, indicating a strong tendency to accommodate high concentration of oxygen vacancies and hence non-stoichiometry. This is explained based on the electronic instabilities caused by the presence of Sc ions which weakens the B-O interactions as well as the increased degree of electron delocalization on the oxygen sublattice. Sc dopants also shift the p-band centre closer to the Fermi level, which can be associated with experimentally reported improvements in oxygen evolution reactions. These findings provide crucial baseline information for the design of better electrocatalysts for oxygen evolution reactions as well as fuel-cell cathode materials.

Room temperature alcohol sensing by oxygen vacancy controlled TiO2 nanotube array

International Nuclear Information System (INIS)

Hazra, A.; Dutta, K.; Bhowmik, B.; Bhattacharyya, P.; Chattopadhyay, P. P.

2014-01-01

Oxygen vacancy (OV) controlled TiO 2 nanotubes, having diameters of 50–70 nm and lengths of 200–250 nm, were synthesized by electrochemical anodization in the mixed electrolyte comprising NH 4 F and ethylene glycol with selective H 2 O content. The structural evolution of TiO 2 nanoforms has been studied by field emission scanning electron microscopy. Variation in the formation of OVs with the variation of the structure of TiO 2 nanoforms has been evaluated by photoluminescence and X-ray photoelectron spectroscopy. The sensor characteristics were correlated to the variation of the amount of induced OVs in the nanotubes. The efficient room temperature sensing achieved by the control of OVs of TiO 2 nanotube array has paved the way for developing fast responding alcohol sensor with corresponding response magnitude of 60.2%, 45.3%, and 36.5% towards methanol, ethanol, and 2-propanol, respectively.

Oxygen vacancy induced magnetization switching in Fe{sub 3}O{sub 4} epitaxial ultrathin films on GaAs(100)

Energy Technology Data Exchange (ETDEWEB)

Huang, Zhaocong, E-mail: zhaocong.huang@gmail.com [Department of Physics, Southeast University, Nanjing 211189 (China); Spintronics and Nanodevice Laboratory, Department of Electronics, University of York, York YO10 5DD (United Kingdom); School of Electronic Science and Engineering, Southeast University, Nanjing 210096 (China); Chen, Qian; Zhai, Ya, E-mail: yazhai@seu.edu.cn, E-mail: jlwang@seu.edu.cn; Wang, Jinlan, E-mail: yazhai@seu.edu.cn, E-mail: jlwang@seu.edu.cn [Department of Physics, Southeast University, Nanjing 211189 (China); Xu, Yongbing [Spintronics and Nanodevice Laboratory, Department of Electronics, University of York, York YO10 5DD (United Kingdom); Wang, Baoping [School of Electronic Science and Engineering, Southeast University, Nanjing 210096 (China)

2015-05-04

The magnetic and transport properties of half metallic Fe{sub 3}O{sub 4}, which are sensitive to the stoichiometry, are the key issue for applications in spintronics. An anomalous enlargement of the saturation magnetic moment is found in a relatively thick sample of epitaxial Fe{sub 3}O{sub 4} film by post-growth oxidation method. The investigation of the thickness dependence of magnetic moment suggests that the enhanced magnetism moment may come from the existence of oxygen vacancies. First-principles calculations reveal that with oxygen vacancies in Fe{sub 3}O{sub 4} crystal the spin of Fe ions in the tetrahedron site near the vacancy is much easier to switch parallel to the Fe ions in the octahedron site by temperature disturbance, supported by the temperature dependence of magnetic moment of Fe{sub 3}O{sub 4} films in experiment.

Vacancy formation in MoO3: hybrid density functional theory and photoemission experiments

KAUST Repository

Salawu, Omotayo Akande

2016-09-29

Molybdenum oxide (MoO3) is an important material that is being considered for numerous technological applications, including catalysis and electrochromism. In the present study, we apply hybrid density functional theory to investigate O and Mo vacancies in the orthorhombic phase. We determine the vacancy formation energies of different defect sites as functions of the electron chemical potential, addressing different charge states. In addition, we investigate the consequences of defects for the material properties. Ultraviolet photoemission spectroscopy is employed to study the valence band of stoichiometric and O defective MoO3. We show that O vacancies result in occupied in-gap states.

Vacancy formation in MoO3: hybrid density functional theory and photoemission experiments

KAUST Repository

Salawu, Omotayo Akande; Chroneos, Alexander; Vasilopoulou, Maria; Kennou, Stella; Schwingenschlö gl, Udo

2016-01-01

Molybdenum oxide (MoO3) is an important material that is being considered for numerous technological applications, including catalysis and electrochromism. In the present study, we apply hybrid density functional theory to investigate O and Mo vacancies in the orthorhombic phase. We determine the vacancy formation energies of different defect sites as functions of the electron chemical potential, addressing different charge states. In addition, we investigate the consequences of defects for the material properties. Ultraviolet photoemission spectroscopy is employed to study the valence band of stoichiometric and O defective MoO3. We show that O vacancies result in occupied in-gap states.

Oxygen Vacancies versus Fluorine at CeO 2 (111) : A Case of Mistaken Identity?

NARCIS (Netherlands)

Kullgren, J.; Wolf, M.J.; Castleton, C.W.M.; Mitev, P.; Briels, Willem J.; Hermansson, K.

2014-01-01

We propose a resolution to the puzzle presented by the surface defects observed with STM at the (111) surface facet of CeO 2 single crystals. In the seminal paper of Esch et al. [Science 309, 752 (2005)] they were identified with oxygen vacancies, but the observed behavior of these defects is

Electric-Field Control of Oxygen Vacancies and Magnetic Phase Transition in a Cobaltite/Manganite Bilayer

Science.gov (United States)

Cui, B.; Song, C.; Li, F.; Zhong, X. Y.; Wang, Z. C.; Werner, P.; Gu, Y. D.; Wu, H. Q.; Saleem, M. S.; Parkin, S. S. P.; Pan, F.

2017-10-01

Manipulation of oxygen vacancies (VO ) in single oxide layers by varying the electric field can result in significant modulation of the ground state. However, in many oxide multilayers with strong application potentials, e.g., ferroelectric tunnel junctions and solid-oxide fuel cells, understanding VO behavior in various layers under an applied electric field remains a challenge, owing to complex VO transport between different layers. By sweeping the external voltage, a reversible manipulation of VO and a corresponding fixed magnetic phase transition sequence in cobaltite/manganite (SrCoO3 -x/La0.45Sr0.55MnO3 -y ) heterostructures are reported. The magnetic phase transition sequence confirms that the priority of electric-field-induced VO formation or annihilation in the complex bilayer system is mainly determined by the VO formation energies and Gibbs free-energy differences, which is supported by theoretical analysis. We not only realize a reversible manipulation of the magnetic phase transition in an oxide bilayer but also provide insight into the electric-field control of VO engineering in heterostructures.

Oxygen vacancy tuned Ohmic-Schottky conversion for enhanced performance in β-Ga{sub 2}O{sub 3} solar-blind ultraviolet photodetectors

Energy Technology Data Exchange (ETDEWEB)

Guo, D. Y.; Wu, Z. P.; An, Y. H.; Guo, X. C.; Chu, X. L.; Sun, C. L.; Tang, W. H., E-mail: whtang@bupt.edu.cn [School of Science, Beijing University of Posts and Telecommunications, Beijing 100876 (China); State Key Laboratory of Information Photonics and Optical Communications, Beijing University of Posts and Telecommunications, Beijing 100876 (China); Li, L. H. [Physics Department, The State University of New York at Potsdam, Potsdam, New York 13676-2294 (United States); Li, P. G., E-mail: pgli@zstu.edu.cn [School of Science, Beijing University of Posts and Telecommunications, Beijing 100876 (China); Center for Optoelectronics Materials and Devices, Department of Physics, Zhejiang Sci-Tech University, Hangzhou, 310018 Zhejiang (China)

2014-07-14

β-Ga{sub 2}O{sub 3} epitaxial thin films were deposited using laser molecular beam epitaxy technique and oxygen atmosphere in situ annealed in order to reduce the oxygen vacancy. Metal/semiconductor/metal structured photodetectors were fabricated using as-grown film and annealed film separately. Au/Ti electrodes were Ohmic contact with the as-grown films and Schottky contact with the annealed films. In compare with the Ohmic-type photodetector, the Schottky-type photodetector takes on lower dark current, higher photoresponse, and shorter switching time, which benefit from Schottky barrier controlling electron transport and the quantity of photogenerated carriers trapped by oxygen vacancy significant decreasing.

Oxygen vacancy induced by La and Fe into ZnO nanoparticles to modify ferromagnetic ordering

International Nuclear Information System (INIS)

Verma, Kuldeep Chand; Kotnala, R.K.

2016-01-01

We reported long-range ferromagnetic interactions in La doped Zn 0.95 Fe 0.05 O nanoparticles that mediated through lattice defects or vacancies. Zn 0.92 Fe 0.05 La 0.03 O (ZFLaO53) nanoparticles were synthesized by a sol–gel process. X-ray fluorescence spectrum of ZFLaO53 detects the weight percentage of Zn, Fe, La and O. X-ray diffraction shows the hexagonal Wurtzite ZnO phase. The Rietveld refinement has been used to calculate the lattice parameters and the position of Zn, Fe, La and O atoms in the Wurtzite unit cell. The average size of ZFLaO53 nanoparticles is 99 nm. The agglomeration type product due to OH ions with La results into ZnO nanoparticles than nanorods that found in pure ZnO and Zn 0.95 Fe 0.05 O sample. The effect of doping concentration to induce Wurtzite ZnO structure and lattice defects has been analyzed by Raman active vibrational modes. Photoluminescence spectra show an abnormal emission in both UV and visible region, and a blue shift at near band edge is formed with doping. The room temperature magnetic measurement result into weak ferromagnetism but pure ZnO is diamagnetic. However, the temperature dependent magnetic measurement using zero-field and field cooling at dc magnetizing field 500 Oe induces long-range ferromagnetic ordering. It results into antiferromagnetic Neel temperature of ZFLaO53 at around 42 K. The magnetic hysteresis is also measured at 200, 100, 50 and 10 K measurement that indicate enhancement in ferromagnetism at low temperature. Overall, the La doping into Zn 0.95 Fe 0.05 O results into enhanced antiferromagnetic interaction as well as lattice defects/vacancies. The role of the oxygen vacancy as the dominant defects in doped ZnO must form Bound magnetic polarons has been described. - Graphical abstract: The long-range ferromagnetic order in Zn 0.92 Fe 0.05 La 0.03 O nanoparticles at low temperature measurements involves oxygen vacancy as the medium of magnetic interactions. - Highlights: • The La and Fe doping

Correlating oxygen vacancies and phase ratio/interface with efficient photocatalytic activity in mixed phase TiO2

International Nuclear Information System (INIS)

Verma, Ranjana; Samdarshi, S.K.

2015-01-01

Graphical abstract: The correlation of interfacial behavior and oxygen vacancies in mixed phase titania nanoparticles on their performance as photocatalyst has been investigated to explain the impact of photoactivity under UV and visible irradiation compared to pristine counterparts. The defects at the junction effectively reduce the band gap as well decrease the carrier recombination to enhance the photocatalytic activity. - Highlights: • Pristine and mixed phases (A/R ratio) TiO 2 synthesized by sol gel route. • Photoactivity variation has been correlated with the changes in the phase ratio. • Enhanced UV and visible activity attributable to oxygen vacancy present at the interface. • Role of A/R ratio and oxygen vacancy in the photoactivity of mixed TiO 2 depicted through a model. - Abstract: The photocatalytic activity is a result of the synergy of a succession of phenomena-photogeneration, separation, and participation of the charge carriers in redox reaction at the catalyst surface. While the extent of photogeneration is assessable in terms of absorption spectrum (band gap), the redox reaction can be correlated to specific surface area. However the respective change in the photocatalytic activity has not been rationally and consistently correlated with the above mentioned parameters. A satisfactory explanation of suppression of recombination based on separation of carriers due to differential mobility/diffusivity in the material phase(s) and/or intrinsic potential barrier exists but its correlation with common identifiable parameter/characteristics is still elusive. This paper attempts to address this issue by correlating the carrier separation with the phase ratio (phase interface) in mixed phase titania and generalizing it with the presence of oxygen vacancy at the phase interface. It essentially appears to complete the quest for identifiable parameters in the sequence of phenomena, which endow a photocatalyst with an efficient activity level. It has

Simple method to enhance positive bias stress stability of In-Ga-Zn-O thin-film transistors using a vertically graded oxygen-vacancy active layer.

Science.gov (United States)

Park, Ji Hoon; Kim, Yeong-Gyu; Yoon, Seokhyun; Hong, Seonghwan; Kim, Hyun Jae

2014-12-10

We proposed a simple method to deposit a vertically graded oxygen-vacancy active layer (VGA) to enhance the positive bias stress (PBS) stability of amorphous indium gallium zinc oxide (a-IGZO) thin-film transistors (TFTs). We deposited a-IGZO films by sputtering (target composition; In2O3:Ga2O3:ZnO = 1:1:1 mol %), and the oxygen partial pressure was varied during deposition so that the front channel of the TFTs was fabricated with low oxygen partial pressure and the back channel with high oxygen partial pressure. Using this method, we were able to control the oxygen vacancy concentration of the active layer so that it varied with depth. As a result, the turn-on voltage shift following a 10 000 s PBS of optimized VGA TFT was drastically improved from 12.0 to 5.6 V compared with a conventional a-IGZO TFT, without a significant decrease in the field effect mobility. These results came from the self-passivation effect and decrease in oxygen-vacancy-related trap sites of the VGA TFTs.

Determination of the vacancy formation enthalpy in chromium by positron annihilation

International Nuclear Information System (INIS)

Loper, G.D.; Smedskjaer, L.C.; Chason, M.K.; Siegel, R.W.

1985-01-01

Doppler broadening of the positron annihilation lineshape in 99.99 at. % pure chromium was measured over the temperature range 296 to 2049 0 K. The chromium sample was encapsulated in sapphire owing to its high vapor pressure near melting. Saturation-like behavior of the lineshape was observed near the melting temperature (2130 0 K). A two-state trapping model fit to the data yielded a vacancy formation enthalpy of 2.0 +- 0.2 eV. This result is discussed in relation to extant empirical relations for vacancy migration and self-diffusion in metals and to data from previous self-diffusion and annealing experiments in chromium. It is concluded that the observed vacancy ensemble is unlikely to be responsible for the measured self-diffusion behavior. The implications of the present results in terms of our understanding of mechanisms for self-diffusion in chromium and other refractory bcc metals are discussed

A Facile Approach to Prepare Black TiO2 with Oxygen Vacancy for Enhancing Photocatalytic Activity

Science.gov (United States)

Chen, Shihao; Xiao, Yang; Hu, Zhengfa; Zhao, Hui; Xie, Wei

2018-01-01

Black TiO2 has triggered worldwide research interest due to its excellent photocatalytic properties. However, the understanding of its structure–property relationships and a more effective, facile and versatile method to produce it remain great challenges. We have developed a facile approach to synthesize black TiO2 nanoparticles with significantly improved light absorption in the visible and infrared regions. The experimental results show that oxygen vacancies are the major factors responsible for black coloration. More importantly, our black TiO2 nanoparticles have no Ti3+ ions. These oxygen vacancies could introduce localized states in the bandgap and act as trap centers, significantly decreasing the electron–hole recombination. The photocatalytic decomposition of both rhodamine B and methylene blue demonstrated that, under ultraviolet light irradiation, better photocatalytic performance is achieved with our black TiO2 nanoparticles than with commercial TiO2 nanoparticles. PMID:29659500

Room temperature alcohol sensing by oxygen vacancy controlled TiO{sub 2} nanotube array

Energy Technology Data Exchange (ETDEWEB)

Hazra, A.; Dutta, K.; Bhowmik, B.; Bhattacharyya, P., E-mail: pb-etc-besu@yahoo.com [Nano-Thin Films and Solid State Gas Sensor Devices Laboratory, Department of Electronics and Telecommunication Engineering, Indian Institute of Engineering Science and Technology (IIEST), Shibpur, Howrah (India); Chattopadhyay, P. P. [Department of Metallurgy and Materials Engineering, Indian Institute of Engineering Science and Technology (IIEST), Shibpur, Howrah (India)

2014-08-25

Oxygen vacancy (OV) controlled TiO{sub 2} nanotubes, having diameters of 50–70 nm and lengths of 200–250 nm, were synthesized by electrochemical anodization in the mixed electrolyte comprising NH{sub 4}F and ethylene glycol with selective H{sub 2}O content. The structural evolution of TiO{sub 2} nanoforms has been studied by field emission scanning electron microscopy. Variation in the formation of OVs with the variation of the structure of TiO{sub 2} nanoforms has been evaluated by photoluminescence and X-ray photoelectron spectroscopy. The sensor characteristics were correlated to the variation of the amount of induced OVs in the nanotubes. The efficient room temperature sensing achieved by the control of OVs of TiO{sub 2} nanotube array has paved the way for developing fast responding alcohol sensor with corresponding response magnitude of 60.2%, 45.3%, and 36.5% towards methanol, ethanol, and 2-propanol, respectively.

Sn doped TiO{sub 2} nanotube with oxygen vacancy for highly efficient visible light photocatalysis

Energy Technology Data Exchange (ETDEWEB)

Li, Jinliang; Xu, Xingtao [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Shanghai Key Laboratory of Magnetic Resonance, School of Physics and Materials Science, Department of Physics, East China Normal University, Shanghai 200062 (China); Liu, Xinjuan [Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Yu, Caiyan; Yan, Dong; Sun, Zhuo [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Shanghai Key Laboratory of Magnetic Resonance, School of Physics and Materials Science, Department of Physics, East China Normal University, Shanghai 200062 (China); Pan, Likun, E-mail: lkpan@phy.ecnu.edu.cn [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Shanghai Key Laboratory of Magnetic Resonance, School of Physics and Materials Science, Department of Physics, East China Normal University, Shanghai 200062 (China)

2016-09-15

Sn doped TiO{sub 2} nanotube with oxygen vacancy (V{sub o}-Sn−TiO{sub 2}) was successfully synthesized via a facile hydrothermal process and subsequent annealing in nitrogen atmosphere. The morphology, structure and photocatalytic performance of V{sub o}-Sn−TiO{sub 2} in the degradation of nitrobenzene were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, UV–vis absorption spectroscopy, nitrogen adsorption-desorption and electrochemical impedance spectra, respectively. The inner diameter, outer diameter and specific surface area of V{sub o}-Sn−TiO{sub 2} are about 5 nm, 15 nm and 235.54 m{sup 2} g{sup −1}, respectively. The experimental results show that the V{sub o}-Sn−TiO{sub 2} exhibits excellent photocatalytic performance with a maximum degradation rate of 92% in 300 min for nitrobenzene and 94% in 100 min for Rhodamine B and corresponding mineralization rates of 68% and 70% under visible light irradiation. The improved photocatalytic performance is ascribed to the enhanced light absorption and specific surface area as well as the reduced electron-hole pair recombination with the presence of oxygen vacancy and Sn doping in the TiO{sub 2} nanotube. - Highlights: • Photocatalysis is an environmental-friendly technology for nitrobenzene removal. • Sn doped TiO{sub 2} nanotube with oxygen vacancy is fabricated for the first time. • It exhibits excellent photocatalytic performance in degradation of nitrobenzene. • A high degradation rate of 92% is achieved under visible light irradiation.

Characteristics of chemical bond and vacancy formation in chalcopyrite-type CuInSe2 and related compounds

International Nuclear Information System (INIS)

Maeda, Tsuyoshi; Wada, Takahiro

2009-01-01

We studied characteristics of chemical bond and vacancy formation in chalcopyrite-type CuInSe 2 (CIS) by first principles calculations. The chalcopyrite-type CIS has two kinds of chemical bonds, Cu-Se and In-Se. The Cu-Se bond is a weak covalent bonding because electrons occupy both bonding and antibonding orbitals of Cu 3d and Se 4p and occupy only the bonding orbital (a 1 ) of Cu 4s and Se 4p and do not occupy the antibonding orbital (a 1 * ) of Cu 4s and Se 4p. On the other hand, the In-Se bond has a partially covalent and partially ionic character because the In 5s orbital covalently interacts with Se 4p; the In 5p orbital is higher than Se 4p and so the electron in the In 5p orbital moves to the Se 4p orbital. The average bond order of the Cu-Se and In-Se bonds can be calculated to be 1/4 and 1, respectively. The bond order of Cu-Se is smaller than that of In-Se. The characteristics of these two chemical bonds are related to the formation of Cu and In vacancies in CIS. The formation energy of the Cu vacancy is smaller than that of the In vacancy under both Cu-poor and In-poor conditions. The displacement (Δl) of the surrounding Se atoms after the formation of the Cu vacancy is smaller than the Δl after the formation of the In vacancy. The interesting and unique characteristics of CIS are discussed on the basis of the characteristics of the chemical bond. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Positron annihilation study of formation of Mg vacancy in MgO

International Nuclear Information System (INIS)

Mizuno, M.; Araki, H.; Shirai, Y.; Inoue, Y.; Sugita, K.; Mizoguchi, T.; Tanaka, I.; Adachi, H.

2004-01-01

We have investigated the formation of Mg vacancy induced by ultra-dilute trivalent impurities in MgO by a combination of positron annihilation measurement and theoretical calculations of positron lifetimes. The undoped MgO yields the shortest positron lifetime of 130 ps that is shorter than that of 166 ps previously reported using a single crystal sample. The positron lifetime of the doped samples increases with the increase of the Al or Ga dopant concentration and is saturated at around 170 ps. This result indicates that the previously reported value of 166 ps is ascribed to not the bulk but the vacancy state induced by impurities. The experimental bulk lifetime of 130 ps, which is obtained by employing trapping model, is well reproduced by the theoretical calculation using the semiconductor model. The calculated defect lifetime is about 20 ps longer than the experimental value. This may be due to the lattice relaxation around Mg vacancy associated with the trapping of positrons. (orig.)

Positron annihilation study of formation of Mg vacancy in MgO

Energy Technology Data Exchange (ETDEWEB)

Mizuno, M.; Araki, H.; Shirai, Y. [Science and Technology Center for Atoms, Molecules and Ions Control, Osaka Univ., Osaka (Japan); Inoue, Y.; Sugita, K. [Dept. of Materials Science and Engineering, Osaka Univ., Osaka (Japan); Mizoguchi, T.; Tanaka, I.; Adachi, H. [Dept. of Materials Science and Engineering, Kyoto Univ., Kyoto (Japan)

2004-07-01

We have investigated the formation of Mg vacancy induced by ultra-dilute trivalent impurities in MgO by a combination of positron annihilation measurement and theoretical calculations of positron lifetimes. The undoped MgO yields the shortest positron lifetime of 130 ps that is shorter than that of 166 ps previously reported using a single crystal sample. The positron lifetime of the doped samples increases with the increase of the Al or Ga dopant concentration and is saturated at around 170 ps. This result indicates that the previously reported value of 166 ps is ascribed to not the bulk but the vacancy state induced by impurities. The experimental bulk lifetime of 130 ps, which is obtained by employing trapping model, is well reproduced by the theoretical calculation using the semiconductor model. The calculated defect lifetime is about 20 ps longer than the experimental value. This may be due to the lattice relaxation around Mg vacancy associated with the trapping of positrons. (orig.)

Ultrathin FeOOH nanolayers with abundant oxygen vacancies on BiVO{sub 4} photoanodes for efficient water oxidation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Beibei [State Key Laboratory for Oxo Synthesis and Selective Oxidation, National Engineering Research Center for Fine Petrochemical Intermediates, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou (China); State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province, and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou (China); Wang, Lei; Zhang, Yajun; Bi, Yingpu [State Key Laboratory for Oxo Synthesis and Selective Oxidation, National Engineering Research Center for Fine Petrochemical Intermediates, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou (China); Ding, Yong [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province, and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou (China)

2018-02-19

Photoelectrochemical (PEC) water splitting is a promising method for storing solar energy in the form of hydrogen fuel, but it is greatly hindered by the sluggish kinetics of the oxygen evolution reaction (OER). Herein, a facile solution impregnation method is developed for growing ultrathin (2 nm) highly crystalline β-FeOOH nanolayers with abundant oxygen vacancies on BiVO{sub 4} photoanodes. These exhibited a remarkable photocurrent density of 4.3 mA cm{sup -2} at 1.23 V (vs. reversible hydrogen electrode (RHE), AM 1.5 G), which is approximately two times higher than that of amorphous FeOOH fabricated by electrodeposition. Systematic studies reveal that the excellent PEC activity should be attributed to their ultrathin crystalline structure and abundant oxygen vacancies, which could effectively facilitate the hole transport/trapping and provide more active sites for water oxidation. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Multi-scale modeling of interaction between vacancies and alloying elements in ferritic alloys

International Nuclear Information System (INIS)

Barouh, Caroline

2015-01-01

This PhD thesis is devoted to the study of interaction between vacancies and alloying elements in Oxide Dispersion Strengthened (ODS) steels, which are promising candidate materials for future nuclear reactors. This work is based on multi-scale modeling of a simplified system composed by oxygen, yttrium and titanium atoms and vacancies in an α-iron lattice. We particularly focused on the role of vacancies which are created in excess during the fabrication of these steels. The stability and mobility of vacancy-solute clusters have been examined using ab initio calculations for oxygen, on one hand, which has been systematically compared to carbon and nitrogen, interstitial solutes frequently present in iron-based materials, and, on the other hand, for substitutional solutes: titanium and yttrium. The three interstitial solutes show very similar energetic and kinetic behaviors. The impact of small mobile vacancy-solute clusters has been verified using a cluster dynamics model based on our ab initio results. It has been thus demonstrated that with over-saturation of vacancies, diffusion of interstitial solutes may be accelerated, while substitutional solutes do not become necessarily faster. These conclusions are consistent with existing experimental observations. All these results have been then used to complete our understanding of nano-clusters formation mechanisms. It appeared that the relative mobility of yttrium and titanium, as well as the number of potential nuclei to form nanoparticles strongly depend on the total vacancy concentration in the system. (author) [fr

A quantum-chemical study of oxygen-vacancy defects in PbTiO3 crystals

International Nuclear Information System (INIS)

Stashans, Arvids; Serrano, Sheyla; Medina, Paul

2006-01-01

Investigation of an oxygen vacancy and F center in the cubic and tetragonal lattices of PbTiO 3 crystals is done by means of quantum-chemical simulations. Displacements of defect-surrounding atoms, electronic and optical properties, lattice relaxation energies and some new effects due to the defects presence are reported and analyzed. A comparison with similar studies is made and conclusions are drawn on the basis of the obtained results

Prediction of high-temperature point defect formation in TiO2 from combined ab initio and thermodynamic calculations

International Nuclear Information System (INIS)

He, J.; Behera, R.K.; Finnis, M.W.; Li, X.; Dickey, E.C.; Phillpot, S.R.; Sinnott, S.B.

2007-01-01

A computational approach that integrates ab initio electronic structure and thermodynamic calculations is used to determine point defect stability in rutile TiO 2 over a range of temperatures, oxygen partial pressures and stoichiometries. Both donors (titanium interstitials and oxygen vacancies) and acceptors (titanium vacancies) are predicted to have shallow defect transition levels in the electronic-structure calculations. The resulting defect formation energies for all possible charge states are then used in thermodynamic calculations to predict the influence of temperature and oxygen partial pressure on the relative stabilities of the point defects. Their ordering is found to be the same as temperature increases and oxygen partial pressure decreases: titanium vacancy → oxygen vacancy → titanium interstitial. The charges on these defects, however, are quite sensitive to the Fermi level. Finally, the combined formation energies of point defect complexes, including Schottky, Frenkel and anti-Frenkel defects, are predicted to limit the further formation of point defects

The modulation of oxygen vacancies by the combined current effect and temperature cycling in La0.7Sr0.3CoO3 film

Science.gov (United States)

Li, J.; Wang, J.; Kuang, H.; Zhao, Y. Y.; Qiao, K. M.; Liu, Y.; Hu, F. X.; Sun, J. R.; Shen, B. G.

2018-05-01

Modulating the oxygen defect concentration has been accepted as an effective method to obtain high catalytic activity in perovskite cobaltites. However, controllably modifying the oxygen vacancy is still a challenge in this type of materials, which strongly obstructs their application. Here, we report a successful oxygen vacancies modulation in the La0.7Sr0.3CoO3 (LSCO) film by using combined current effect and temperature cycling. The temperature dependent transport properties of the LSCO/LAO film were investigated. The results revealed that the resistance of the film keeps increasing under the repeated measurements. It was found that the accumulation of the oxygen vacancy by current effect transforms the Co4+ ion into Co3+ ion, which results in the enhancement of the resistance and thus the transport switching behavior. Moreover, the resistance in the cooling process was found to be much higher than that in previous cooling and heating processes, which indicates that the oxygen escapes more quickly in the high temperature region. On the other hand, our analysis indicates that the CoO6 distortion may contribute to the switching of transport behaviors in the low temperature region. Our work provides an effective and controllable way to modulate oxygen defect in the perovskite-type oxides.

Wide-range tunable bandgap in Bi1−xCaxFe1−yTiyO3−δ nanoparticles via oxygen vacancy induced structural modulations at room temperature

International Nuclear Information System (INIS)

Mocherla, Pavana S V; Sudakar, C; Gautam, Sanjeev; Chae, Keun Hwa; Rao, M S Ramachandra

2015-01-01

We demonstrate that oxygen vacancies (V O ) produced by aliovalent (Ca 2+ ) doping in BiFeO 3 (BCFO) and associated structural changes due to V O ordering result in systematic alteration of the bandgap (E g ) over a wide range from 1.5 eV to 2.3 eV. By contrast, the change in the bandgap of a Ca 2+ and Ti 4+ co-doped BiFeO 3 (BCFTO) system, wherein the V O formation is suppressed, is negligible. These contrastive results strongly confirm the role of oxygen vacancies in altering the bandgap of BCFO. Irrespective of doping, microstrain, which is found to be large (0.3 to 1.2%) below a critical size (d c ∼ 60 nm) also produces a small, yet linear change in the bandgap (E g from 2.0 to 2.3 eV). The cubic phase stabilizes gradually in BCFO for x > 0.1 through an orthorhombic phase (for 0.05 < x < 0.1), whereas it directly transforms for x > 0.1 in BCFTO. This change in BCFO at 300 K suggests a high-pressure-like (or high-temperature-like) effect of the oxygen vacancies and dopants on the structure. Systematic variations in the relative intensities and peak positions of Fe d–d transitions in BCFO reveal the local changes in Fe–O–Fe coordination. These results along with XANES and HRTEM studies substantiate the observed structural changes. (paper)

Vacancy formation energy of Li(H,D) and Na(H,D) systems

International Nuclear Information System (INIS)

Islam, A.K.M.A.

1993-06-01

Vacancy defect formation energy (Schottky defect) of lighter hydrides and deuterides of alkali metals are discussed with reference to conductivity measurements and the recent computer simulation calculations. An empirical relation with Debye temperature is found to yield values of Schottky defect formation energies of Li(H,D) systems in agreement with experiments. The relationship is also utilized to obtain the formation energies for Na(H,D) systems for which experimental values are available in the literature. (author). 37 refs, 1 fig., 1 tab

Positron annihilation study of vacancy-type defects in fast-neutron-irradiated MgO·nAl2O3

International Nuclear Information System (INIS)

Rahman, Abu Zayed Mohammad Saliqur; Li, Zhuoxin; Cao, Xingzhong; Wang, Baoyi; Wei, Long; Xu, Qiu; Atobe, Kozo

2014-01-01

Highlights: •Detection of Al monovacancy by positron lifetime spectroscopy in fast neutron-irradiated MgO·nAl 2 O 3 (n=2). •Concentration of defects is also estimated for Al monovacancy. •O atom peak was observed by using coincidence Doppler broadening spectroscopy. -- Abstract: The positron lifetimes of fast-neutron-irradiated MgO·nAl 2 O 3 single crystals were measured to investigate the formation of cation vacancies. Al monovacancy was possibly observed in samples irradiated by fast neutrons at ultra-low temperatures. Additionally, vacancy-oxygen complex centers were possibly observed in samples irradiated at higher temperatures and fast neutron fluences. Coincidence Doppler broadening (CDB) spectra were measured to obtain information regarding the vicinity of vacancy-type defects. A peak at approximately 11 × 10 −3 m 0 c was observed, which may be due to the presence of oxygen atoms in the neighborhood of the vacancies

Photocatalytic Conversion of Nitrogen to Ammonia with Water on Surface Oxygen Vacancies of Titanium Dioxide.

Science.gov (United States)

Hirakawa, Hiroaki; Hashimoto, Masaki; Shiraishi, Yasuhiro; Hirai, Takayuki

2017-08-09

Ammonia (NH 3 ) is an essential chemical in modern society. It is currently manufactured by the Haber-Bosch process using H 2 and N 2 under extremely high-pressure (>200 bar) and high-temperature (>673 K) conditions. Photocatalytic NH 3 production from water and N 2 at atmospheric pressure and room temperature is ideal. Several semiconductor photocatalysts have been proposed, but all suffer from low efficiency. Here we report that a commercially available TiO 2 with a large number of surface oxygen vacancies, when photoirradiated by UV light in pure water with N 2 , successfully produces NH 3 . The active sites for N 2 reduction are the Ti 3+ species on the oxygen vacancies. These species act as adsorption sites for N 2 and trapping sites for the photoformed conduction band electrons. These properties therefore promote efficient reduction of N 2 to NH 3 . The solar-to-chemical energy conversion efficiency is 0.02%, which is the highest efficiency among the early reported photocatalytic systems. This noble-metal-free TiO 2 system therefore shows a potential as a new artificial photosynthesis for green NH 3 production.

Electronic structure and O vacancy formation/migration in La0.825(Mg/Ca/Ba)0.125CoO3

KAUST Repository

Omotayo Akande, Salawu

2016-05-05

The effect of A-site hole doping (Mg2+, Ca2+ or Ba2+) on the electronic and magnetic properties as well as the O vacancy formation and migration in perovskite LaCoO3 is studied using first-principles calculations. All three dopants are found to facilitate O vacancy formation. Substitution of La3+ with Ba2+/Mg2+ yields the lowest O vacancy formation energy for low/intermediate spin Co, implying that not only the structure but also the spin state of Co is a key parameter. Only for low spin Co the ionic radius is correlated with the O migration barrier. Enhanced migration for intermediate spin Co is ascribed to the availability of additional space at the transition state. © CopyrightEPLA, 2016.

Oxygen vacancy effect on photoluminescence of KNb3O8 nanosheets

Science.gov (United States)

Li, Rui; Liu, Liying; Ming, Bangming; Ji, Yuhang; Wang, Ruzhi

2018-05-01

Fungus-like potassium niobate (KNb3O8) nanosheets have been synthesized on indium-doped tin oxide (ITO) glass substrates by a simple and environmental friendly two-step hydrothermal process. The prepared samples have been characterized by using X-ray Diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), High Resolution Transmission Electron Microscope (HRTEM), Fourier Transform Infra-Red Spectroscopy (FTIR), Raman Spectroscopy and X-ray Photoelectron Spectroscopy (XPS). Furthermore, the photoluminescence (PL) of KNb3O8 nanosheets have been systematically studied. The results showed that the PL spectrum is between 300 and 645 nm with a 325 nm light excitation, which is divided into some sub-peaks. It is different from the perfect KNb3O8 nanosheets whose PL emission peaks located at near 433 nm. It should be originated from the effect of the oxygen (O) vacancies in the KNb3O8 nanosheets, which the PLs peaks can be found at about 490 nm and 530 nm by different position of O vacancy. The experimental results are in accordance with the first-principles calculations. Our results may present a feasible clue to estimate the defect position in KNb3O8 by the shape analysis of its spectrum of PLs.

Electronic structure of vacancies and vacancy clusters in simple metals

International Nuclear Information System (INIS)

Manninen, M.; Nieminen, R.M.

1978-05-01

The self-consistent density functional approach has been applied in a study of electronic properties of vacancies and vacancy clusters in simple metals. The electron density profiles and potentials have been obtained for spherical voids of varying size. The formation energies and residual resistivities have been calculated for vacancies using both perturbational and variational inclusion of discrete lattice effects. The relation of the void properties to the plane surface ones is studied, and the inadequacy of the jellium-based methods to high-index faces is demonstrated. (author)

First-principles studies of various crystallographic phases and neutral atomic vacancies in KNbO3 and KTaO3

International Nuclear Information System (INIS)

Shigemi, A.; Koyama, T.; Wada, T.

2006-01-01

We evaluated enthalpies of formation and formation energies of neutral vacancies in KNbO 3 and KTaO 3 using a plane-wave pseudopotential method within a density functional formalism. The KNbO 3 (R3mR) phase with the lowest symmetry was found to have the lowest enthalpy of formation. On the other hand, the various virtual KTaO 3 phases (P4mm, Bmm2 and R3mR) with the lower symmetry were found to be approximately equal to the enthalpy of formation of a cubic KTaO 3 phase at 0 K. For both KNbO 3 and KTaO 3 , the formation energy of a K vacancy was found to be the lowest under an oxidizing atmosphere and that of an O vacancy was found to be the lowest under a reducing atmosphere. The formation energy of a Nb/Ta vacancy was the highest under both oxygen-rich and -poor conditions. These results are in good agreement with the empirical rule that B site defects in perovskite-type oxide do not exist. (copyright 2006 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Simultaneous modulation of surface composition, oxygen vacancies and assembly in hierarchical Co3O4 mesoporous nanostructures for lithium storage and electrocatalytic oxygen evolution

DEFF Research Database (Denmark)

Sun, Hongyu; Zhao, Yanyan; Mølhave, Kristian

2017-01-01

in superior electrochemical properties when used as the anode materials for lithium-ion batteries and as an electrocatalyst for the oxygen evolution reaction. The excellent electrochemical performance is attributed to the synergistic effects of novel hierarchical morphology, crystal structure of the active...... materials, the improvement of intrinsic conductivity and inner surface area induced by the oxygen vacancies. The present strategy not only provides a facile method to assemble novel hierarchical architectures, but also paves a way to control surface structures (chemical composition and crystal defects...

Theory of the temperature dependence of positron bulk lifetimes-implications for vacancy formation enthalpy measurements via positron experiments

International Nuclear Information System (INIS)

Tam, S.W.; Sinha, S.K.; Siegel, R.W.

1977-02-01

Temperature dependent effects, which may have a bearing on determinations of vacancy formation enthalpies in metals by positron annihilation, have been observed in certain metals. These effects have been observed to occur both at temperatures below those at which positron annihilation is most sensitive to equilibrium vacancies and at temperatures well within the vacancy-sensitive region. The effect of thermal lattice displacements on positron lifetimes in metals was investigated to help understand these phenomena

Defect production and formation of helium-vacancy clusters due to cascades in α-iron

International Nuclear Information System (INIS)

Yang, L.; Zu, X.T.; Xiao, H.Y.; Gao, F.; Heinisch, H.L.; Kurtz, R.J.

2007-01-01

Displacement cascades are simulated by molecular dynamics methods in α-Fe containing different concentrations of substitutional He atoms. Primary knock-on atom (PKA) energies, E p , from 0.5 to 5 keV are considered at the irradiation temperature of 100 K. The concentration of He in Fe varies from 1 to 5 at%, and the results are compared with the simulations performed in pure α-Fe. We find that the total number of point defects increases with increasing He concentration. The present studies reveal the formation and the configurations of He-vacancy clusters in the cascades of α-Fe. Furthermore, the production efficiency of He-vacancy clusters increases with increasing He concentration and PKA energy. The nucleation mechanisms of He-vacancy clusters in displacement cascades are discussed in detail

Dynamics of ordering processes in annealed dilute systems: Island formation, vacancies at domain boundaries, and compactification

DEFF Research Database (Denmark)

Shah, Peter Jivan; Mouritsen, Ole G.

1990-01-01

The dynamics of the ordering processes in two-dimensional lattice models with annealed vacancies and nonconserved order parameter is studied as a function of temperature and vacancy concentration by means of Monte Carlo temperature-quenching simulations. The models are Ising antiferromagnets...... with couplings leading to twofold-degenerate as well as fourfold-degenerate ordering. The models are quenched into a phase-separation region, which makes it possible for both types of ordering to observe the following scenario of ordering processes: (i) early-time nucleation and growth of ordered domains, (ii......) intermediate-time trapping of the mobile vacancies at the domain boundaries, and (iii) late-time diffusion of vacancies along the domain-boundary network towards the surface. In the case of high dilution, the ordering processes correspond to early-time island formation and late-time coarsening...

Oxygen-Vacancy Abundant Ultrafine Co3O4/Graphene Composites for High-Rate Supercapacitor Electrodes.

Science.gov (United States)

Yang, Shuhua; Liu, Yuanyue; Hao, Yufeng; Yang, Xiaopeng; Goddard, William A; Zhang, Xiao Li; Cao, Bingqiang

2018-04-01

The metal oxides/graphene composites are one of the most promising supercapacitors (SCs) electrode materials. However, rational synthesis of such electrode materials with controllable conductivity and electrochemical activity is the topical challenge for high-performance SCs. Here, the Co 3 O 4 /graphene composite is taken as a typical example and develops a novel/universal one-step laser irradiation method that overcomes all these challenges and obtains the oxygen-vacancy abundant ultrafine Co 3 O 4 nanoparticles/graphene (UCNG) composites with high SCs performance. First-principles calculations show that the surface oxygen vacancies can facilitate the electrochemical charge transfer by creating midgap electronic states. The specific capacitance of the UCNG electrode reaches 978.1 F g -1 (135.8 mA h g -1 ) at the current densities of 1 A g -1 and retains a high capacitance retention of 916.5 F g -1 (127.3 mA h g -1 ) even at current density up to 10 A g -1 , showing remarkable rate capability (more than 93.7% capacitance retention). Additionally, 99.3% of the initial capacitance is maintained after consecutive 20 000 cycles, demonstrating enhanced cycling stability. Moreover, this proposed laser-assisted growth strategy is demonstrated to be universal for other metal oxide/graphene composites with tuned electrical conductivity and electrochemical activity.

Efficient Visible Light Nitrogen Fixation with BiOBr Nanosheets of Oxygen Vacancies on the Exposed {001} Facets.

Science.gov (United States)

Li, Hao; Shang, Jian; Ai, Zhihui; Zhang, Lizhi

2015-05-20

Even though the well-established Haber-Bosch process has been the major artificial way to "fertilize" the earth, its energy-intensive nature has been motivating people to learn from nitrogenase, which can fix atmospheric N2 to NH3 in vivo under mild conditions with its precisely arranged proteins. Here we demonstrate that efficient fixation of N2 to NH3 can proceed under room temperature and atmospheric pressure in water using visible light illuminated BiOBr nanosheets of oxygen vacancies in the absence of any organic scavengers and precious-metal cocatalysts. The designed catalytic oxygen vacancies of BiOBr nanosheets on the exposed {001} facets, with the availability of localized electrons for π-back-donation, have the ability to activate the adsorbed N2, which can thus be efficiently reduced to NH3 by the interfacial electrons transferred from the excited BiOBr nanosheets. This study might open up a new vista to fix atmospheric N2 to NH3 through the less energy-demanding photochemical process.

Vacancy complexes induce long-range ferromagnetism in GaN

KAUST Repository

Zhang, Zhenkui

2014-11-14

By means of density functional theory, we argue that ferromagnetism in GaN can be induced by vacancy complexes. Spin polarization originates from the charge compensation between neutral N and Ga vacancies. Defect formation energy calculations predict that a vacancy complex of two positively charged N vacancies and one doubly negative Ga vacancy is likely to form. This defect complex induces a net moment of 1 μB, which is localized around the negative Ga center and exhibits pronounced in-plane ferromagnetic coupling. In contrast to simple Ga vacancy induced ferromagnetism, the proposed picture is in line with the fact that N vacancies have a low formation energy. Formation energies indicate mutual stabilization of the intrinsic defects in GaN.

Vacancy complexes induce long-range ferromagnetism in GaN

Energy Technology Data Exchange (ETDEWEB)

Zhang, Zhenkui; Schwingenschlögl, Udo, E-mail: Udo.Schwingenschlogl@kaust.edu.sa, E-mail: Iman.Roqan@kaust.edu.sa; Roqan, Iman S., E-mail: Udo.Schwingenschlogl@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)

2014-11-14

By means of density functional theory, we argue that ferromagnetism in GaN can be induced by vacancy complexes. Spin polarization originates from the charge compensation between neutral N and Ga vacancies. Defect formation energy calculations predict that a vacancy complex of two positively charged N vacancies and one doubly negative Ga vacancy is likely to form. This defect complex induces a net moment of 1 μ{sub B}, which is localized around the negative Ga center and exhibits pronounced in-plane ferromagnetic coupling. In contrast to simple Ga vacancy induced ferromagnetism, the proposed picture is in line with the fact that N vacancies have a low formation energy. Formation energies indicate mutual stabilization of the intrinsic defects in GaN.

Vacancy complexes induce long-range ferromagnetism in GaN

KAUST Repository

Zhang, Zhenkui; Schwingenschlö gl, Udo; Roqan, Iman S.

2014-01-01

By means of density functional theory, we argue that ferromagnetism in GaN can be induced by vacancy complexes. Spin polarization originates from the charge compensation between neutral N and Ga vacancies. Defect formation energy calculations predict that a vacancy complex of two positively charged N vacancies and one doubly negative Ga vacancy is likely to form. This defect complex induces a net moment of 1 μB, which is localized around the negative Ga center and exhibits pronounced in-plane ferromagnetic coupling. In contrast to simple Ga vacancy induced ferromagnetism, the proposed picture is in line with the fact that N vacancies have a low formation energy. Formation energies indicate mutual stabilization of the intrinsic defects in GaN.

Decrease of oxygen vacancy by Zn-doped for improving solar-blind photoelectric performance in β-Ga2O3 thin films

Science.gov (United States)

Guo, Daoyou; Qin, Xinyuan; Lv, Ming; Shi, Haoze; Su, Yuanli; Yao, Guosheng; Wang, Shunli; Li, Chaorong; Li, Peigang; Tang, Weihua

2017-11-01

Highly (201) oriented Zn-doped β-Ga2O3 thin films with different dopant concentrations were grown on (0001) sapphire substrates by radio frequency magnetron sputtering. With the increase of Zn dopant concentration, the crystal lattice expands, the energy band gap shrinks, and the oxygen vacancy concentration decreases. Both the metal semiconductor metal (MSM) structure photodetectors based on the pure and Zn-doped β-Ga2O3 thin films exhibit solar blind UV photoelectric property. Compared to the pure β-Ga2O3 photodetector, the Zn-doped one exhibits a lower dark current, a higher photo/dark current ratio, a faster photoresponse speed, which can be attributed to the decreases of oxygen vacancy concentration.[Figure not available: see fulltext.

A quantum-chemical study of oxygen-vacancy defects in PbTiO{sub 3} crystals

Energy Technology Data Exchange (ETDEWEB)

Stashans, Arvids [Laboratorio de Fisica, Escuela de Electronica y Telecomunicaciones, Universidad Tecnica Particular de Loja, Apartado 11-01-608, Loja (Ecuador)]. E-mail: arvids@utpl.edu.ec; Serrano, Sheyla [Centro de Investigacion en Fisica de Materia Condensada, Corporacion de Fisica Fundamental y Aplicada, Apartado 17-12-637, Quito (Ecuador); Escuela de Ingenierias, Universidad Politecnica Salesiana, Campus Sur, Rumichaca s/n y Moran Valverde, Apartado 17-12-536, Quito (Ecuador); Medina, Paul [Centro de Investigacion en Fisica de Materia Condensada, Corporacion de Fisica Fundamental y Aplicada, Apartado 17-12-637, Quito (Ecuador)

2006-05-31

Investigation of an oxygen vacancy and F center in the cubic and tetragonal lattices of PbTiO{sub 3} crystals is done by means of quantum-chemical simulations. Displacements of defect-surrounding atoms, electronic and optical properties, lattice relaxation energies and some new effects due to the defects presence are reported and analyzed. A comparison with similar studies is made and conclusions are drawn on the basis of the obtained results.

Vacancies in thermal equilibrium in Nb

International Nuclear Information System (INIS)

Nielsen, B.; Lynn, K.G.; Hurst, J.; Vehanen, A.; Schultz, P.J.

1985-06-01

We have measured the diffusion of positrons in Nb(110) in the temperature range from 300K to 2450K utilizing a variable energy positron beam. The purpose was to study the vacancy formation. However, no significant sign of vacancy trapping was observed. This could be due to a high detrapping rate caused by a low positron binding energy or due to a high vacancy formation enthalpy H/sub IV//sup F/. The last possibility is consistent with recent studies of the vacancy migration and with calculation of the positron binding energy. In this case we find the H/sub IV//sup F/ > 3 eV

Detection of oxygen vacancy defect states in capacitors with ultrathin Ta2O5 films by zero-bias thermally stimulated current spectroscopy

International Nuclear Information System (INIS)

Lau, W.S.; Leong, L.L.; Han, Taejoon; Sandler, Nathan P.

2003-01-01

Defect state D (0.8 eV) was experimentally detected in Ta 2 O 5 capacitors with ultrathin (physical thickness 2 O 5 films using zero-bias thermally stimulated current spectroscopy and correlated with leakage current. Defect state D can be more efficiently suppressed by using N 2 O rapid thermal annealing (RTA) instead of using O 2 RTA for postdeposition annealing and by using TiN instead of Al for top electrode. We believe that defect D is probably the first ionization level of the oxygen vacancy deep double donor. Other important defects are Si/O-vacancy complex single donors and C/O-vacancy complex single donors

A new method for determining the formation energy of a vacancy in concentrated alloys

International Nuclear Information System (INIS)

Kinoshita, C.; Kitajima, S.; Eguchi, T.

1978-01-01

The disadvantages in the conventional method which determines the formation energy of a vacancy in concentrated alloys from their kinetic behavior during annealing after quenching are pointed out, and an alternative method for overcoming these disadvantages is proposed. (Auth.)

Positron annihilation study of vacancy-type defects in fast-neutron-irradiated MgO·nAl{sub 2}O{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Rahman, Abu Zayed Mohammad Saliqur, E-mail: zayed82000@yahoo.com [Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, 19B Yuquanlu Shijingshan District, Beijing 100049 (China); Li, Zhuoxin; Cao, Xingzhong; Wang, Baoyi; Wei, Long [Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, 19B Yuquanlu Shijingshan District, Beijing 100049 (China); Xu, Qiu [Reactor Research Institute, Kyoto University 2, Asashiro-Nishi, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Atobe, Kozo [Nuclear Safety Technology Center, 9-15, 1-chome, Utsubohonmachi, Nishi Ku, Osaka 550-0004 (Japan)

2014-09-15

Highlights: •Detection of Al monovacancy by positron lifetime spectroscopy in fast neutron-irradiated MgO·nAl{sub 2}O{sub 3}(n=2). •Concentration of defects is also estimated for Al monovacancy. •O atom peak was observed by using coincidence Doppler broadening spectroscopy. -- Abstract: The positron lifetimes of fast-neutron-irradiated MgO·nAl{sub 2}O{sub 3} single crystals were measured to investigate the formation of cation vacancies. Al monovacancy was possibly observed in samples irradiated by fast neutrons at ultra-low temperatures. Additionally, vacancy-oxygen complex centers were possibly observed in samples irradiated at higher temperatures and fast neutron fluences. Coincidence Doppler broadening (CDB) spectra were measured to obtain information regarding the vicinity of vacancy-type defects. A peak at approximately 11 × 10{sup −3} m{sub 0}c was observed, which may be due to the presence of oxygen atoms in the neighborhood of the vacancies.

Positron lifetime in vacancy clusters. Application to the study of vacancy-impurity interactions

International Nuclear Information System (INIS)

Corbel, C.

1986-02-01

Positron lifetime measurements are used to study the vacancy recovery (77-650 K) in 20 K electron irradiated dilute gold or iron alloys in stainless steels. Positron lifetimes in clusters of various shapes and structures are calculated to precise the information obtained by measuring the positron lifetime in a vacancy cluster of unknown size and configuration. From the calculations, we have drawn the following conclusions: - the minimal size of an unknown cluster can be deduced from the measurement of the positron lifetime in the cluster; - a decrease of the positron lifetime when the structure of the cluster evolves, means either a decrease of the size of the cluster, or, the appearance of a relaxed configuration. - The positron lifetime is very useful to discriminate between a spatial planar or relaxed configuration and a tri-dimensional one. In AuGe, AuSb, AuTn alloys, vacancy clusters decorated by solute atoms appear at 250 K. Their configurations are different from those in pure Au. Mobile vacancy-solutes complexes are involved in the clustering process in AuGe, AuSb. The clusters are probably decorated by several solute atoms in AuGe and AuSb where the resistivity evidences a clustering of solute atoms. In AuFe, vacancy-single or multi-complexes stable up to 670 K prevent cluster formation. In FeTi, FeSb, FeAu, vacancy migration is hindered by the formation of vacancy-solute complexes up to 315 K (Ti), up to 670 K (Sb), up to 700 K (Au). In FeSi, FeCu, FeAg, tri-dimensional clusters grow less easily than Fe. This is likely due to the formation of several kinds of small decorated clusters with relaxed or planar configurations. They are peculiarly stable, surviving up to 700 K at least. In Si (resp. Ti) doped 59Fe25Ni16Cr, solute atoms retain the vacancies up to 300 K (resp. 320 K) [fr

Effect of oxygen vacancy and dopant concentration on the magnetic properties of high spin Co2+ doped TiO2 nanoparticles

International Nuclear Information System (INIS)

Choudhury, B.; Choudhury, A.; Maidul Islam, A.K.M.; Alagarsamy, P.; Mukherjee, M.

2011-01-01

Co doped TiO 2 nanoparticles have been synthesized by a simple sol-gel route taking 7.5, 9.5 and 10.5 mol% of cobalt concentration. Formation of nanoparticles is confirmed by XRD and TEM. Increase in d-spacing occurs for (0 0 4) and (2 0 0) peak with increase in impurity content. Valence states of Co and its presence in the doped material is confirmed by XPS and EDX. The entire vacuum annealed samples show weak ferromagnetism. Increased magnetization is found for 9.5 mol% but this value again decreases for 10.5 mol% due to antiferromagnetic interactions. A blocking temperature of 37.9 K is obtained, which shows shifting to high temperature as the dopant concentration is increased. The air annealed sample shows only paramagnetic behavior. Temperature dependent magnetic measurements for the air annealed sample shows antiferromagnetic behavior with a Curie-Weiss temperature of -16 K. Here we report that oxygen vacancy and cobalt aggregates are a key factor for inducing ferromagnetism-superparamagnetism in the vacuum annealed sample. Appearance of negative Curie-Weiss temperature reveals the presence of antiferromagnetic Co 3 O 4 , which is the oxidation result of metallic Co or cobalt clusters present on the host TiO 2 . - Research highlights: → Oxygen vacancy induces ferromagnetism in cobalt doped anatase TiO2 nanoparticles. → On air annealing the sample loses ferromagnetism giving rise to paramagnetism. → Saturation magnetization decreases at higher doping concentration. → Blocking of magnetic moment occurs due to the presence of cobalt clusters.

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

International Nuclear Information System (INIS)

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.

Charge doping and large lattice expansion in oxygen-deficient heteroepitaxial WO3

Science.gov (United States)

Mattoni, Giordano; Filippetti, Alessio; Manca, Nicola; Zubko, Pavlo; Caviglia, Andrea D.

2018-05-01

Tungsten trioxide (WO3) is a versatile material with widespread applications ranging from electrochromics and optoelectronics to water splitting and catalysis of chemical reactions. For technological applications, thin films of WO3 are particularly appealing, taking advantage from a high surface-to-volume ratio and tunable physical properties. However, the growth of stoichiometric crystalline thin films is challenging because the deposition conditions are very sensitive to the formation of oxygen vacancies. In this paper, we show how background oxygen pressure during pulsed laser deposition can be used to tune the structural and electronic properties of WO3 thin films. By performing x-ray diffraction and low-temperature electrical transport measurements, we find changes in the WO3 lattice volume of up to 10% concomitantly with a resistivity drop of more than five orders of magnitude at room temperature as a function of increased oxygen deficiency. We use advanced ab initio calculations to describe in detail the properties of the oxygen vacancy defect states and their evolution in terms of excess charge concentration. Our results depict an intriguing scenario where structural, electronic, optical, and transport properties of WO3 single-crystal thin films can all be purposely tuned by controlling the oxygen vacancy formation during growth.

Migration mechanisms and diffusion barriers of vacancies in Ga2O3

Science.gov (United States)

Kyrtsos, Alexandros; Matsubara, Masahiko; Bellotti, Enrico

2017-06-01

We employ the nudged elastic band and the dimer methods within the standard density functional theory (DFT) formalism to study the migration of the oxygen and gallium vacancies in the monoclinic structure of β -Ga2O3 . We identify all the first nearest neighbor paths and calculate the migration barriers for the diffusion of the oxygen and gallium vacancies. We also identify the metastable sites of the gallium vacancies which are critical for the diffusion of the gallium atoms. The migration barriers for the diffusion of the gallium vacancies are lower than the migration barriers for oxygen vacancies by 1 eV on average, suggesting that the gallium vacancies are mobile at lower temperatures. Using the calculated migration barriers we estimate the annealing temperature of these defects within the harmonic transition state theory formalism, finding excellent agreement with the observed experimental annealing temperatures. Finally, we suggest the existence of percolation paths which enable the migration of the species without utilizing all the migration paths of the crystal.

An Unusual Strong Visible-Light Absorption Band in Red Anatase TiO2 Photocatalyst Induced by Atomic Hydrogen-Occupied Oxygen Vacancies.

Science.gov (United States)

Yang, Yongqiang; Yin, Li-Chang; Gong, Yue; Niu, Ping; Wang, Jian-Qiang; Gu, Lin; Chen, Xingqiu; Liu, Gang; Wang, Lianzhou; Cheng, Hui-Ming

2018-02-01

Increasing visible light absorption of classic wide-bandgap photocatalysts like TiO 2 has long been pursued in order to promote solar energy conversion. Modulating the composition and/or stoichiometry of these photocatalysts is essential to narrow their bandgap for a strong visible-light absorption band. However, the bands obtained so far normally suffer from a low absorbance and/or narrow range. Herein, in contrast to the common tail-like absorption band in hydrogen-free oxygen-deficient TiO 2 , an unusual strong absorption band spanning the full spectrum of visible light is achieved in anatase TiO 2 by intentionally introducing atomic hydrogen-mediated oxygen vacancies. Combining experimental characterizations with theoretical calculations reveals the excitation of a new subvalence band associated with atomic hydrogen filled oxygen vacancies as the origin of such band, which subsequently leads to active photo-electrochemical water oxidation under visible light. These findings could provide a powerful way of tailoring wide-bandgap semiconductors to fully capture solar light. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Breakdown of the Arrhenius Law in Describing Vacancy Formation Energies: The Importance of Local Anharmonicity Revealed by Ab initio Thermodynamics

Directory of Open Access Journals (Sweden)

A. Glensk

2014-02-01

Full Text Available We study the temperature dependence of the Gibbs energy of vacancy formation in Al and Cu from T=0  K up to the melting temperature, fully taking into account anharmonic contributions. Our results show that the formation entropy of vacancies is not constant as often assumed but increases almost linearly with temperature. The resulting highly nonlinear temperature dependence in the Gibbs formation energy naturally explains the differences between positron annihilation spectroscopy and differential dilatometry data and shows that nonlinear thermal corrections are crucial to extrapolate high-temperature experimental data to T=0  K. Employing these corrections—rather than the linear Arrhenius extrapolation that is commonly assumed in analyzing experimental data—revised formation enthalpies are obtained that differ up to 20% from the previously accepted ones. Using the revised experimental formation enthalpies, we show that a large part of the discrepancies between DFT-GGA and unrevised experimental vacancy formation energies disappears. The substantial shift between previously accepted and the newly revised T=0  K formation enthalpies also has severe consequences in benchmarking ab initio methods against experiments, e.g., in deriving corrections that go beyond commonly used LDA and GGA exchange-correlation functionals such as the AM05 functional.

Oxygen vacancy induced two-dimensional electron system in disordered-crystalline LaAlO{sub 3}/KTaO{sub 3} heterostructures

Energy Technology Data Exchange (ETDEWEB)

Zapf, Michael; Gabel, Judith; Scheiderer, Philipp; Dudy, Lenart; Sing, Michael; Claessen, Ralph [Physikalisches Institut and Roentgen Center for Complex Material Systems (RCCM), Universitaet Wuerzburg (Germany); Schlueter, Christoph; Lee, Tien-Lin [Diamond Light Source Ltd., Didcot (United Kingdom)

2016-07-01

Two-dimensional electron systems (2DESs) in oxide heterostructures based on SrTiO{sub 3} are considered to be a promising platform for future microelectronic technology. A variety of interesting properties such as ferromagnetism, resistive switching and superconductivity are linked to interfacial n-doping involving oxygen vacancies. The introduction of a high Z-cation with large spin-orbit coupling like Ta offers an exciting new parameter. We report on a new oxygen vacancy induced 2DES located at the interface of disordered LaAlO{sub 3} and crystalline KTaO{sub 3}, which exhibits remarkably high electron mobilities and charge carrier concentrations. The number of charge carriers can be readily manipulated by the film thickness and irradiation with intense X-rays. Our synchrotron-based hard X-ray photoemission experiments provide a direct probe of the Ta 5d charge carriers at the buried interface to obtain information on the charge carrier density, its depth distribution, and the band structure.

Vacancy ordering and superstructure formation in dry and hydrated strontium tantalate perovskites: A TEM perspective

DEFF Research Database (Denmark)

Ashok, Anuradha M.; Haavik, Camilla; Norby, Poul

2014-01-01

Crystal structures of Sr4(Sr2Ta2)O11 and Sr4(Sr1.92Ta2.08)O11.12, synthesized by solid state reaction technique in dry and hydrated state have been studied mainly using Transmission Electron Microscopy. Due to the lesser ability of X-rays to probe details in oxygen sublattice, the change in crystal...... and corresponding unit cells of all the perovskites based on the ordering of oxygen vacancies is deduced. Crystal unit cells based on the observations are proposed with ideal atomic coordinates. Finally an attempt is made to explain the water uptake behaviour of these perovskites based on the proposed crystal...

High-performance gas sensing achieved by mesoporous tungsten oxide mesocrystals with increased oxygen vacancies

KAUST Repository

Wang, Dong

2013-01-01

The inner structure of W18O49 mesocrystals was observed by electron microscopy with the help of ultramicrotomy and focused ion beam techniques. The results showed that these mesocrystals contain irregular mesopores formed through partial fusion of self-assembled nanowires, and consequently have long-range structural ordering in one dimension and short-range ordering in the other two dimensions. The W18O 49 mesocrystals exhibit superior performance in gas sensing applications, which is considered to be associated with the presence of more oxygen vacancy sites in the unique mesoporous structure. © 2013 The Royal Society of Chemistry.

Surface oxygen vacancy and oxygen permeation flux limits of perovskite ion transport membranes

KAUST Repository

Hunt, Anton

2015-09-01

© 2015 Elsevier B.V. The mechanisms and quantitative models for how oxygen is separated from air using ion transport membranes (ITMs) are not well understood, largely due to the experimental complexity for determining surface exchange reactions at extreme temperatures (>800°C). This is especially true when fuels are present at the permeate surface. For both inert and reactive (fuels) operations, solid-state oxygen surface vacancies (δ) are ultimately responsible for driving the oxygen flux, JO2. In the inert case, the value of δ at either surface is a function of the local PO2 and temperature, whilst the magnitude of δ dictates both the JO2 and the inherent stability of the material. In this study values of δ are presented based on experimental measurements under inert (CO2) sweep: using a permeation flux model and local PO2 measurements, collected by means of a local gas-sampling probe in our large-scale reactor, we can determine δ directly. The ITM assessed was La0.9Ca0.1FeO3-δ (LCF); the relative resistances to JO2 were quantified using the pre-defined permeation flux model and local PO2 values. Across a temperature range from 825°C to 1056°C, δ was found to vary from 0.007 to 0.029 (<1%), safely within material stability limits, whilst the permeate surface exchange resistance dominates. An inert JO2 limit was identified owing to a maximum sweep surface δ, δmaxinert. The physical presence of δmaxinert is attributed to a rate limiting step shift from desorption to associative electron transfer steps on the sweep surface as PO2 is reduced. Permeate surface exchange limitations under non-reactive conditions suggest that reactive (fuel) operation is necessary to accelerate surface chemistry for future work, to reduce flux resistance and push δpast δmaxinert in a stable manner.

Vacancy formation enthalpies in bcc and fcc FeCo by positron annihilation

International Nuclear Information System (INIS)

Jackman, J.A.; Kim, S.M.; Buyers, W.J.L.

1982-01-01

A long slit angular correlation apparatus was used to measure the peak coincidence count rate in stoichiometric FeCo from 290 K to 1510 K. The count rate did not change significantly at the order-disorder phase transition (1008 K), but decreased sharply by 3.2% at the bcc-fcc phase transition at 1258 K. The threshold temperatures for the trapping of positrons in vacancies are measured to be 1125 K for the bcc phase and 1260 K for the fcc phase. The vacancy formation enthalpies in the bcc and fcc phases are determined to be 1.45 +- 0.05 eV and 1.63 +- 0.05 eV. The activation energies for self-diffusion have been estimated from the threshold temperatures, and are found to be 2.45 eV and 2.74 eV for the bcc and fcc phases respectively. (Auth.)

Oxygen vacancy rich Cu2O based composite material with nitrogen doped carbon as matrix for photocatalytic H2 production and organic pollutant removal.

Science.gov (United States)

Lu, Lele; Xu, Xinxin; Yan, Jiaming; Shi, Fa-Nian; Huo, Yuqiu

2018-02-06

A nitrogen doped carbon matrix supported Cu 2 O composite material (Cu/Cu2O@NC) was fabricated successfully with a coordination polymer as precursor through calcination. In this composite material, Cu 2 O particles with a size of about 6-10 nm were dispersed evenly in the nitrogen doped carbon matrix. After calcination, some coordinated nitrogen atoms were doped in the lattice of Cu 2 O and replace oxygen atoms, thus generating a large number of oxygen vacancies. In Cu/Cu2O@NC, the existence of oxygen vacancies has been confirmed by electron spin resonance (ESR) and X-ray photoelectron spectroscopy (XPS). Under visible light irradiation, Cu/Cu2O@NC exhibits excellent H 2 production with the rate of 379.6 μmol h -1 g -1 . Its photocatalytic activity affects organic dyes, such as Rhodamine B (RhB) and methyl orange (MO). In addition to photocatalysis, Cu/Cu2O@NC also exhibits striking catalytic activity in reductive conversion of 4-nitrophenol to 4-aminophenol with in presence of sodium borohydride (NaBH 4 ). The conversion efficiency reaches almost 100% in 250 s with the quantity of Cu/Cu2O@NC as low as 5 mg. The outstanding H 2 production and organic pollutants removal are attributed to the oxygen vacancy. We expect that Cu/Cu2O@NC will find its way as a new resource for hydrogen energy as well as a promising material in water purification.

Formation of hydrogen-related traps in electron-irradiated n-type silicon by wet chemical etching

International Nuclear Information System (INIS)

Tokuda, Yutaka; Shimada, Hitoshi

1998-01-01

Interaction of hydrogen atoms and vacancy-related defects in 10 MeV electron-irradiated n-type silicon has been studied by deep-level transient spectroscopy. Hydrogen has been incorporated into electron-irradiated n-type silicon by wet chemical etching. The reduction of the concentration of the vacancy-oxygen pair and divacancy occurs by the incorporation of hydrogen, while the formation of the NH1 electron trap (E c - 0.31 eV) is observed. Further decrease of the concentration of the vacancy-oxygen pair and further increase of the concentration of the NH1 trap are observed upon subsequent below-band-gap light illumination. It is suggested that the trap NH1 is tentatively ascribed to the vacancy-oxygen pair which is partly saturated with hydrogen

Manipulating multiple order parameters via oxygen vacancies: The case of E u0.5B a0.5Ti O3 -δ

Science.gov (United States)

Li, Weiwei; He, Qian; Wang, Le; Zeng, Huizhong; Bowlan, John; Ling, Langsheng; Yarotski, Dmitry A.; Zhang, Wenrui; Zhao, Run; Dai, Jiahong; Gu, Junxing; Shen, Shipeng; Guo, Haizhong; Pi, Li; Wang, Haiyan; Wang, Yongqiang; Velasco-Davalos, Ivan A.; Wu, Yangjiang; Hu, Zhijun; Chen, Bin; Li, Run-Wei; Sun, Young; Jin, Kuijuan; Zhang, Yuheng; Chen, Hou-Tong; Ju, Sheng; Ruediger, Andreas; Shi, Daning; Borisevich, Albina Y.; Yang, Hao

2017-09-01

Controlling functionalities, such as magnetism or ferroelectricity, by means of oxygen vacancies (VO) is a key issue for the future development of transition-metal oxides. Progress in this field is currently addressed through VO variations and their impact on mainly one order parameter. Here we reveal a mechanism for tuning both magnetism and ferroelectricity simultaneously by using VO. Combining experimental and density-functional theory studies of E u0.5B a0.5Ti O3 -δ , we demonstrate that oxygen vacancies create T i3 +3 d1 defect states, mediating the ferromagnetic coupling between the localized Eu 4 f7 spins, and increase an off-center displacement of Ti ions, enhancing the ferroelectric Curie temperature. The dual function of Ti sites also promises a magnetoelectric coupling in the E u0.5B a0.5Ti O3 -δ .

Role of vacancy defects in Al doped ZnO thin films for optoelectronic devices

Science.gov (United States)

Rotella, H.; Mazel, Y.; Brochen, S.; Valla, A.; Pautrat, A.; Licitra, C.; Rochat, N.; Sabbione, C.; Rodriguez, G.; Nolot, E.

2017-12-01

We report on the electrical, optical and photoluminescence properties of industry-ready Al doped ZnO thin films grown by physical vapor deposition, and their evolution after annealing under vacuum. Doping ZnO with Al atoms increases the carrier density but also favors the formation of Zn vacancies, thereby inducing a saturation of the conductivity mechanism at high aluminum content. The electrical and optical properties of these thin layered materials are both improved by annealing process which creates oxygen vacancies that releases charge carriers thus improving the conductivity. This study underlines the effect of the formation of extrinsic and intrinsic defects in Al doped ZnO compound during the fabrication process. The quality and the optoelectronic response of the produced films are increased (up to 1.52 mΩ \\cdotcm and 3.73 eV) and consistent with the industrial device requirements.

Vacancies and defect levels in III–V semiconductors

KAUST Repository

Tahini, H. A.

2013-08-13

Using electronic structure calculations, we systematically investigate the formation of vacancies in III-V semiconductors (III = Al, Ga, and In and V = P, As, and Sb), for a range of charges ( −3≤q≤3 ) as a function of the Fermi level and under different growth conditions. The formation energies were corrected using the scheme due to Freysoldt et al. [Phys. Rev. Lett. 102, 016402 (2009)] to account for finite size effects. Vacancy formation energies were found to decrease as the size of the group V atom increased. This trend was maintained for Al-V, Ga-V, and In-V compounds. The negative-U effect was only observed for the arsenic vacancy in GaAs, which makes a charge state transition from +1 to –1. It is also found that even under group III rich conditions, group III vacancies dominate in AlSb and GaSb. For InSb, group V vacancies are favoured even under group V rich conditions.

Vacancies and defect levels in III–V semiconductors

KAUST Repository

Tahini, H. A.; Chroneos, Alexander; Grimes, R. W.; Murphy, S. T.; Schwingenschlö gl, Udo

2013-01-01

Using electronic structure calculations, we systematically investigate the formation of vacancies in III-V semiconductors (III = Al, Ga, and In and V = P, As, and Sb), for a range of charges ( −3≤q≤3 ) as a function of the Fermi level and under different growth conditions. The formation energies were corrected using the scheme due to Freysoldt et al. [Phys. Rev. Lett. 102, 016402 (2009)] to account for finite size effects. Vacancy formation energies were found to decrease as the size of the group V atom increased. This trend was maintained for Al-V, Ga-V, and In-V compounds. The negative-U effect was only observed for the arsenic vacancy in GaAs, which makes a charge state transition from +1 to –1. It is also found that even under group III rich conditions, group III vacancies dominate in AlSb and GaSb. For InSb, group V vacancies are favoured even under group V rich conditions.

Oxygen vacancies at the spinel/perovskite γ-Al{sub 2}O{sub 3}/SrTiO{sub 3} heterointerface probed by resonant photoelectron spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Schuetz, Philipp; Pfaff, Florian; Zapf, Michael; Gabel, Judith; Dudy, Lenart; Berner, Goetz; Sing, Michael; Claessen, Ralph [Physikalisches Institut and Roentgen Center for Complex Material Systems (RCCM), Universitaet Wuerzburg (Germany); Chen, Yunzhong; Pryds, Nini [Department of Energy Conversion and Storage, Technical University of Denmark, Risoe (Denmark); Schlueter, Christoph; Lee, Tien-Lin [Diamond Light Source Ltd., Harwell Science and Innovation Campus, Didcot (United Kingdom)

2016-07-01

The spinel/perovskite heterointerface between the band insulators γ-Al{sub 2}O{sub 3} and SrTiO{sub 3} hosts a two-dimensional electron system (2DES) with exceptionally high electron mobility. Soft x-ray resonant photoelectron spectroscopy at the Ti L absorption edge is used to probe the Ti 3d derived interface states. Marked differences in the resonance behavior are found for the SrTiO{sub 3} valence band and the different interface states, which are observed in the band gap of SrTiO{sub 3}. A comparison to X-ray absorption spectra of Ti 3d{sup 0} and Ti 3d{sup 1} systems reveals the presence of different types of electronic states with Ti 3d character, i.e., oxygen vacancy induced, trapped in-gap states and itinerant states contributing to the 2DES. Exposure to low doses of oxygen during irradiation allows for the reversible manipulation of the oxygen stoichiometry, thus revealing the presence of an oxygen vacancy-induced state, which is characteristic for this spinel/perovskite interface.

Changes in the vibrational energies and interatomic spacings upon the formation of vacancies in the volume and in the cores of crystallite conjugation regions of polycrystalline transition metals with cubic lattices

International Nuclear Information System (INIS)

Klotsman, S.M.; Timofeev, A.N.

2008-01-01

Measured changes (ε vac ) i,j of vibrational energy on vacancies formation in i-fields (in volumes and nuclei of crystallite conjugation regions of polycrystalline metals (CCR-PM)): Cr, Mo, Ta, W, Cu, Ir are presented. Changes ε vol of vibrational energy of vacancy nearest environment formed in the metal volume, changes ε FCC of vibrational energy when vacancies formation in CCR nuclei of BCC- and FCC lattices transition metals are discussed. Measured changes ε FCC of vibrational energy, u FCC potential energy and determined sign of interatomic distances changes Δa FCC when formation of split vacancy in the FCC-lattice CCR-PM, changes ε BCC of vibrational energy, u BCC potential energy and determined sign of Δa BCC changes of interatomic distances when vacancies formation in the BCC-lattice CCR-PM are demonstrated. It is noted that the increase of interatomic distances when vacancies formation in the BCC-lattice CCR nucleus of transition metals is conditioned by the the appearance of vacancies alternative structure. Properties of CCR-PM nuclei are more sensitive to interatomic distances changes in the vacancies environment, than to changes of its nearest neighbours numbers [ru

Pre-transitional effects for vacancy formation and mobility in bcc 3He

International Nuclear Information System (INIS)

Chapellier, M.; Bassou, M.; Devoret, M.; Delrieu, J.M.; Sullivan, N.S.

1983-01-01

The mobility μ proportional to exp(a/xi). This conclusion would be different if one allows for an entropy of formation S(V/sub m/) for the vacancies. NMR measures μ exp(H(V/sub m/)/k/sub B/T) where the enthalpy H(V/sub m/) = Phi(V/sub m/) - TS(V/sub m/) and the T-independent factor is μ exp S(V/sub m/) and not simply μ. The striking V-dependence observed for this factor (4 decades for 23.0 3 /mole) could also be understood in terms of an increase in the entropy of formation on approaching V/sub m//sup max/. 4 references

Effect of calcination routes on phase formation of BaTiO3 and their electronic and magnetic properties

Science.gov (United States)

Majumder, Supriyo; Choudhary, R. J.; Tripathi, M.; Phase, D. M.

2018-05-01

We have investigated the phase formation and correlation between electronic and magnetic properties of oxygen deficient BaTiO3 ceramics, synthesized by solid state reaction method, following different calcination paths. The phase analysis divulge that a higher calcination temperature above 1000° C is favored for tetragonal phase formation than the cubic phase. The core level X-ray photo electron spectroscopy measurements confirm the presence of oxygen vacancies and oxygen vacancy mediated Ti3+ states. As the calcination temperature and calcination time increases these oxygen vacancies and hence Ti3+ concentrations reduce in the sample. The temperature dependent magnetization curves suggest unexpected magnetic ordering, which may be due to the presence of unpaired electron at the t2g state (d1) of nearest-neighbor Ti atoms. In magnetization vs magnetic field isotherms, the regular decrease of saturation moment value with increasing calcination temperature and calcination time, can be discussed considering the amount of oxygen deficiency induced Ti3+ concentrations, present in the sample.

Stress dependence of oxygen diffusion in ZrO2 film

International Nuclear Information System (INIS)

Yamamoto, Yasunori; Morishita, Kazunori; Iwakiri, Hirotomo; Kaneta, Yasunori

2013-01-01

First principles calculations were performed to evaluate the effect of stress on the diffusion process of oxygen atoms in monoclinic and tetragonal ZrO 2 . The formation and migration energies of an oxygen vacancy were obtained as a function of applied stress. Our results show that the formation and migration energies increase when the compressive stress is applied, which causes a reduction in the diffusion coefficient of an oxygen atom in ZrO 2 . This may explain the experimental observation that the oxide film grows in proportion to the cubic root of time

Vacancies in transition metals

International Nuclear Information System (INIS)

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)

O vacancy formation in (Pr/Gd)BaCo2O5.5 and the role of antisite defects

KAUST Repository

Omotayo Akande, Salawu; Chroneos, Alexander; Schwingenschlö gl, Udo

2017-01-01

that O vacancy formation is significantly easier in PrBaCo2O5.5 than in GdBaCo2O5.5, the difference in formation energy being hardly modified by antisite defects. While pyramidally coordinated Co atoms are not affected, we show that the presence

Stress dependence of oxygen diffusion in ZrO{sub 2} film

Energy Technology Data Exchange (ETDEWEB)

Yamamoto, Yasunori, E-mail: yasu-yamamoto@iae.kyoto-u.ac.jp [Graduate School of Energy Science, Kyoto University, Uji, Kyoto 611-0011 (Japan); Morishita, Kazunori [Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011 (Japan); Iwakiri, Hirotomo [Faculty of Education, University of the Ryukyus, Nakagami-gun, Okinawa 903-0213 (Japan); Kaneta, Yasunori [Akita National College of Technology, Akita, Akita 011-8511 (Japan)

2013-05-15

First principles calculations were performed to evaluate the effect of stress on the diffusion process of oxygen atoms in monoclinic and tetragonal ZrO{sub 2}. The formation and migration energies of an oxygen vacancy were obtained as a function of applied stress. Our results show that the formation and migration energies increase when the compressive stress is applied, which causes a reduction in the diffusion coefficient of an oxygen atom in ZrO{sub 2}. This may explain the experimental observation that the oxide film grows in proportion to the cubic root of time.

Positron annihilation studies on the behaviour of vacancies in LaAlO3/SrTiO3 heterostructures

Science.gov (United States)

Yuan, Guoliang; Li, Chen; Yin, Jiang; Liu, Zhiguo; Wu, Di; Uedono, Akira

2012-11-01

The formation and diffusion of vacancies are studied in LaAlO3/SrTiO3 heterostructures. Oxygen vacancies (VOS) appear easily in the SrTiO3 substrate during LaAlO3 film growth at 700 °C and 10-4 Pa oxygen pressure rather than at 10-3-10-1 Pa, thus the latter two-dimensional electron gas should come from the polarity discontinuity at the (LaO)+/(TiO2)0 interface. For SrTiO3-δ/LaAlO3/SrTiO3, high-density VOS of the SrTiO3-δ film can pass through the LaAlO3 film and then diffuse to 1.7 µm depth in the SrTiO3 substrate, suggesting that LaAlO3 has VOS at its middle-deep energy levels within the band gap. Moreover, high-density VOS may combine with a strontium/titanium vacancy (VSr/Ti) to form VSr/Ti-O complexes in the SrTiO3 substrate at 700 °C.

Oxygen vacancy induces self-doping effect and metalloid LSPR in non-stoichiometric tungsten suboxide synergistically contributing to the enhanced photoelectrocatalytic performance of WO3-x/TiO2-x heterojunction.

Science.gov (United States)

Huang, Weicheng; Wang, Jinxin; Bian, Lang; Zhao, Chaoyue; Liu, Danqing; Guo, Chongshen; Yang, Bin; Cao, Wenwu

2018-06-27

A WO3-x/TiO2-x nanotube array (NTA) heterojunction photoanode was strategically designed to improve photoelectrocatalytic (PEC) performance by establishing a synergistic vacancy-induced self-doping effect and localized surface plasmon resonance (LSPR) effect of metalloid non-stoichiometric tungsten suboxide. The WO3-x/TiO2-x NTA heterojunction photoanode was synthesized through a successive process of anodic oxidation to form TiO2 nanotube arrays, magnetron sputtering to deposit metalloid WO3-x, and post-hydrogen reduction to engender oxygen vacancy in TiO2-x as well as crystallization. On the merits of such a synergistic effect, WO3-x/TiO2-x shows higher light-harvesting ability, stronger photocurrent response, and resultant improved photoelectrocatalytic performance than the contrast of WO3-x/TiO2, WO3/TiO2 and TiO2, confirming the importance of oxygen vacancies in improving PEC performance. Theoretical calculation based on density functional theory was applied to investigate the electronic structural features of samples and reveal how the oxygen vacancy determines the optical property. The carrier density tuning mechanism and charge transfer model were considered to be associated with the synergistic effect of self-doping and metalloid LSPR effect in the WO3-x/TiO2-x NTA.

Mixed oxygen ion/electron-conducting ceramics for oxygen separation

Energy Technology Data Exchange (ETDEWEB)

Stevenson, J.W.; Armstrong, T.R.; Armstrong, B.L. [Pacific Northwest National Lab., Richland, WA (United States)

1996-08-01

Mixed oxygen ion and electron-conducting ceramics are unique materials that can passively separate high purity oxygen from air. Oxygen ions move through a fully dense ceramic in response to an oxygen concentration gradient, charge-compensated by an electron flux in the opposite direction. Compositions in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, perovskites where M=Sr, Ca, and Ba, and N=Mn, Ni, Cu, Ti, and Al, have been prepared and their electrical, oxygen permeation, oxygen vacancy equilibria, and catalytic properties evaluated. Tubular forms, disks, and asymmetric membrane structures, a thin dense layer on a porous support of the same composition, have been fabricated for testing purposes. In an oxygen partial gradient, the passive oxygen flux through fully dense structures was highly dependent on composition. An increase in oxygen permeation with increased temperature is attributed to both enhanced oxygen vacancy mobility and higher vacancy populations. Highly acceptor-doped compositions resulted in oxygen ion mobilities more than an order of magnitude higher than yttria-stabilized zirconia. The mixed conducting ceramics have been utilized in a membrane reactor configuration to upgrade methane to ethane and ethylene. Conditions were established to balance selectivity and throughput in a catalytic membrane reactor constructed from mixed conducting ceramics.

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

Energy Technology Data Exchange (ETDEWEB)

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

Thermodynamic, electronic, and magnetic properties of intrinsic vacancy defects in antiperovskite Ca3SnO

Science.gov (United States)

Batool, Javaria; Alay-e-Abbas, Syed Muhammad; Amin, Nasir

2018-04-01

The density functional theory based total energy calculations are performed to examine the effect of charge neutral and fully charged intrinsic vacancy defects on the thermodynamic, electronic, and magnetic properties of Ca3SnO antiperovskite. The chemical stability of Ca3SnO is evaluated with respect to binary compounds CaO, CaSn, and Ca2Sn, and the limits of atomic chemical potentials of Ca, Sn, and O atoms for stable synthesis of Ca3SnO are determined within the generalized gradient approximation parametrization scheme. The electronic properties of the pristine and the non-stoichiometric forms of this compound have been explored and the influence of isolated intrinsic vacancy defects (Ca, Sn, and O) on the structural, bonding, and electronic properties of non-stoichiometric Ca3SnO are analyzed. We also predict the possibility of achieving stable ferromagnetism in non-stoichiometric Ca3SnO by means of charge neutral tin vacancies. From the calculated total energies and the valid ranges of atomic chemical potentials, the formation energetics of intrinsic vacancy defects in Ca3SnO are evaluated for various growth conditions. Our results indicate that the fully charged calcium vacancies are thermodynamically stable under the permissible Sn-rich condition of stable synthesis of Ca3SnO, while tin and oxygen vacancies are found to be stable under the extreme Ca-rich condition.

Oxygen vacancy induced fast lithium storage and efficient organics photodegradation over ultrathin TiO{sub 2} nanolayers grafted graphene sheets

Energy Technology Data Exchange (ETDEWEB)

Xie, Yu, E-mail: xieyu_121@163.com [Nanchang Hangkong University, Department of Material Chemistry, Nanchang, Jiangxi Province (China); Hu, Dongsheng [Nanchang Hangkong University, Department of Material Chemistry, Nanchang, Jiangxi Province (China); Liu, Lianjun, E-mail: liul@uwm.edu [University of Wisconsin-Milwaukee, Mechanical Engineering Department, Milwaukee, WI (United States); Zhou, Panpan; Xu, Jiangwei; Ling, Yun [Nanchang Hangkong University, Department of Material Chemistry, Nanchang, Jiangxi Province (China)

2016-11-15

Highlights: • Oxygen vacancy is tailored by adjusting the treatment conditions. • Unltrathin TiO{sub 2} nanolayers are grafted on the graphene sheets. • Oxygen vacancy is located on the surface of TiO{sub 2}/graphene treated by H{sub 2}. • Improved lithium storage and organic pollutants removal efficiency. - Abstract: In this work we have developed a unique structure of ultrathin (5 nm) TiO{sub 2} nanolayers grafted graphene nanosheets (TiO{sub 2}/G) and integrated oxygen vacancy (V{sub O}) into TiO{sub 2} to enhance its lithium storage and photocatalytic performances. The defective TiO{sub 2}/G was synthesized by a solvothermal and subsequent thermal treatment method. When treated in a H{sub 2} atmosphere, the resulting TiO{sub 2-x}/G(H{sub 2}) has lower crystallinity, smaller crystal size, richer surface V{sub O}, higher surface area, larger pore volume, and lower charge transfer resistance than that reduced by NaBH{sub 4} solid, i.e., TiO{sub 2-x}/G(NaBH{sub 4}). More importantly, the surface V{sub O} in the TiO{sub 2-x}/G(H{sub 2}) could remarkably inhibit the recombination of photogenerated electron-hole pairs compared with the bulk Vo in the TiO{sub 2-x}/G(NaBH{sub 4}). As a result, the combination of all the factors contributed to the superiority of TiO{sub 2-x}/G(H{sub 2}), which demonstrated not only 70% higher specific capacity, longer cycling performance (1000 cycles) and better rate capability for lithium-ion battery, but also higher photocatalytic activity and 1.5 times faster degradation rate for organic pollutants removal than TiO{sub 2-x}/G(NaBH{sub 4}). The findings in this work will benefit the fundamental understanding of TiO{sub 2}/G surface chemistry and advance the design and preparation of functional materials for energy storage and water treatment.

Pre-transitional effects for vacancy formation and mobility in bcc /sup 3/He

Energy Technology Data Exchange (ETDEWEB)

Chapellier, M.; Bassou, M.; Devoret, M.; Delrieu, J.M.; Sullivan, N.S.

1983-01-01

The mobility ..mu.. proportional to exp(a/xi). This conclusion would be different if one allows for an entropy of formation S(V/sub m/) for the vacancies. NMR measures ..mu.. exp(H(V/sub m/)/k/sub B/T) where the enthalpy H(V/sub m/) = Phi(V/sub m/) - TS(V/sub m/) and the T-independent factor is ..mu.. exp S(V/sub m/) and not simply ..mu... The striking V-dependence observed for this factor (4 decades for 23.0 < V/sub m/ < 24.9 cm/sup 3//mole) could also be understood in terms of an increase in the entropy of formation on approaching V/sub m//sup max/. 4 references.

Enhancement of oxygen vacancies and solar photocatalytic activity of zinc oxide by incorporation of nonmetal

International Nuclear Information System (INIS)

Patil, Ashokrao B.; Patil, Kashinath R.; Pardeshi, Satish K.

2011-01-01

B-doped ZnO and N-doped ZnO powders have been synthesized by mechanochemical method and characterized by TG–DTA, XRD, SEM–EDX, XPS, UV–visible and photoluminescence (PL) spectra. X-ray diffraction data suggests the hexagonal wurtzite structure for modified ZnO crystallites and the incorporation of nonmetal expands the lattice constants of ZnO. The room temperature PL spectra suggest more number of oxygen vacancies exist in nonmetal-doped ZnO than that of undoped zinc oxide. XPS analysis shows the substitution of some of the O atoms of ZnO by nonmetal atoms. Solar photocatalytic activity of B-doped ZnO, N-doped ZnO and undoped ZnO was compared by means of oxidative photocatalytic degradation (PCD) of Bisphenol A (BPA). B-doped ZnO showed better solar PCD efficiency as compare to N-doped ZnO and undoped ZnO. The PCD of BPA follows first order reaction kinetics. The detail mechanism of PCD of Bisphenol A was proposed with the identification of intermediates such as hydroquinone, benzene-1,2,4-triol and 4-(2-hydroxypropan-2-yl) phenol. - Graphical Abstract: B-doped ZnO and N-doped ZnO synthesized by mechanochemical method were characterized by various techniques. Solar photocatalytic degradation of Bisphenol-A is in the order of B-ZnO>N-ZnO>ZnO. Highlights: ► B-doped ZnO and N-doped ZnO powders have been synthesized by mechanochemical method. ► PL spectra suggest oxygen vacancies are in order of B-doped ZnO>N-doped ZnO>ZnO. ► Solar PCD efficiency is in order of B-doped ZnO>N-doped ZnO>ZnO for Bisphenol A.

Zinc Vacancy-Induced Room-Temperature Ferromagnetism in Undoped ZnO Thin Films

Directory of Open Access Journals (Sweden)

Hongtao Ren

2012-01-01

Full Text Available Undoped ZnO thin films are prepared by polymer-assisted deposition (PAD and treated by postannealing at different temperatures in oxygen or forming gases (95%  Ar+5% H2. All the samples exhibit ferromagnetism at room temperature (RT. SQUID and positron annihilation measurements show that post-annealing treatments greatly enhance the magnetizations in undoped ZnO samples, and there is a positive correlation between the magnetization and zinc vacancies in the ZnO thin films. XPS measurements indicate that annealing also induces oxygen vacancies that have no direct relationship with ferromagnetism. Further analysis of the results suggests that the ferromagnetism in undoped ZnO is induced by Zn vacancies.

Effect of oxygen incorporation on the structure and elasticity of Ti-Al-O-N coatings synthesized by cathodic arc and high power pulsed magnetron sputtering

Energy Technology Data Exchange (ETDEWEB)

Hans, M., E-mail: hans@mch.rwth-aachen.de; Baben, M. to; Music, D.; Ebenhöch, J.; Schneider, J. M. [Materials Chemistry, RWTH Aachen University, Kopernikusstr. 10, D-52074 Aachen (Germany); Primetzhofer, D. [Department of Physics and Astronomy, Uppsala University, Lägerhyddsvägen 1, S-75120 Uppsala (Sweden); Kurapov, D.; Arndt, M.; Rudigier, H. [Oerlikon Balzers Coating AG, Iramali 18, LI-9496 Balzers, Principality of Liechtenstein (Liechtenstein)

2014-09-07

Ti-Al-O-N coatings were synthesized by cathodic arc and high power pulsed magnetron sputtering. The chemical composition of the coatings was determined by means of elastic recoil detection analysis and energy dispersive X-ray spectroscopy. The effect of oxygen incorporation on the stress-free lattice parameters and Young's moduli of Ti-Al-O-N coatings was investigated by X-ray diffraction and nanoindentation, respectively. As nitrogen is substituted by oxygen, implications for the charge balance may be expected. A reduction in equilibrium volume with increasing O concentration is identified by X-ray diffraction and density functional theory calculations of Ti-Al-O-N supercells reveal the concomitant formation of metal vacancies. Hence, the oxygen incorporation-induced formation of metal vacancies enables charge balancing. Furthermore, nanoindentation experiments reveal a decrease in elastic modulus with increasing O concentration. Based on ab initio data, two causes can be identified for this: First, the metal vacancy-induced reduction in elasticity; and second, the formation of, compared to the corresponding metal nitride bonds, relatively weak Ti-O and Al-O bonds.

Effect of oxygen incorporation on the structure and elasticity of Ti-Al-O-N coatings synthesized by cathodic arc and high power pulsed magnetron sputtering

International Nuclear Information System (INIS)

Hans, M.; Baben, M. to; Music, D.; Ebenhöch, J.; Schneider, J. M.; Primetzhofer, D.; Kurapov, D.; Arndt, M.; Rudigier, H.

2014-01-01

Ti-Al-O-N coatings were synthesized by cathodic arc and high power pulsed magnetron sputtering. The chemical composition of the coatings was determined by means of elastic recoil detection analysis and energy dispersive X-ray spectroscopy. The effect of oxygen incorporation on the stress-free lattice parameters and Young's moduli of Ti-Al-O-N coatings was investigated by X-ray diffraction and nanoindentation, respectively. As nitrogen is substituted by oxygen, implications for the charge balance may be expected. A reduction in equilibrium volume with increasing O concentration is identified by X-ray diffraction and density functional theory calculations of Ti-Al-O-N supercells reveal the concomitant formation of metal vacancies. Hence, the oxygen incorporation-induced formation of metal vacancies enables charge balancing. Furthermore, nanoindentation experiments reveal a decrease in elastic modulus with increasing O concentration. Based on ab initio data, two causes can be identified for this: First, the metal vacancy-induced reduction in elasticity; and second, the formation of, compared to the corresponding metal nitride bonds, relatively weak Ti-O and Al-O bonds

Formation of vacancies in thermal equilibrium in α-range alloys

International Nuclear Information System (INIS)

Hehenkamp, Th.

1982-01-01

A model for aggregates (complexes) between vacancies and one or more impurity atoms is described for nearest neighbor interactions. Binding enthalpies in the different complexes have been unambigeously derived therefrom employing a variety of experimental techniques for the determination of vacancy concentrations as function of composition and temperature, (resistivity, positron annihilation, calorimetry, dl/l - da/a techniques), for some noble metals alloys. Solvent diffusion in these alloys has been found to be essentially governed by the increase of vacancy concentrations as function of these variables. Approximation for changes in the migration and correlation permits one to obtain the different binding enthalpies from measurements of solvent diffusion enhancement in an independent fashion and gives comparable results to the former techniques. (author)

Effects of the oxygenation level on formation of different reactive oxygen species during photodynamic therapy.

Science.gov (United States)

Price, Michael; Heilbrun, Lance; Kessel, David

2013-01-01

We examined the effect of the oxygenation level on efficacy of two photosensitizing agents, both of which target lysosomes for photodamage, but via different photochemical pathways. Upon irradiation, the chlorin termed NPe6 forms singlet oxygen in high yield while the bacteriopheophorbide WST11 forms only oxygen radicals (in an aqueous environment). Photokilling efficacy by WST11 in cell culture was impaired when the atmospheric oxygen concentration was reduced from 20% to 1%, while photokilling by NPe6 was unaffected. Studies in a cell-free system revealed that the rates of photobleaching of these agents, as a function of the oxygenation level, were correlated with results described above. Moreover, the rate of formation of oxygen radicals by either agent was more sensitive to the level of oxygenation than was singlet oxygen formation by NPe6. These data indicate that the photochemical process that leads to oxygen radical formation is more dependent on the oxygenation level than is the pathway leading to formation of singlet oxygen. © 2013 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2013 The American Society of Photobiology.

Vacancy identification in Co+ doped rutile TiO2 crystal with positron annihilation spectroscopy

International Nuclear Information System (INIS)

Ma Minyang; Qin Xiubo; Wang Baoyi; Wu Weiming

2013-01-01

Background: Room temperature Diluted Magnetic Semiconductor (DMS) is a critical path in the study of spin-electronic devices, but there are many disputes in the intrinsic properties and origin of the room temperature ferromagnetism. Positron annihilation spectroscopy (PAS) is a powerful technique for evaluating vacancy-type defects. Purpose: We aim to establish the relationship between the defect structure and ferromagnetism of the materials by analyzing the parameters of positron annihilation. Methods: Co-doped rutile TiO 2 films were synthesized by ion implantation and extensively studied by variable energy positron annihilation Doppler broadening spectroscopy (DBS) and coincidence Doppler broadening (CDB) measurements with variable energy slow positron beam for identification of the vacancies. Results: The results of DBS showed that a newly formed type of vacancy could be concluded by the S-W plot and the CDB results indicated that the oxygen vacancy (Vo) complex Ti-Co-Vo and/or Ti-Vo were formed with Co ions implantation and the vacancy concentration increased with increasing dopant dose. Conclusion: We identify that the generation of Ti-Vo and/or Ti-Co-Vo vacancy complex are induced by the existence of excess Ti 3d electrons around the oxygen vacancy. (authors)

Effect of vacancy loops on swelling of metals under irradiation

International Nuclear Information System (INIS)

Golubov, S.I.

1981-01-01

Subsequent analysis of vacancy loops formation in metals under irradiation is carried out and effect of vacancy loops on vacancy porosity is studied. Expression for quasistationary function of vacancy loops distribution according to sizes taking into consideration two mechanisms of their initiation-cascade and fluctuational ones - is obtained. It is shown that rate of vacancy absorption and interstitials by vacancy loops in quasiequilibrium state is similar and depends only on summary length of loops, for its calculations the self-coordinated procedure is formulated. For the rate of metal swelling under irradiation obtained is the expression taking into consideration the presence of vacancy loops [ru

Tungsten oxides. I. Effects of oxygen vacancies and doping on electronic and optical properties of different phases of WO3

Science.gov (United States)

Migas, D. B.; Shaposhnikov, V. L.; Rodin, V. N.; Borisenko, V. E.

2010-11-01

In this part we present results of our ab initio calculations indicating that dispersion of the bands near the gap region for different phases of WO3 (namely, ɛ-WO3, δ-WO3, γ-WO3, β-WO3, orth-WO3, α-WO3, and hex-WO3) is rather close. The rapid increase in the absorption coefficient starts at the lower energy range for α-WO3 and hex-WO3 than for the other phases in accordance with the calculated band gaps. An oxygen vacancy has turned out to decrease the gap by 0.50 eV and to shift the absorption coefficient to the lower energy range in the room temperature γ-WO3 phase. We have also traced changes caused by molybdenum and sulfur doping of γ-WO3. Only sulfur doped γ-WO3 has been revealed to display the formation of the impurity band along with a sizable reduction in the gap and the shift in the absorption coefficient to the lower energy range.

Theoretical study of the influence of cation vacancies on the catalytic properties of vanadium antimonate

International Nuclear Information System (INIS)

Messina, S.; Juan, A.; Larrondo, S.; Irigoyen, B.; Amadeo, N.

2008-01-01

We have theoretically studied the influence of antimony and vanadium cation vacancies in the electronic structure and reactivity of vanadium antimonate, using molecular orbital methods. From the analysis of the electronic properties of the VSbO 4 crystal structure, we can infer that both antimony and vanadium vacancies increase the oxidation state of closer V cations. This would indicate that, in the rutile-type VSbO 4 phase the Sb and V cations defects stabilize the V in a higher oxidation state (V 4+ ). Calculations of the adsorption energy for different toluene adsorption geometries on the VSbO 4 (1 1 0) surface have also been performed. The oxidation state of Sb, V and O atoms and the overlap population of metal-oxygen bonds have been evaluated. Our results indicate that the cation defects influence in the toluene adsorption reactions is slight. We have computed different alternatives for the reoxidation of the VSbO 4 (1 1 0) surface active sites which were reduced during the oxygenated products formation. These calculations indicate that the V cations in higher oxidation state (V 4+ ) are the species, which preferentially incorporate lattice oxygen to the reduced Sb cations. Thus, the cation defects would stabilize the V 4+ species in the VSbO 4 structure, determining its ability to provide lattice oxygen as a reactant

Effects of grain boundaries at the electrolyte/cathode interfaces on oxygen reduction reaction kinetics of solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Choi, Min Gi; Koo, Ja Yang; Ahn, Min Woo; Lee, Won Young [Dept. of Mechanical Engineering, Sungkyunkwan University, Suwon (Korea, Republic of)

2017-04-15

We systematically investigated the effects of grain boundaries (GBs) at the electrolyte/cathode interface of two conventional electrolyte materials, i.e., yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC). We deposited additional layers by pulsed laser deposition to control the GB density on top of the polycrystalline substrates, obtaining significant improvements in peak power density (two-fold for YSZ and three-fold for GDC). The enhanced performance at high GB density in the additional layer could be ascribed to the accumulation of oxygen vacancies, which are known to be more active sites for oxygen reduction reactions (ORR) than grain cores. GDC exhibited a higher enhancement than YSZ, due to the easier formation, and thus higher concentration, of oxygen vacancies for ORR. The strong relation between the concentration of oxygen vacancies and the surface exchange characteristics substantiated the role of GBs at electrolyte/cathode interfaces on ORR kinetics, providing new design parameters for highly performing solid oxide fuel cells.

On the stability and mobility of di-vacancies in tungsten

Science.gov (United States)

Heinola, K.; Djurabekova, F.; Ahlgren, T.

2018-02-01

Properties of small vacancy clusters in tungsten were studied with first-principles calculations. The binding and formation energies of the vacancy clusters increase with the cluster size. Dynamic characteristics of a di-vacancy were specified between room temperature and 700 K with lattice kinetic Monte Carlo calculations, which were parametrised with the present first-principles results for the dissociation barriers. An Arrhenius fit for the di-vacancy diffusion yielded \

Oxygen vacancy-induced room-temperature ferromagnetism in D—D neutron irradiated single-crystal TiO2 (001) rutile

Science.gov (United States)

Xu, Nan-Nan; Li, Gong-Ping; Pan, Xiao-Dong; Wang, Yun-Bo; Chen, Jing-Sheng; Bao, Liang-Man

2014-10-01

Remarkable room temperature ferromagnetism in pure single-crystal rutile TiO2 (001) samples irradiated by D—D neutron has been investigated. By combining X-ray diffraction and positron annihilation lifetime, the contracted lattice has been clearly identified in irradiated TiO2, where Ti4+ ions can be easily reduced to the state of Ti3+. As there were no magnetic impurities that could contaminate the samples during the whole procedure, some Ti3+ ions reside on interstitial or substituted sites accompanied by oxygen vacancies should be responsible for the ferromagnetism.

Synergistic effect of oxygen vacancy and nitrogen doping on enhancing the photocatalytic activity of Bi{sub 2}O{sub 2}CO{sub 3} nanosheets with exposed {0 0 1} facets for the degradation of organic pollutants

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yafei [School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 (China); Zhu, Gangqiang, E-mail: zgq2006@snnu.edu.cn [School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 (China); Hojamberdiev, Mirabbos [School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 (China); Department of Natural and Mathematic Sciences, Turin Polytechnic University in Tashkent, Kichik Halqa Yo’li 17, Tashkent 100095 (Uzbekistan); Gao, Jianzhi [School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 (China); Hao, Jing [Xi' an Rejee Industry Development Co., Ltd., Xi’an 710016 (China); Zhou, Jianping; Liu, Peng [School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 (China)

2016-05-15

Highlights: • Nitrogen-doped Bi{sub 2}O{sub 2}CO{sub 3} flower-like microstructures were synthesized by hydrothermal method. • Surface oxygen vacancy were obtained by irradiating the nitrogen-doped Bi{sub 2}O{sub 2}CO{sub 3} with UV light. • Photocatalytic activity was studied by degrading Rhodamine B. • A synergistic effect between oxygen vacancy and nitrogen doping in Bi{sub 2}O{sub 2}CO{sub 3}. - Abstract: Single-crystalline bare Bi{sub 2}O{sub 2}CO{sub 3} (BOC) nanosheets with exposed {0 0 1} facets and nitrogen-doped Bi{sub 2}O{sub 2}CO{sub 3} (NBOC) flower-like microstructures were synthesized by a simple hydrothermal method. The nitrogen-doped Bi{sub 2}O{sub 2}CO{sub 3} flower-like microstructures with oxygen vacancy (UV-NBOC) were obtained by irradiating the NBOC microstructures with UV light for 2 h in ethanol. The UV–vis diffuse reflectance spectra showed that the NBOC and UV-NBOC nanosheets exhibit an obvious red shift in light absorption band compared with the pure BOC nanosheets. Rhodamine B (RhB) was chosen as a model organic pollutant to verify the influence of oxygen vacancy and nitrogen doping on the photocatalytic activity of Bi{sub 2}O{sub 2}CO{sub 3} under simulated solar light irradiation. Judging from the kinetics of RhB photodegradation over the synthesized samples, a synergistic effect between oxygen vacancy and nitrogen doping was found with a remarkable increase (more than 10 and 2 times) in the photocatalytic activity of UV-NBOC compared with BOC and NBOC, respectively. Moreover, the UV-NBOC also exhibited an excellent cyclability and superior photocatalytic activity toward degradation of other organic pollutants (methylene blue, Congo red, Bisphenol A) under simulated solar light irradiation.

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

Energy Technology Data Exchange (ETDEWEB)

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

Stability of V₂O₅ Supported on Titania in the Presence of Water, Bulk Oxygen Vacancies, and Adsorbed Oxygen Atoms

DEFF Research Database (Denmark)

Kristoffersen, Henrik Høgh; Neilson, Hunter L.; Buratto, Steven K.

2017-01-01

). In the case of oxidative dehydrogenation of alkanes and methanol, the reaction produces water, oxygen vacancies, and hydrogen atoms bound to the surface. For this article we use density functional theory to examine how the presence of these species on the surface affects a V2O5 cluster, which we assume......A catalyst consisting of vanadium oxide submonolayers supported on rutile titanium dioxide is used for a variety of reactions. One important question is the difference between the activity of monomeric clusters (having one vanadium atom) and polymeric clusters (having more than one vanadium atom...

The effect of different oxygen exchange layers on TaO x based RRAM devices

Science.gov (United States)

Alamgir, Zahiruddin; Holt, Joshua; Beckmann, Karsten; Cady, Nathaniel C.

2018-01-01

In this work, we investigated the effect of the oxygen exchange layer (OEL) on the resistive switching properties of TaO x based memory cells. It was found that the forming voltage, SET-RESET voltage, R off, R on and retention properties are strongly correlated with the oxygen scavenging ability of the OEL, and the resulting oxygen vacancy formation ability of this layer. Higher forming voltage was observed for OELs having lower electronegativity/lower Gibbs free energy for oxide formation, and devices fabricated with these OELs exhibited an increased memory window, when using similar SET-RESET voltage range.

Investigation of the oxygen-vacancy (A-center) defect complex profile in neutron irradiated high resistivity silicon junction particle detectors

International Nuclear Information System (INIS)

Li, Zheng; Kraner, H.W.; Verbitskaya, E.; Eremin, V.; Ivanov, A.; Rubinelli, F.A.; Fonash, S.J.

1992-02-01

Distributions of the A-center (oxygen-vacancy) in neutron silicon detectors have been studied using Deep Level Transient Spectroscopy. A-centers have been found to be nearly uniformly distributed in the silicon water depth for medium resistivity (0.1 - 0.2 kΩ-cm) silicon detectors. A positive filling pulse was needed to detect the A-centers in high resistivity (>4 kΩ-cm) silicon detectors, and this effect was found to be dependent on the oxidation temperature. A discussion of this effect is presented. 16 refs

Vacancy identification in Co+ doped rutile TiO2 crystal with positron annihilation spectroscopy

Science.gov (United States)

Qin, X. B.; Zhang, P.; Liang, L. H.; Zhao, B. Z.; Yu, R. S.; Wang, B. Y.; Wu, W. M.

2011-01-01

Co-doped rutile TiO2 films were synthesized by ion implantation. Variable energy positron annihilation Doppler broadening spectroscopy and coincidence Doppler broadening measurements were performed for identification of the vacancies. A newly formed type of vacancy can be concluded by the S-W plot and the CDB results indicated that the oxygen vacancy (VO) complex Ti-Co-VO and/or Ti-VO are formed with Co ions implantation and the vacancy concentration is increased with increase of dopant dose.

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

Energy Technology Data Exchange (ETDEWEB)

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

Vacancy dynamic in Ni-Mn-Ga ferromagnetic shape memory alloys

Energy Technology Data Exchange (ETDEWEB)

Merida, D., E-mail: david.merida@ehu.es [Fisika Aplikatua II Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain); Elektrizitate eta Elektronika Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain); García, J. A. [Fisika Aplikatua II Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain); BC Materials (Basque Centre for Materials, Application and Nanostructures), 48040 Leioa (Spain); Sánchez-Alarcos, V.; Pérez-Landazábal, J. I.; Recarte, V. [Departamento de Física, Universidad Pública de Navarra, Campus de Arrosadia, 31006 Pamplona (Spain); Plazaola, F. [Elektrizitate eta Elektronika Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain)

2014-06-09

Vacancies control any atomic ordering process and consequently most of the order-dependent properties of the martensitic transformation in ferromagnetic shape memory alloys. Positron annihilation spectroscopy demonstrates to be a powerful technique to study vacancies in NiMnGa alloys quenched from different temperatures and subjected to post-quench isothermal annealing treatments. Considering an effective vacancy type the temperature dependence of the vacancy concentration has been evaluated. Samples quenched from 1173 K show a vacancy concentration of 1100 ± 200 ppm. The vacancy migration and formation energies have been estimated to be 0.55 ± 0.05 eV and 0.90 ± 0.07 eV, respectively.

Vacancies in quantal Wigner crystals near melting

International Nuclear Information System (INIS)

Barraza, N.; Colletti, L.; Tosi, M.P.

1999-04-01

We estimate the formation energy of lattice vacancies in quantal Wigner crystals of charged particles near their melting point at zero temperature, in terms of the crystalline Lindemann parameter and of the static dielectric function of the fluid phase near freezing. For both 3D and 2D crystals of electrons our results suggest the presence of vacancies in the ground state at the melting density. (author)

Contribution to the study of vacancies in silver and uranium (1962); Contribution a l'etude des lacunes dans l'argent et l'uranium (1962)

Energy Technology Data Exchange (ETDEWEB)

Quere, Y [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1961-12-15

In metals, high temperature vacancies can be retained by quenching. Results are given for the quenching of uranium (in liquid helium) and of silver (in liquid nitrogen). In this last case the energy of formation (1.06 eV) and the energy of mobility (0.86 eV) of the vacancies have been measured as well as the energy of mobility of the divacancies (0.58 eV). If the quenching is slow, it is shown that it is possible to trap the vacancies on the impurities of the metal. This leads to increases in the electrical resistivity observed by annealing after quenching, the vacancies being released before disappearing into sinks. The vacancy-impurity binding energy (the impurity being probably oxygen which is present in the silver used at a concentration of 20 ppm. atom.) can thus be estimated to be 0.4 eV. (author) [French] Dans un metal, les lacunes de haute temperature peuvent etre retenues par trempe. On presente des experiences de trempe d'uranium (dans l'helium liquide) et d'argent (dans l'azote liquide). Dans ce dernier cas, on mesure l'energie de formation (1,06 eV) et l'energie de mobilite (0,86 eV) des lacunes ainsi que l'energie de mobilite des bilacunes (0,58 eV). Si la trempe est lente, on montre que l'on peut pieger des lacunes sur les impuretes du metal. On interprete de cette facon des augmentations de resistivite electrique observees par recuit apres trempe, les lacunes se depiegeant avant de disparaitre dans des puits. L'energie de liaison lacune-impurete (l'impurete etant probablement l'oxygene dont l'argent utilise contient 20 ppm. atom.) peut alors etre evalue 0,4 eV. (auteur)

Adsorption and Formation of Small Na Clusters on Pristine and Double-Vacancy Graphene for Anodes of Na-Ion Batteries.

Science.gov (United States)

Liang, Zhicong; Fan, Xiaofeng; Zheng, Weitao; Singh, David J

2017-05-24

Layered carbon is a likely anode material for Na-ion batteries (NIBs). Graphitic carbon has a low capacity of approximately 35 (mA h)/g due to the formation of NaC 64 . Using first-principles methods including van der Waals interactions, we analyze the adsorption of Na ions and clusters on graphene in the context of anodes. The interaction between Na ions and graphene is found to be weak. Small Na clusters are not stable on the surface of pristine graphene in the electrochemical environment of NIBs. However, we find that Na ions and clusters can be stored effectively on defected graphene that has double vacancies. In addition, the adsorption energy of small Na clusters near a double vacancy is found to decrease with increasing cluster size. With high concentrations of vacancies the capacity of Na on defective graphene is found to be as much as 10-30 times higher than that of graphitic carbon.

Electronic structure and O vacancy formation/migration in La0.825(Mg/Ca/Ba)0.125CoO3

KAUST Repository

Omotayo Akande, Salawu; Gan, Li-Yong; Schwingenschlö gl, Udo

2016-01-01

The effect of A-site hole doping (Mg2+, Ca2+ or Ba2+) on the electronic and magnetic properties as well as the O vacancy formation and migration in perovskite LaCoO3 is studied using first-principles calculations. All three dopants are found

Oxygen nonstoichiometry and defects in Mn-doped Gd2Ti2O7+x

International Nuclear Information System (INIS)

Porat, O.; Tuller, H.L.

1996-01-01

The oxygen nonstoichiometry in Mn-doped Gd 2 Ti 2 O 7 , Gd 2 (Ti 0.975 Mn 0.025 ) 2 O 7+x , was measured electrochemically, as a function of temperature and oxygen partial pressure, with the aid of an oxygen titration cell. The analysis of the data shows that the defect equilibrium can be described by considering the dominant point defects to be neutral oxygen interstitials, doubly charged oxygen vacancies, and trivalent and quadrivalent Mn ions substituted in the Ti sites. The enthalpies for the formation of neutral oxygen interstitials and trivalent Mn are determined

Migration of O vacancies in α-quartz: The effect of excitons and electron holes

International Nuclear Information System (INIS)

Song, Jakyoung; Corrales, L. Rene; Kresse, Georg; Jonsson, Hannes

2001-01-01

We have used density-functional theory and the nudged elastic-band method to calculate migration pathways and estimated the activation energy for the diffusion of oxygen vacancies in α-quartz. While the energy barrier for the diffusion of a neutral vacancy is very high, 4.1 eV, the binding of a triplet-state exciton to the vacancy lowers the barrier to 1.7 eV and the attachment of a hole lowers the barrier to 1.9 eV, making the vacancy mobile at commonly used annealing temperatures

Ionized zinc vacancy mediated ferromagnetism in copper doped ZnO thin films

Directory of Open Access Journals (Sweden)

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.

Low-temperature positron lifetime and Doppler-broadening measurements for single-crystal nickel oxide containing cation vacancies

International Nuclear Information System (INIS)

Waber, J.T.; Snead, C.L. Jr.; Lynn, K.G.

1985-01-01

Lifetime and Doppler-broadening measurements for positron annihilation in substoichiometric nickelous oxide have been made concomitantly from liquid-helium to room temperature. The concentration of cation vacancies is readily controlled by altering the ambient oxygen pressure while annealing the crystals at 1673 0 K. It was found that neither of the three lifetimes observed or their relative intensities varied significantly with the oxygen pressure, and the bulk rate only increased slightly when the specimen was cooled from room to liquid-helium temperatures. These results are interpreted as indicating that some of the positrons are trapped by the existing cation vacancies and a smaller fraction by vacancy clusters

Sr{sub 2}MgMoO{sub 6−δ} thin films fabricated using pulsed-laser deposition with high concentrations of oxygen vacancies

Energy Technology Data Exchange (ETDEWEB)

Shigematsu, K. [Department of Chemistry, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan); Chikamatsu, A., E-mail: chikamatsu@chem.s.u-tokyo.ac.jp; Fukumura, T. [Department of Chemistry, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan); JST-CREST, Bunkyo-ku, Tokyo 113-0033 (Japan); Toyoda, S. [Department of Materials Science and Engineering, Kyoto University, Yoshida-honmachi, Kyoto 606-8501 (Japan); Ikenaga, E. [JASRI/SPring-8, Mikazuki-cho, Hyogo 679-5198 (Japan); Hasegawa, T. [Department of Chemistry, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan); JST-CREST, Bunkyo-ku, Tokyo 113-0033 (Japan); Kanagawa Academy of Science and Technology (KAST), Kawasaki, Kanagawa 213-0012 (Japan)

2014-06-30

We fabricated epitaxial thin films of oxygen-vacant Sr{sub 2}MgMoO{sub 6−δ} using pulsed laser deposition. The films showed low resistivity of the order of 10{sup −2} Ω cm at 300 K. X-ray diffraction analyses revealed that Mg and Mo ions in the Sr{sub 2}MgMoO{sub 6−δ} films were considerably disordered, compared to those in bulk Sr{sub 2}MgMoO{sub 6−δ}. The proportion of oxygen vacancies estimated through hard x-ray photoemission measurements was as large as 0.37, and correlated well with the Mg/Mo ordering.

Vacancy formation energy near an edge dislocation: A hybrid quantum-classical study

International Nuclear Information System (INIS)

Tavazza, F.; Wagner, R.; Chaka, A.M.; Levine, L.E.

2005-01-01

In this work, the formation energy of a single vacancy in aluminum at different distances from an edge dislocation core is studied using a new, hybrid ab initio-classical potential methodology. Such an approach allows us to conduct large-scale atomistic simulations with a simple classical potential (embedded atom method (EAM), for instance) while simultaneously using the more accurate ab initio approach (first principles quantum mechanics) for critical embedded regions. The coupling is made through shared shells of atoms where the two atomistic modeling approaches are relaxed in an iterative, self-consistent manner. The small, critical region is relaxed using all electron density functional theory (DFT) and the much larger cell in which this is embedded is relaxed using a minimization algorithm with EAM potentials

Detection of current-induced vacancies in thin aluminum endash copper lines using positrons

International Nuclear Information System (INIS)

Asoka-Kumar, P.; OBrien, K.; Lynn, K.G.; Simpson, P.J.; Rodbell, K.P.

1996-01-01

In situ depth-resolved positron annihilation spectroscopy (PAS) is used to show dynamic formation of vacancies in 1 μmx1 μm Al-0.5 wt% Cu lines under current flow. We show that the number of vacancies in these lines increases when a dc current (8x10 4 A/cm 2 ) is applied. This increase in vacancy concentration is substantially greater than that due to thermal vacancy generation alone (4x10 18 cm -3 versus 3x10 17 cm -3 ). Isothermal measurements (with no current flow) yield a vacancy formation energy of 0.60±0.02 eV. These results show that PAS can be used to examine the initial stages of interconnect damage due to electromigration. copyright 1996 American Institute of Physics

Oxygen Transport Membranes

Energy Technology Data Exchange (ETDEWEB)

S. Bandopadhyay

2008-08-30

small polaron conduction mechanism. Scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) were used to develop strategies to detect and characterize vacancy creation, dopant segregations and defect association in the oxygen conducting membrane material. The pO{sub 2} and temperature dependence of the conductivity, non-stoichiometry and thermal-expansion behavior of compositions with increasing complexity of substitution on the perovskite A and B sites were studied. Studies with the perovskite structure show anomalous behavior at low oxygen partial pressures (<10{sup -5} atm). The anomalies are due to non-equilibrium effects and can be avoided by using very strict criteria for the attainment of equilibrium. The slowness of the oxygen equilibration kinetics arises from two different mechanisms. In the first, a two phase region occurs between an oxygen vacancy ordered phase such as brownmillerite SrFeO{sub 2.5} and perovskite SrFeO{sub 3-x}. The slow kinetics is associated with crossing the two phase region. The width of the miscibility gap decreases with increasing temperature and consequently the effect is less pronounced at higher temperature. The preferred kinetic pathway to reduction of perovskite ferrites when the vacancy concentration corresponds to the formation of significant concentrations of Fe{sup 2+} is via the formation of a Ruddlesden-Popper (RP) phases as clearly observed in the case of La{sub 0.5}Sr{sub 0.5}FeO{sub 3-x} where LaSrFeO{sub 4} is found together with Fe. In more complex compositions, such as LSFTO, iron or iron rich phases are observed locally with no evidence for the presence of discrete RP phase. Fracture strength of tubular perovskite membranes was determined in air and in reducing atmospheric conditions. The strength of the membrane decreased with temperature and severity of reducing conditions although the strength distribution (Weibull parameter, m) was relatively unaltered. Surface and volume

Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO{sub 2} in the decomposition of high concentration ozone

Energy Technology Data Exchange (ETDEWEB)

Ding, Yanhua; Zhang, Xiaolei [Shanghai Institute of Technology, Shanghai 200235 (China); Chen, Li [East China Normal University, Shanghai 200062 (China); Wang, Xiaorui [Shanghai Institute of Technology, Shanghai 200235 (China); Zhang, Na, E-mail: nzhang@sit.edu.cn [Shanghai Institute of Technology, Shanghai 200235 (China); Liu, Yufeng [Shanghai Institute of Technology, Shanghai 200235 (China); Fang, Yongzheng, E-mail: fyz1003@sina.com [Shanghai Institute of Technology, Shanghai 200235 (China)

2017-06-15

The catalytic decomposition of gaseous ozone (O{sub 3}) is investigated using anatase TiO{sub 2} (A-TiO{sub 2}) and Aluminum-reduced A-TiO{sub 2} (ARA-TiO{sub 2}) at high concentration and high relative humidity (RH) without light illumination. Compared with the pristine A-TiO{sub 2}, the ARA-TiO{sub 2} sample possesses a unique crystalline core-amorphous shell structure. It is proved to be an excellent solar energy “capture” for solar thermal collectors due to lots of oxygen vacancies. The results indicate that the overall decomposition efficiency of O{sub 3} without any light irradiation has been greatly improved from 4.8% on A-TiO{sub 2} to 100% on ARA-TiO{sub 2} under the RH=100% condition. The ozone conversion over T500/ARA-TiO{sub 2} catalyst is still maintained at 95% after a 72 h test under the reaction condition of 18.5 g/m{sup 3} ozone initial concentration, and RH=90%. The results can be explained that T500/ARA-TiO{sub 2} possesses the largest amorphous contour, the lowest crystallinity, the most surface-active Ti{sup 3+}/T{sup i4+}couples, and the most oxygen vacancies. This result opens a new door to widen the application of TiO{sub 2} in the thermal-catalytic field. - Graphical abstract: The anatase-TiO{sub 2} with various oxidation states and oxygen vacancies have been obtained by aluminum-reduction, and the decomposition efficiency of O{sub 3} has been greatly improved from 4.8% to 100% without irradiation under the RH=100% condition. - Highlights: • The decomposition of gaseous ozone over Al reduced TiO2 (ARA-TiO{sub 2}) is firstly reported. • The decomposition efficiency is up to 100% without any light irradiation on ARA-TiO{sub 2} under RH=100% condition. • The ozone conversion is maintained at 95% after a 72 h test, when C{sub inlet}=18.5 g/m{sup 3} and RH=90%.

Interfacial oxygen and nitrogen induced dipole formation and vacancy passivation for increased effective work functions in TiN/HfO[sub 2] gate stacks

KAUST Repository

Hinkle, C. L.

2010-03-09

Effective work function (EWF) changes of TiN/HfO2annealed at low temperatures in different ambient environments are correlated with the atomic concentration of oxygen in the TiN near the metal/dielectric interface. EWF increases of 550 meV are achieved with anneals that incorporate oxygen throughout the TiN with [O]=2.8×1021 cm−3 near the TiN/HfO2interface. However, further increasing the oxygen concentration via more aggressive anneals results in a relative decrease of the EWF and increase in electrical thickness. First-principles calculations indicate the exchange of O and N atoms near the TiN/HfO2interface cause the formation of dipoles that increase the EWF.

Vacancy-induced ferromagnetism in ZnO probed by spin-polarized positron annihilation spectroscopy

Science.gov (United States)

Maekawa, Masaki; Abe, Hiroshi; Miyashita, Atsumi; Sakai, Seiji; Yamamoto, Shunya; Kawasuso, Atsuo

2017-04-01

We investigated the ferromagnetism of ZnO induced by oxygen implantation by using spin-polarized positron annihilation spectroscopy together with magnetization measurements. The magnetization measurements showed the appearance of ferromagnetism after oxygen implantation and its disappearance during post-implantation annealing at temperatures above 573 K. The Doppler broadening of annihilation radiation (DBAR) spectrum showed asymmetry upon field reversal after oxygen implantation. The obtained differential DBAR spectrum between positive and negative magnetic fields was well-explained with a theoretical calculation considering zinc vacancies. The disappearance of the field-reversal asymmetry of the DBAR spectrum as a result of annealing agreed with the observations of ferromagnetism by magnetization measurements. These results suggest the radiation-induced zinc vacancies to be the source of the observed ferromagnetism of ZnO.

Mobility and stability of large vacancy and vacancy-copper clusters in iron: An atomistic kinetic Monte Carlo study

Energy Technology Data Exchange (ETDEWEB)

Castin, N., E-mail: ncastin@sckcen.be [Studiecentrum voor Kernenergie - Centre d' Etudes de l' energie Nucleaire (SCK-CEN), Nuclear Materials Science Institute, Unit Structural Materials Modelling and Microstructure-Boeretang 200, B2400 Mol (Belgium); Pascuet, M.I., E-mail: pascuet@cnea.gov.ar [Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), Av. Rivadavia 1917, C1033AAJ Buenos Aires (Argentina); Malerba, L. [Studiecentrum voor Kernenergie - Centre d' Etudes de l' energie Nucleaire (SCK-CEN), Nuclear Materials Science Institute, Unit Structural Materials Modelling and Microstructure-Boeretang 200, B2400 Mol (Belgium)

2012-10-15

The formation of Cu-rich precipitates under irradiation is a major cause for changes in the mechanical response to load of reactor pressure vessel steels. In previous works, it has been shown that the mechanism under which precipitation occurs is governed by diffusion of vacancy-copper (VCu) complexes, also in the absence of irradiation. Coarse-grained computer models (such as object kinetic Monte Carlo) aimed at simulating irradiation processes in model alloys or steels should therefore explicitly include the mobility of Cu precipitates, as a consequence of vacancy hops at their surface. For this purpose, in this work we calculate diffusion coefficients and lifetimes for a large variety of VCu complexes. We use an innovative atomistic model, where vacancy migration energies are calculated with little approximations, taking into account all effects of static relaxation and long-range chemical interaction as predicted by an interatomic potential. Our results show that, contrary to what intuition might suggest, saturation in vacancies tend to slow down the transport of Cu atoms.

Magnetic properties of ZnO nanowires with Li dopants and Zn vacancies

Energy Technology Data Exchange (ETDEWEB)

Guan, Xinhong; Cai, Ningning [Key Laboratory of Information Photonics and Optical Communications (Beijing University of Posts and Telecommunications), Ministry of Education, P.O. Box 72, Beijing 100876 (China); Yang, Chuanghua [School of Physics and Telecommunication Engineering, Shanxi University of Technology (SNUT), Hanzhong 723001, Shanxi (China); Chen, Jun [Beijing Applied Physics and Computational Mathematics, Beijing 100088 (China); Lu, Pengfei, E-mail: photon.bupt@gmail.com [Key Laboratory of Information Photonics and Optical Communications (Beijing University of Posts and Telecommunications), Ministry of Education, P.O. Box 72, Beijing 100876 (China)

2016-04-30

The electronic and magnetic properties of ZnO nanowire with Li dopants and vacancies have been investigated using first-principles density functional theory. It is found that the Zn vacancy can induce magnetism while increasing the formation energy of the system. However, the calculated results indicate that the introduction of Li-dopants will reduce the formation energy of system. We also have studied the magnetic couplings with vacancies as well as their corresponding configurations with Li-dopants for four configurations of ZnO nanowires. The results show that ferromagnetic properties can be improved/reversed after the introduction of Li-dopants. Ferromagnetic mechanism is originated from the fierce p–p hybridization of O near the Fermi level. We find that ferromagnetism of Li-doped ZnO nanowires with Zn vacancies can be realized at room temperature and they are promising spintronic materials. - Highlights: • Li-dopants will reduce the formation energy of ZnO nanowires with Zn vacancy. • The fierce p–p hybridization of O near Fermi level is responsible for FM properties. • Li-doped ZnO–V{sub Zn} nanowire is a promising FM semiconductor material.

Evaluation of the energetics of copper-vacancy clusters in Fe

Energy Technology Data Exchange (ETDEWEB)

Morishita, Kazunori, E-mail: morishita@iae.kyoto-u.ac.jp; Nakasuji, Toshiki; Ruan, Xiaoyong

2017-02-15

Highlights: • Thermodynamics evaluation of the nucleation process of copper-vacancy clusters in Fe is performed. • Nucleation free energy of copper-vacancy clusters in Fe is formulated. • With this energetics, two different nucleation paths of clusters are found as a function of the damage rate. - Abstract: A theoretical study is conducted to evaluate the nucleation free energy of copper-vacancy clusters in Fe as a function of the numbers of copper atoms and of vacancies in a cluster. Using this free energy value, cluster nucleation processes during irradiation are investigated. The results clearly show that there are two different types of cluster nucleation paths on the free energy surface; one is the formation of empty voids by jumping over the ridge of the free energy surface, and the other corresponds to a path for the formation of copper clusters by going around the ridge. The dependence of easy nucleation paths on the damage rate is discussed.

The structure and properties of vacancies in Si nano-crystals calculated by real space pseudopotential methods

International Nuclear Information System (INIS)

Beckman, S.P.; Chelikowsky, James R.

2007-01-01

The structure and properties of vacancies in a 2 nm Si nano-crystal are studied using a real space density functional theory/pseudopotential method. It is observed that a vacancy's electronic properties and energy of formation are directly related to the local symmetry of the vacancy site. The formation energy for vacancies and Frenkel pair are calculated. It is found that both defects have lower energy in smaller crystals. In a 2 nm nano-crystal the energy to form a Frenkel pair is 1.7 eV and the energy to form a vacancy is no larger than 2.3 eV. The energy barrier for vacancy diffusion is examined via a nudged elastic band algorithm

Identification of vacancy defect complexes in transparent semiconducting oxides ZnO, In2O3 and SnO2

International Nuclear Information System (INIS)

Makkonen, Ilja; Korhonen, Esa; Prozheeva, Vera; Tuomisto, Filip

2016-01-01

Positron annihilation spectroscopy, when combined with supporting high-quality modeling of positron states and annihilation in matter, is a powerful tool for detailed defect identification of vacancy-type defects in semiconductors and oxides. Here we demonstrate that the Doppler broadening of the positron annihilation radiation is a very sensitive means for observing the oxygen environment around cation vacancies, the main open-volume defects trapping positrons in measurements made for transparent semiconducting oxides. Changes in the positron annihilation signal due to external manipulation such as irradiation and annealing can be correlated with the associated changes in the sizes of the detected vacancy clusters. Our examples for ZnO, In 2 O 3 and SnO 2 demonstrate that oxygen vacancies in oxides can be detected directly using positron annihilation spectroscopy when they are complexed with cation vacancies. (paper)

Identification of vacancy defect complexes in transparent semiconducting oxides ZnO, In2O3 and SnO2

Science.gov (United States)

Makkonen, Ilja; Korhonen, Esa; Prozheeva, Vera; Tuomisto, Filip

2016-06-01

Positron annihilation spectroscopy, when combined with supporting high-quality modeling of positron states and annihilation in matter, is a powerful tool for detailed defect identification of vacancy-type defects in semiconductors and oxides. Here we demonstrate that the Doppler broadening of the positron annihilation radiation is a very sensitive means for observing the oxygen environment around cation vacancies, the main open-volume defects trapping positrons in measurements made for transparent semiconducting oxides. Changes in the positron annihilation signal due to external manipulation such as irradiation and annealing can be correlated with the associated changes in the sizes of the detected vacancy clusters. Our examples for ZnO, In2O3 and SnO2 demonstrate that oxygen vacancies in oxides can be detected directly using positron annihilation spectroscopy when they are complexed with cation vacancies.

Experimental identification of nitrogen-vacancy complexes in nitrogen implanted silicon

Science.gov (United States)

Adam, Lahir Shaik; Law, Mark E.; Szpala, Stanislaw; Simpson, P. J.; Lawther, Derek; Dokumaci, Omer; Hegde, Suri

2001-07-01

Nitrogen implantation is commonly used in multigate oxide thickness processing for mixed signal complementary metal-oxide-semiconductor and System on a Chip technologies. Current experiments and diffusion models indicate that upon annealing, implanted nitrogen diffuses towards the surface. The mechanism proposed for nitrogen diffusion is the formation of nitrogen-vacancy complexes in silicon, as indicated by ab initio studies by J. S. Nelson, P. A. Schultz, and A. F. Wright [Appl. Phys. Lett. 73, 247 (1998)]. However, to date, there does not exist any experimental evidence of nitrogen-vacancy formation in silicon. This letter provides experimental evidence through positron annihilation spectroscopy that nitrogen-vacancy complexes indeed form in nitrogen implanted silicon, and compares the experimental results to the ab initio studies, providing qualitative support for the same.

Synthesis and oxygen vacancy related NO{sub 2} gas sensing properties of ZnO:Co nanorods arrays gown by a hydrothermal method

Energy Technology Data Exchange (ETDEWEB)

Zou, Changwei, E-mail: qingyihaiyanas@163.com; Liang, Feng; Xue, Shuwen

2015-10-30

Highlights: • Co doped ZnO:Co nanorods were grown by hydrothermal method. • The NO{sub 2} response reaches a maximum value of 88 at 210 °C. • The stability of NO{sub 2} on ZnO is enhanced with the presence of V{sub O}. - Abstract: Highly ordered Co doped ZnO:Co nanorods arrays with Co concentrations of 1.6, 1.9 and 3.1 at% were uniformly grown on FTO glass substrate by hydrothermal method. The X-ray diffraction patterns of the undoped and Co doped ZnO nanorods revealed characteristic peaks of (1 0 0), (0 0 2), (1 0 1), (1 0 3) and (1 1 2), corresponding to the hexagonal wurtzite phase of ZnO. For ZnO:Co nanorods with Co concentrations of 3.1 at%, the NO{sub 2} response reached a maximum value of 88 at temperature of 210 °C. However, the response of ZnO:Co nanorods with Co concentrations of 3.1 at% decreased from 82 to 29 with the increasing of O{sub 2} annealing temperature from 0 to 700 °C. As confirmed by the XPS, PL, Raman and I–V results, the oxygen vacancies and electron concentrations were the dominating effects and an oxygen vacancy mediated NO{sub 2} sensing mechanism was presented and discussed.

Effects of alloy composition and Si-doping on vacancy defect formation in (InxGa1-x)2O3 thin films

Science.gov (United States)

Prozheeva, V.; Hölldobler, R.; von Wenckstern, H.; Grundmann, M.; Tuomisto, F.

2018-03-01

Various nominally undoped and Si-doped (InxGa1-x)2O3 thin films were grown by pulsed laser deposition in a continuous composition spread mode on c-plane α-sapphire and (100)-oriented MgO substrates. Positron annihilation spectroscopy in the Doppler broadening mode was used as the primary characterisation technique in order to investigate the effect of alloy composition and dopant atoms on the formation of vacancy-type defects. In the undoped samples, we observe a Ga2O3-like trend for low indium concentrations changing to In2O3-like behaviour along with the increase in the indium fraction. Increasing indium concentration is found to suppress defect formation in the undoped samples at [In] > 70 at. %. Si doping leads to positron saturation trapping in VIn-like defects, suggesting a vacancy concentration of at least mid-1018 cm-3 independent of the indium content.

Effect of vacancies on the mechanical properties of phosphorene nanotubes

Science.gov (United States)

Sorkin, V.; Zhang, Y. W.

2018-06-01

Using density functional tight-binding method, we studied the mechanical properties, deformation and failure of armchair (AC) and zigzag (ZZ) phosphorene nanotubes (PNTs) with monovacancies and divacancies subjected to uniaxial tensile strain. We found that divacancies in AC PNTs and monovacancies in ZZ PNTs possess the lowest vacancy formation energy, which decreases with the tube diameter in AC PNTs and increases in ZZ PNTs. The Young’s modulus is reduced, while the radial and thickness Poisson’s ratios are increased by hosted vacancies. In defective AC PNTs, deformation involves fracture of the intra-pucker bonds and formation of the new inter-pucker bonds at a critical strain, and the most stretched bonds around the vacancy rupture first, triggering a sequence of the structural transformations terminated by the ultimate failure. The critical strain of AC PNTs is reduced significantly by hosted vacancies, whereas their effect on the critical stress is relatively weaker. Defective ZZ PNTs fail in a brittle-like manner once the most stretched bonds around a vacancy rupture, and vacancies are able to significantly reduce the failure strain but only moderately reduce the failure stress of ZZ PNTs. The understandings revealed here on the mechanical properties and the deformation and failure mechanisms of PNTs provide useful guidelines for their design and fabrication as building blocks in nanodevices.

Mechanism of formation of a zone without vacancy pores along a surface under electron irradiation of a metal in the high-volt electron microscope

International Nuclear Information System (INIS)

Golubov, S.I.; Konobeev, Yu.V.; Ryabov, V.A.

1981-01-01

Formation mechanism of zones free of vacancy pores near the vacant surface of a metal preliminary irradiated at a high neutron dose when irradiating with electrons in a high-voltage electron microscope has been suggested. It was assumed to explain experimentally observed values of width and time of such zone formation that interstitial atoms are reflected from foil surface while boundary serves as an ideal sink for the vacancies. The carried out calculation of stationary equations of vacancy and interstitial diffusion with the mentioned boundary condition has shown that determination of a stable zone width is possible only in assumption on a variable in a depth of dislocation density. Theoretical evaluations of a zone width being in good agreement with an experiment and with the results of numerical calculations have been obtained in negligence of recombination of point defects as well as for the case of total reflection of interstitials. Discussed are different mechanisms of weak capture of proper interstitial atoms diffusing to it with the metal surface [ru

Formation of tungsten oxide nanowires by ion irradiation and vacuum annealing

Science.gov (United States)

Zheng, Xu-Dong; Ren, Feng; Wu, Heng-Yi; Qin, Wen-Jing; Jiang, Chang-Zhong

2018-04-01

Here we reported the fabrication of tungsten oxide (WO3-x ) nanowires by Ar+ ion irradiation of WO3 thin films followed by annealing in vacuum. The nanowire length increases with increasing irradiation fluence and with decreasing ion energy. We propose that the stress-driven diffusion of the irradiation-induced W interstitial atoms is responsible for the formation of the nanowires. Comparing to the pristine film, the fabricated nanowire film shows a 106-fold enhancement in electrical conductivity, resulting from the high-density irradiation-induced vacancies on the oxygen sublattice. The nanostructure exhibits largely enhanced surface-enhanced Raman scattering effect due to the oxygen vacancy. Thus, ion irradiation provides a powerful approach for fabricating and tailoring the surface nanostructures of semiconductors.

Assessing hafnium on hafnia as an oxygen getter

International Nuclear Information System (INIS)

O'Hara, Andrew; Demkov, Alexander A.; Bersuker, Gennadi

2014-01-01

Hafnium dioxide or hafnia is a wide band gap dielectric used in a range of electronic applications from field effect transistors to resistive memory. In many of these applications, it is important to maintain control over oxygen stoichiometry, which can be realized in practice by using a metal layer, specifically hafnium, to getter oxygen from the adjacent dielectric. In this paper, we employ density functional theory to study the thermodynamic stability of an interface between (100)-oriented monoclinic hafnia and hafnium metal. The nudged elastic band method is used to calculate the energy barrier for migration of oxygen from the oxide to the metal. Our investigation shows that the presence of hafnium lowers the formation energy of oxygen vacancies in hafnia, but more importantly the oxidation of hafnium through the migration of oxygen from hafnia is favored energetically

Interplay of Cu and oxygen vacancy in optical transitions and screening of excitons in ZnO:Cu films

International Nuclear Information System (INIS)

Darma, Yudi; Rusydi, Andrivo; Seng Herng, Tun; Marlina, Resti; Fauziah, Resti; Ding, Jun

2014-01-01

We study room temperature optics and electronic structures of ZnO:Cu films as a function of Cu concentration using a combination of spectroscopic ellipsometry, photoluminescence, and ultraviolet-visible absorption spectroscopy. Mid-gap optical states, interband transitions, and excitons are observed and distinguishable. We argue that the mid-gap states are originated from interactions of Cu and oxygen vacancy (Vo). They are located below conduction band (Zn4s) and above valence band (O2p) promoting strong green emission and narrowing optical band gap. Excitonic states are screened and its intensities decrease upon Cu doping. Our results show the importance of Cu and Vo driving the electronic structures and optical transitions in ZnO:Cu films

Interplay of Cu and oxygen vacancy in optical transitions and screening of excitons in ZnO:Cu films

Science.gov (United States)

Darma, Yudi; Seng Herng, Tun; Marlina, Resti; Fauziah, Resti; Ding, Jun; Rusydi, Andrivo

2014-02-01

We study room temperature optics and electronic structures of ZnO:Cu films as a function of Cu concentration using a combination of spectroscopic ellipsometry, photoluminescence, and ultraviolet-visible absorption spectroscopy. Mid-gap optical states, interband transitions, and excitons are observed and distinguishable. We argue that the mid-gap states are originated from interactions of Cu and oxygen vacancy (Vo). They are located below conduction band (Zn4s) and above valence band (O2p) promoting strong green emission and narrowing optical band gap. Excitonic states are screened and its intensities decrease upon Cu doping. Our results show the importance of Cu and Vo driving the electronic structures and optical transitions in ZnO:Cu films.

Energetic, structural and electronic properties of metal vacancies in strained AlN/GaN interfaces.

Science.gov (United States)

Kioseoglou, J; Pontikis, V; Komninou, Ph; Pavloudis, Th; Chen, J; Karakostas, Th

2015-04-01

AlN/GaN heterostructures have been studied using density-functional pseudopotential calculations yielding the formation energies of metal vacancies under the influence of local interfacial strains, the associated charge distribution and the energies of vacancy-induced electronic states. Interfaces are built normal to the polar direction of the wurtzite structure by joining two single crystals of AlN and GaN that are a few atomic layers thick; thus, periodic boundary conditions generate two distinct heterophase interfaces. We show that the formation energy of vacancies is a function of their distance from the interfaces: the vacancy-interface interaction is found repulsive or attractive, depending on the type of the interface. When the interaction is attractive, the vacancy formation energy decreases with increasing the associated electric charge, and hence the equilibrium vacancy concentration at the interface is greater. This finding can reveal the well-known morphological differences existing between the two types of investigated interfaces. Moreover, we found that the electric charge is strongly localized around the Ga vacancy, while in the case of Al vacancies is almost uniformly distributed throughout the AlN/GaN heterostructure. Crucially, for the applications of heterostructures, metal vacancies introduce deep states in the calculated bandgap at energy levels from 0.5 to 1 eV above the valence band maximum (VBM). It is, therefore, predicted that vacancies could initiate 'green luminescence' i.e. light emission in the energy range of 2.5 eV stemming from electronic transitions between these extra levels, and the conduction band, or energy levels, due to shallow donors.

Quasi-two-dimensional electron gas at the epitaxial alumina/SrTiO{sub 3} interface: Control of oxygen vacancies

Energy Technology Data Exchange (ETDEWEB)

Kormondy, Kristy J.; Posadas, Agham B.; Demkov, Alexander A., E-mail: demkov@physics.utexas.edu [Department of Physics, University of Texas at Austin, Austin, Texas 78712 (United States); Ngo, Thong Q.; Ekerdt, John G. [Department of Chemical Engineering, University of Texas at Austin, Austin, Texas 78712 (United States); Lu, Sirong; Smith, David J.; McCartney, Martha R. [Department of Physics, Arizona State University, Tempe, Arizona 85287 (United States); Goble, Nicholas; Gao, Xuan P. A. [Department of Physics, Case Western Reserve University, Cleveland, Ohio 44106 (United States); Jordan-Sweet, Jean [IBM T.J. Watson Research Center, Yorktown Heights, New York 10598 (United States)

2015-03-07

In this paper, we report on the highly conductive layer formed at the crystalline γ-alumina/SrTiO{sub 3} interface, which is attributed to oxygen vacancies. We describe the structure of thin γ-alumina layers deposited by molecular beam epitaxy on SrTiO{sub 3} (001) at growth temperatures in the range of 400–800 °C, as determined by reflection-high-energy electron diffraction, x-ray diffraction, and high-resolution electron microscopy. In situ x-ray photoelectron spectroscopy was used to confirm the presence of the oxygen-deficient layer. Electrical characterization indicates sheet carrier densities of ∼10{sup 13 }cm{sup −2} at room temperature for the sample deposited at 700 °C, with a maximum electron Hall mobility of 3100 cm{sup 2}V{sup −1}s{sup −1} at 3.2 K and room temperature mobility of 22 cm{sup 2}V{sup −1}s{sup −1}. Annealing in oxygen is found to reduce the carrier density and turn a conductive sample into an insulator.

Formation of neutrophil extracellular traps under low oxygen level

Directory of Open Access Journals (Sweden)

Katja Branitzki-Heinemann

2016-11-01

Full Text Available Since their discovery, neutrophil extracellular traps (NETs have been characterized as a fundamental host innate immune defense mechanism. Conversely, excessive NET release may have a variety of detrimental consequences for the host. A fine balance between NET formation and elimination is necessary to sustain a protective effect during an infectious challenge. Our own recently published data revealed that stabilization of hypoxia inducible factor 1α (HIF-1α by the iron chelating HIF-1α-agonist desferoxamine or AKB-4924 enhanced the release of phagocyte extracellular traps. Since HIF-1α is a global regulator of the cellular response to low oxygen, we hypothesized that NET formation may be similarly increased under low oxygen conditions. Hypoxia occurs in tissues during infection or inflammation, mostly due to overconsumption of oxygen by pathogens and recruited immune cells. Therefore, experiments were performed to characterize the formation of NETs under hypoxic oxygen conditions compared to normoxia. Human blood-derived neutrophils were isolated and incubated under normoxic (21% oxygen level and compared to hypoxic (1% conditions. Dissolved oxygen levels were monitored in the primary cell culture using a Fibox4-PSt3 measurement system. The formation of NETs was quantified by fluorescence microscopy in response to the known NET-inducer phorbol 12-myristate 13-acetate (PMA or S. aureus wildtype and a nuclease-deficient mutant. In contrast to our hypothesis, spontaneous NET formation of neutrophils incubated under hypoxia was distinctly reduced compared to control neutrophils incubated under normoxia. Furthermore, neutrophils incubated under hypoxia showed significantly reduced formation of NETs in response to PMA. Gene expression analysis revealed that mRNA level of hif-1α as well as hif-1α target genes was not altered. However, in good correlation to the decreased NET formation under hypoxia, the cholesterol content of the neutrophils was

Study of the oxygen and substrate bias effects on the defect structure of reactive sputter-deposited SnOx films

International Nuclear Information System (INIS)

Misheva, M.; Nancheva, N.; Docheva, P.; Hadjijska, P.; Djourelov, N.; Elenkov, D.

1999-01-01

The effects of oxygen and substrate bias on the defect structure of reactive sputter-deposited SnOx films were investigated. Samples were analysed using transmission electron microscopy (TEM), transmission electron diffraction (TED), X-ray diffraction (XRD) and positron annihilation spectroscopy (PAS). The oxygen played an important role in the film growth and surface morphology. TEM, TED and XRD showed that increasing of the oxygen partial pressure leads to the formation of films with different crystal phases. The void sizes also depended on oxygen partial pressure. The positron lifetimes and their relative intensities depended on the void concentration, the partial annealing of the vacancies and oxidation of SnO to SnOx. This investigation also showed that the mechanical strength of the films obtained at negative substrate bias is higher and the concentration of vacancy defects is smaller, than in the films, prepared without substrate bias. (author)

Vacancy defects in epitaxial La0.7Sr0.3MnO3 thin films probed by a slow positron beam

International Nuclear Information System (INIS)

Jin, S W; Zhou, X Y; Wu, W B; Zhu, C F; Weng, H M; Wang, H Y; Zhang, X F; Ye, B J; Han, R D

2004-01-01

Vacancy defects in epitaxial La 0.7 Sr 0.3 MnO 3 (LSMO) thin films on LaAlO 3 substrates were detected using a variable energy positron beam. The line-shape S parameter of the epitaxial thin films deposited at different oxygen pressures was measured as a function of the implanting positron energy E. Our results show that the S parameter of the films changes non-monotonically with their deposition oxygen pressures. For the films deposited at lower oxygen pressures, the increase in S value in the films is attributed to the increase in oxygen vacancies and/or related defect-V O complexes, and for those deposited at higher oxygen pressures, the larger S parameter of the films is caused by the grain boundaries and/or metallic ion vacancies. The surface morphology of the films was also characterized to analyse the open volume defects in the LSMO films

Mechanical control of magnetism in oxygen deficient perovskite SrTiO3.

Science.gov (United States)

Zhang, Yajun; Wang, Jie; Sahoo, M P K; Shimada, Takahiro; Kitamura, Takayuki

2015-10-28

Mechanical control of magnetism in perovskite oxides is an important and promising approach in spintronics. Based on the first-principles calculations, we demonstrate that a negative pressure leads to a great enhancement of magnetic moment in deficient SrTiO3 with oxygen vacancies, whereas a positive pressure results in the gradual disappearance of magnetism. Spin charge density, Bader charge analysis and electronic density of states successfully elucidate the origin and underlying physics of the enhancement and disappearance of magnetism. It is found that the split electronic states of dz(2), dyz and dzx in the 3d orbitals of Ti atoms remarkably contribute to the occupancy of majority spin states under negative pressure, which induces a large magnetic moment. Under positive pressure, however, the equal occupancy of both majority and minority t2g and eg states leads to the disappearance of magnetization. In addition, both negative and positive pressures can largely lower the vacancy formation enthalpy, suggesting that the oxygen vacancy is preferable with pressure. Our findings may provide a mechanism to achieve the pressure control of magnetization in nonmagnetic perovskite oxides.

Reconstruction of mono-vacancies in carbon nanotubes: Atomic relaxation vs. spin polarization

Energy Technology Data Exchange (ETDEWEB)

Berber, S. [Institute of Physics, University of Tsukuba, 1-1-1 Tennodai, Tsukuba 305-8571 (Japan)]. E-mail: berber@comas.frsc.tsukuba.ac.jp; Oshiyama, A. [Institute of Physics, University of Tsukuba, 1-1-1 Tennodai, Tsukuba 305-8571 (Japan)

2006-04-01

We have investigated the reconstruction of mono-vacancies in carbon nanotubes using density functional theory (DFT) geometry optimization and electronic structure calculations, employing a numerical basis set. We considered mono-vacancies in achiral nanotubes with diameter range {approx}4-9A. Contrary to previous tight-binding calculations, our results indicate that mono-vacancies could have several metastable geometries, confirming the previous plane-wave DFT results. Formation energy of mono-vacancies is 4.5-5.5eV, increasing with increasing tube diameter. Net magnetic moment decreases from ideal mono-vacancy value after reconstruction, reflecting the reduction of the number of dangling bonds. In spite of the existence of a dangling bond, ground state of mono-vacancies in semiconducting tubes have no spin polarization. Metallic carbon nanotubes show net magnetic moment for most stable structure of mono-vacancy, except for very small diameter tubes.

Reconstruction of mono-vacancies in carbon nanotubes: Atomic relaxation vs. spin polarization

International Nuclear Information System (INIS)

Berber, S.; Oshiyama, A.

2006-01-01

We have investigated the reconstruction of mono-vacancies in carbon nanotubes using density functional theory (DFT) geometry optimization and electronic structure calculations, employing a numerical basis set. We considered mono-vacancies in achiral nanotubes with diameter range ∼4-9A. Contrary to previous tight-binding calculations, our results indicate that mono-vacancies could have several metastable geometries, confirming the previous plane-wave DFT results. Formation energy of mono-vacancies is 4.5-5.5eV, increasing with increasing tube diameter. Net magnetic moment decreases from ideal mono-vacancy value after reconstruction, reflecting the reduction of the number of dangling bonds. In spite of the existence of a dangling bond, ground state of mono-vacancies in semiconducting tubes have no spin polarization. Metallic carbon nanotubes show net magnetic moment for most stable structure of mono-vacancy, except for very small diameter tubes

An oxygen-vacancy-rich Z-scheme g-C3N4/Pd/TiO2 heterostructure for enhanced visible light photocatalytic performance

Science.gov (United States)

Guo, Yanru; Xiao, Limin; Zhang, Min; Li, Qiuye; Yang, Jianjun

2018-05-01

An oxygen-vacancy-rich Z-scheme g-C3N4/Pd/TiO2 ternary nanocomposite was fabricated using nanotubular titanic acid as precursors via a simple photo-deposition of Pd nanoparticles and calcination process. The prepared nanocomposites were investigated by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-visible diffuse reflectance spectroscopy, respectively. For g-C3N4/TiO2 binary nanocomposites, at the optimal content of g-C3N4 (2%), the apparent photocatalytic activity of 2%g-C3N4/TiO2 was 9 times higher than that of pure TiO2 under visible-light illumination. After deposition of Pd (1 wt%) at the contact interface between g-C3N4 and TiO2, the 2%g-C3N4/Pd/TiO2 ternary nanocomposites demonstrated the highest visible-light-driven photocatalytic activity for the degradation of gaseous propylene, which was 16- and 2-fold higher activities than pure TiO2 and 2%g-C3N4/TiO2, respectively. The mechanism for the enhanced photocatalytic performance of the g-C3N4/Pd/TiO2 photo-catalyst is proposed to be based on the efficient separation of photo-generated electron-hole pairs through Z-scheme system, in which uniform dispersity of Pd nanoparticles at contact interface between g-C3N4 and TiO2 and oxygen vacancies promote charge separation.

Effects of recoil-implanted oxygen on depth profiles of defects and annealing processes in P{sup +}-implanted Si studied using monoenergetic positron beams

Energy Technology Data Exchange (ETDEWEB)

Uedono, Akira; Moriya, Tsuyoshi; Tanigawa, Shoichiro [Tsukuba Univ., Ibaraki (Japan). Inst. of Materials Science; Kitano, Tomohisa; Watanabe, Masahito; Kawano, Takao; Suzuki, Ryoichi; Ohdaira, Toshiyuki; Mikado, Tomohisa

1996-04-01

Effects of oxygen atoms recoiled from SiO{sub 2} films on depth profiles of defects and annealing processes in P{sup +}-implanted Si were studied using monoenergetic positron beams. For an epitaxial Si specimen, the depth profile of defects was found to be shifted toward the surface by recoil implantation of oxygen atoms. This was attributed to the formation of vacancy-oxygen complexes and a resultant decrease in the diffusion length of vacancy-type defects. The recoiled oxygen atoms stabilized amorphous regions introduced by P{sup +}-implantation, and the annealing of these regions was observed after rapid thermal annealing (RTA) at 700degC. For a Czochralski-grown Si specimen fabricated by through-oxide implantation, the recoiled oxygen atoms introduced interstitial-type defects upon RTA below the SiO{sub 2}/Si interface, and such defects were dissociated by annealing at 1000degC. (author)

Impurity decoration of native vacancies in Ga and N sublattices of gallium nitride

OpenAIRE

Hautakangas, Sami

2005-01-01

The effects of impurity atoms as well as various growth methods to the formation of vacancy type defects in gallium nitride (GaN) have been studied by positron annihilation spectroscopy. It is shown that vacancy defects are formed in Ga or N sublattices depending on the doping of the material. Vacancies are decorated with impurity atoms leading to the compensation of the free carriers of the samples. In addition, the vacancy clusters are found to be present in significant concentrations in n-...

Characterisation and modelling of vacancy dynamics in Ni–Mn–Ga ferromagnetic shape memory alloys

Energy Technology Data Exchange (ETDEWEB)

Merida, D., E-mail: david.merida@ehu.es [Fisika Aplikatua II Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain); Elektrizitate eta Elektronika Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain); García, J.A. [Fisika Aplikatua II Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain); BC Materials (Basque Centre for Materials, Application and Nanostructures), 48040 Leioa (Spain); Sánchez-Alarcos, V. [Departamento de Física, Universidad Pública de Navarra, Campus de Arrosadia, 31006 Pamplona (Spain); Pérez-Landazábal, J.I.; Recarte, V. [Departamento de Física, Universidad Pública de Navarra, Campus de Arrosadia, 31006 Pamplona (Spain); Institute for Advanced Materials (INAMAT), Universidad Pública de Navarra, Campus de Arrosadía, 31006 Pamplona (Spain); Plazaola, F. [Elektrizitate eta Elektronika Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain)

2015-08-05

Highlights: • We study the dynamics of vacancies for three different Ni–Mn–Ga alloy samples. • The formation and migration energies have been obtained experimentally. • The entropic factor and the distance a vacancy has to reach a sink are measured. • We present a theoretical model to explain the dynamics of vacancies. • Results are applicable for any thermal treatment and extensible to other alloys. - Abstract: The dynamics of vacancies in Ni–Mn–Ga shape memory alloys has been studied by positron annihilation lifetime spectroscopy. The temperature evolution of the vacancy concentration for three different Ni–Mn–Ga samples, two polycrystalline and one monocrystalline, have been determined. The formation and migration energies and the entropic factors are quite similar in all cases, but vary slightly according to composition. However, the number of jumps a vacancy has to overtake to reach a sink is five times higher in the single crystal. This is an expected result, due to the role that surfaces and grain boundaries should play in balancing the vacancy concentration. In all cases, the initial vacancy concentration for the samples quenched from 1173 K lies between 1000 ppm and 2000 ppm. A phenomenological model able to explain the dynamics of vacancies has been developed in terms of the previous parameters. The model can reproduce the vacancy dynamics for any different kind of thermal history and can be easily extended to other alloys.

Vacancy-type defects induced by grinding of Si wafers studied by monoenergetic positron beams

Energy Technology Data Exchange (ETDEWEB)

Uedono, Akira; Yoshihara, Nakaaki [Division of Applied Physics, Faculty of Pure and Applied Science, University of Tsukuba, Tsukuba, Ibaraki 305-8573 (Japan); Mizushima, Yoriko [Devices and Materials Labs Fujitsu Laboratories Ltd., Atsugi, Kanagawa 243-0197 (Japan); ICE Cube Center, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Kim, Youngsuk [ICE Cube Center, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Disco Corporation, Ota, Tokyo 143-8580 (Japan); Nakamura, Tomoji [Devices and Materials Labs Fujitsu Laboratories Ltd., Atsugi, Kanagawa 243-0197 (Japan); Ohba, Takayuki [ICE Cube Center, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Oshima, Nagayasu; Suzuki, Ryoichi [Research Institute of Instrumentation Frontier, National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568 (Japan)

2014-10-07

Vacancy-type defects introduced by the grinding of Czochralski-grown Si wafers were studied using monoenergetic positron beams. Measurements of Doppler broadening spectra of the annihilation radiation and the lifetime spectra of positrons showed that vacancy-type defects were introduced in the surface region (<98 nm), and the major defect species were identified as (i) relatively small vacancies incorporated in dislocations and (ii) large vacancy clusters. Annealing experiments showed that the defect concentration decreased with increasing annealing temperature in the range between 100 and 500°C. After 600–700°C annealing, the defect-rich region expanded up to about 170 nm, which was attributed to rearrangements of dislocation networks, and a resultant emission of point defects toward the inside of the sample. Above 800°C, the stability limit of those vacancies was reached and they started to disappear. After the vacancies were annealed out (900°C), oxygen-related defects were the major point defects and they were located at <25 nm.

Mobility-electron density relation probed via controlled oxygen vacancy doping in epitaxial BaSnO3

Directory of Open Access Journals (Sweden)

Koustav Ganguly

2017-05-01

Full Text Available The recently discovered high room temperature mobility in wide band gap semiconducting BaSnO3 is of exceptional interest for perovskite oxide heterostructures. Critical open issues with epitaxial films include determination of the optimal dopant and understanding the mobility-electron density (μ-n relation. These are addressed here through a transport study of BaSnO3(001 films with oxygen vacancy doping controlled via variable temperature vacuum annealing. Room temperature n can be tuned from 5 × 1019 cm−3 to as low as 2 × 1017 cm−3, which is shown to drive a weak- to strong-localization transition, a 104-fold increase in resistivity, and a factor of 28 change in μ. The data reveal μ ∝ n0.65 scaling over the entire n range probed, important information for understanding mobility-limiting scattering mechanisms.

Photoluminescence related to Gd3+:N-vacancy complex in GaN:Gd multi-quantum wells

International Nuclear Information System (INIS)

Almokhtar, Mohamed; Emura, Shuichi; Koide, Akihiro; Fujikawa, Takashi; Asahi, Hajime

2015-01-01

Highlights: • We grew Gd-doped GaN multi-quantum wells (MQWs) with quantum layer thickness of one nm by MBE. • The X-ray absorption near edge structure spectra observed at Gd LIII-edge indicate a nitrogen vacancy adjacent to Gd substituting the Ga ion in Gd-doped GaN MQW. • The photoluminescence of the samples is discussed considering the formation of a Gd 3+ :Nitrogen-vacancy complex. • A model is presented considering exciton-polaron formation trapped in defect sites around the Gd 3+ :N-vacancy complex in Gd-doped GaN MQWs. - Abstract: The photoluminescence of Gd-doped GaN multi-quantum wells (MQWs) is presented and discussed considering the formation of a Gd 3+ :Nitrogen-vacancy (N-vacancy) complex. A lower energy photoluminescence peak was observed for the Gd-doped GaN MQW sample with respect to the main peak assigned to a neutral donor bound exciton (D 0 X) of the undoped GaN MQW sample. The X-ray absorption near edge structure spectrum observed at Gd L III -edge indicates a nitrogen vacancy adjacent to the Gd substituting the Ga ion in Gd-doped GaN MQW sample. Local stresses around the Gd dopants in Gd-doped GaN matrix generated due to the larger diameter of the Gd 3+ ion with respect to the Ga 3+ ion can be relieved by the creation of vacancies. The lower formation energy of N-vacancies in GaN matrix introduce them as a preferred candidate to relieve the generated stresses. A Gd 3+ :N-vacancy complex consisting of a Gd 3+ ion and the created nitrogen vacancy adjacent to the Gd 3+ dopant is likely to form in GaN:Gd matrix. The lower photoluminescence peak energy observed in the Gd-doped GaN MQW sample is assigned to the recombination of an exciton captured at the Gd 3+ :N-vacancy complex forming a small polaron-like state. A model is presented considering the small exciton-polaron population in defect sites captured around the Gd 3+ ions in the Gd-doped GaN

Oxygen transport and GeO2 stability during thermal oxidation of Ge

Science.gov (United States)

da Silva, S. R. M.; Rolim, G. K.; Soares, G. V.; Baumvol, I. J. R.; Krug, C.; Miotti, L.; Freire, F. L.; da Costa, M. E. H. M.; Radtke, C.

2012-05-01

Oxygen transport during thermal oxidation of Ge and desorption of the formed Ge oxide are investigated. Higher oxidation temperatures and lower oxygen pressures promote GeO desorption. An appreciable fraction of oxidized Ge desorbs during the growth of a GeO2 layer. The interplay between oxygen desorption and incorporation results in the exchange of O originally present in GeO2 by O from the gas phase throughout the oxide layer. This process is mediated by O vacancies generated at the GeO2/Ge interface. The formation of a substoichiometric oxide is shown to have direct relation with the GeO desorption.

Interaction of nitrogen with vacancy defects in N+-implanted ZnO studied using a slow positron beam

International Nuclear Information System (INIS)

Chen, Z.Q.; Maekawa, M.; Kawasuso, A.; Suzuki, R.; Ohdaira, T.

2005-01-01

ZnO crystals were implanted with N + , O + , and Al + , and co-implanted with O + /N + and Al + /N + ions. Positron annihilation measurements indicate introduction of vacancy clusters upon implantation. In the N + -implanted and Al + /N + co-implanted samples, these vacancy clusters are only partially annealed at 800 deg. C, as compared with their entire recovery in the O + - and Al + -implanted samples at 800-900 deg. C, suggesting a strong interaction between nitrogen and vacancy clusters. However, in the O + /N + co-implanted sample, most vacancy clusters disappear at 800 deg. C. Probably oxygen scavenges nitrogen to enhance the annealing of the vacancy clusters. Upon further annealing at 1000-1100 deg. C, nitrogen also forms stable complexes with thermally generated vacancies. These nitrogen-related vacancy complexes need high-temperature annealing at 1200-1250 deg. C to be fully removed

Internal positron source production with a cyclotron and vacancy study in silicon

Energy Technology Data Exchange (ETDEWEB)

Kawasuso, Atsuo; Masuno, Shin-ichi; Okada, Sohei [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment; Hasegawa, Masayuki; Suezawa, Masashi

1997-03-01

In order to detect thermal vacancies in Si, in situ positron annihilation measurement has been performed using an internal source method. An increase (decrease) in S-parameter (W-parameter) was observed above 1200degC. It was explained in terms of the formation of thermal vacancies. (author)

Effect of defects on the small polaron formation and transport properties of hematite from first-principles calculations.

Science.gov (United States)

Smart, Tyler J; Ping, Yuan

2017-10-04

Hematite (α-Fe 2 O 3 ) is a promising candidate as a photoanode material for solar-to-fuel conversion due to its favorable band gap for visible light absorption, its stability in an aqueous environment and its relatively low cost in comparison to other prospective materials. However, the small polaron transport nature in α-Fe 2 O 3 results in low carrier mobility and conductivity, significantly lowering its efficiency from the theoretical limit. Experimentally, it has been found that the incorporation of oxygen vacancies and other dopants, such as Sn, into the material appreciably enhances its photo-to-current efficiency. Yet no quantitative explanation has been provided to understand the role of oxygen vacancy or Sn-doping in hematite. We employed density functional theory to probe the small polaron formation in oxygen deficient hematite, N-doped as well as Sn-doped hematite. We computed the charged defect formation energies, the small polaron formation energy and hopping activation energies to understand the effect of defects on carrier concentration and mobility. This work provides us with a fundamental understanding regarding the role of defects on small polaron formation and transport properties in hematite, offering key insights into the design of new dopants to further improve the efficiency of transition metal oxides for solar-to-fuel conversion.

Adsorption and magnetism of bilayer graphene on the MnO polar surface with oxygen vacancies in the interface: First principles study

Science.gov (United States)

Ilyasov, Victor V.; Ershov, Igor V.; Popova, Inna G.; Pham, Khang D.; Nguyen, Chuong V.

2018-05-01

In this paper, we investigate systematically the structural, electronic, magnetic and adsorption properties of Bernal-stacked bilayer graphene on MnO(111) surface terminated by an oxygen atom, as a function of nonstoichiometric composition of the BLG/MnOx(111) interface. For additional functionalization of the BLG/MnOx(111) system, we also studied the adsorption properties of oxygen adsorbed on the BLG/MnOx(111) interface. Our results showed that the BLG is bound to the MnOx(111) substrate by the weak interaction for both spin-up and spin-down. Furthermore, we found that BLG adsorbed on the MnOx(111) substrate with a reduced oxygen symmetry in the interface is accompanied with a downshift of the Fermi level, which identifies the band structure of BLG as a p-type semiconductor. Upon interaction between BLG and MnOx(111) substrate, a forbidden gap of about 350 meV was opened between its bonding and antibonding π bands. A forbidden gap and the local magnetic moments in bilayer graphene can be controlled by changing the oxygen nonstoichometry or by oxygen adsorption. Additionally, magnetism has been predicted in the bilayer graphene adsorbed on the polar MnOx(111) surface with oxygen vacancies in the BLG/MnOx(111) interface, and its nature has also been discussed in this work. These results showed that the adsorption of bilayer graphene on the MnO(111) substrate can be used for developing novel generation of electronic and spintronic devices.

Vacancies and atomic processes in intermetallics - From crystals to quasicrystals and bulk metallic glasses

Energy Technology Data Exchange (ETDEWEB)

Schaefer, Hans-Eckhardt [Institute of Theoretical and Applied Physics, Stuttgart University, Pfaffenwaldring 57, 70569 Stuttgart (Germany); Baier, Falko [Voith Turbo Comp., Alexanderstr. 2, 89552 Heidenheim (Germany); Mueller, Markus A. [GFT Technologies A. G., Filderhauptstr. 142, 70599 Stuttgart (Germany); Reichle, Klaus J. [Philipp-Matthaeus-Hahn School, Jakob-Beutter-Str. 15, 72336 Balingen (Germany); Reimann, Klaus [NXP Semiconductors, Central Research and Development, High Tech Campus 4, 5656 AE Eindhoven (Netherlands); Rempel, Andrey A. [Institute of Solid State Chemistry, Russian Academy of Sciences, Ul. Pervomaiskaya 91, 620041 Ekaterinburg (Russian Federation); Sato, Kiminori [Tokyo Gakugei University, Nukuikita 4-1-1, Koganei, Tokyo 184-8501 (Japan); Ye, Feng [State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, 30 Xue Yuan Road, Beijing 100083 (China); Zhang, Xiangyi [Yanshan University, Qinhuangdao 066004 (China); Sprengel, Wolfgang [Institute of Materials Physics, Graz University of Technology, Petersgasse 16, 8010 Graz (Austria)

2011-10-15

A review is given on atomic vacancies in intermetallic compounds. The intermetallic compounds cover crystalline, quasicrystalline, and bulk metallic glass (BMG) structures. Vacancies can be specifically characterized by their positron lifetimes, by the coincident measurement of the Doppler broadening of the two quanta emitted by positron-electron annihilation, or by time-differential dilatometry. By these techniques, high concentrations and low mobilities of thermal vacancies were found in open-structured B2 intermetallics such as FeAl or NiAl, whereas the concentrations of vacancies are low and their mobilities high in close-packed structure as, e.g., L1{sub 2}-Ni{sub 3}Al. The activation volumes of vacancy formation and migration are determined by high-pressure experiments. The favorable sublattice for vacancy formation is found to be the majority sublattice in Fe{sub 61}Al{sub 39} and in MoSi{sub 2}. In the icosahedral quasicrystal Al{sub 70}Pd{sub 21}Mn{sub 9} the thermal vacancy concentration is low, whereas in the BMG Zr{sub 57}Cu{sub 15.4}Ni{sub 12.6}Nb{sub 3}Al{sub 10} thermal vacancies are found in high concentrations with low mobilities. This may determine the basic mechanisms of the glass transition. Making use of the experimentally determined vacancy data, the main features of atomic diffusion studies in crystalline intermetallics, in quasicrystals, and in BMGs can be understood. Manfred Faehnle and his group have substantially contributed to the theoretical understanding of vacancies and diffusion mechanisms in intermetallics. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Benign Synthesis of Black Microspheres of Anatase TiO2 with Paramagnetic Oxygen Vacancies through NH3 Treatment.

Science.gov (United States)

Maqbool, Qysar; Srivastava, Aasheesh

2017-10-09

Coloured TiO 2 is coveted for its ability to extract energy from the visible region of electromagnetic spectrum. Here a facile synthesis of black anatase titania microspheres (B-TiO 2 ) through a two-step process is reported. In the first step, amorphous white TiO 2 microspheres (W-TiO 2 ) are obtained by hydrolysing titanium tetraisopropoxide by ammonia vapours in ethanol. In the second step, the W-TiO 2 is thermally annealed at 500 °C to obtain B-TiO 2 . The diffuse reflectance analysis showed that B-TiO 2 absorbs across visible spectrum with absorption extending well into NIR region. Raman scattering together with EPR analysis showed compelling evidence of the existence of oxygen deficiency within the crystal in B-TiO 2 that induces black colouration in the sample. The defects present in the black anatase sample were confirmed to be single-electron-trapped (or paramagnetic) oxygen vacancies (V o ⋅) by XPS and EPR studies. The magnetic susceptibility studies showed existence of antiferromagnetic interactions between these unpaired electron spins. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Positron annihilation studies of vacancies in Ag-Zn alloys

International Nuclear Information System (INIS)

Chabik, S.

1982-01-01

The temperature dependence of annihilation rate, F(T), at the peak of angular correlation curve has been measured for Ag-29.2%at Zn and Ag-50%at Zn alloys. By applying the trapping model the vacancy formation energy for Ag-29.2%at Zn alloy has been found to be equal to 0.94+-0.06 eV. It has been found that the course of the F(T) curve for Ag-50%at Zn depends on the phase composition and thermal history of the investigated sample. For alloys containing not more than 50%at Zn, the concentration dependence of the vacancy formation energy for Ag-Zn alloys is very similar to that for Cu-Zn alloys. (Auth.)

Clustering and segregation of small vacancy clusters near tungsten (0 0 1) surface

Science.gov (United States)

Duan, Guohua; Li, Xiangyan; Xu, Yichun; Zhang, Yange; Jiang, Yan; Hao, Congyu; Liu, C. S.; Fang, Q. F.; Chen, Jun-Ling; Luo, G.-N.; Wang, Zhiguang

2018-01-01

Nanoporous metals have been shown to exhibit radiation-tolerance due to the trapping of the defects by the surface. However, the behavior of vacancy clusters near the surface is not clear which involves the competition between the self-trapping and segregation of small vacancy clusters (Vn) nearby the surface. In this study, we investigated the energetic and kinetic properties of small vacancy clusters near tungsten (0 0 1) surface by combining molecular statics (MS) calculations and object Kinetic Monte Carlo (OKMC) simulations. Results show that vacancies could be clustered with the reduced formation energy and migration energy of the single vacancy around a cluster as the respective energetic and kinetic driving forces. The small cluster has a migration energy barrier comparable to that for the single vacancy; the migration energy barriers for V1-5 and V7 are 1.80, 1.94, 2.17, 2.78, 3.12 and 3.11 eV, respectively. Clusters and become unstable near surface (0 0 1) and tend to dissociate into the surface. At the operation temperature of 1000 K, the single vacancy, V2, 2 V 3 V3 and V4 were observed to segregate to the surface within a time of one hour. Meanwhile, larger clusters survived near the surface, which could serve as nucleating center for voids near the surface. Our results suggest that under a low radiation dose, surface (0 0 1) could act as a sink for small vacancy clusters, alleviating defect accumulation in the material under a low radiation dose. We also obtained several empirical expressions for the vacancy cluster formation energy, binding energy, and trapping radius as a function of the number of vacancies in the cluster.

On the calculation of the energies of dissociation, cohesion, vacancy formation, electron attachment, and the ionization potential of small metallic clusters containing a monovacancy

Science.gov (United States)

Pogosov, V. V.; Reva, V. I.

2017-09-01

In terms of the model of stable jellium, self-consistent calculations of spatial distributions of electrons and potentials, as well as of energies of dissociation, cohesion, vacancy formation, electron attachment, and ionization potentials of solid clusters of Mg N , Li N (with N ≤ 254 ) and of clusters containing a vacancy ( N ≥ 12) have been performed. The contribution of a monovacancy to the energy of the cluster and size dependences of its characteristics and of asymptotics have been discussed. Calculations have been performed using a SKIT-3 cluster at Glushkov Institute of Cybernetics, National Academy of Sciences, Ukraine (Rpeak = 7.4 Tflops).

Effect of oxygen vacancies on magnetic and transport properties of Sr2IrO4

Science.gov (United States)

Dwivedi, Vinod Kumar; Mukhopadhyay, Soumik

2018-05-01

Iridates have recently attracted growing interest because of their potential for realizing various interesting phases like interaction driven Mott-type insulator and magnetically driven Slater-type. In this paper, we present the magnetic and electrical transport properties of polycrystalline Sr2IrO4 synthesized by solid state reaction route. We find a ferromagnetic transition at 240 K. The Curie-Weiss law behavior hold good above the magnetic transition temperature TMag = 240 K with a small effective paramagnetic magnetic moment μeff = 0.25 µB/f.u. and a Curie-Weiss temperature, θCW = +100 K. Zero field cooled (ZFC) magnetization shows a gradual dcrease below 150 K, while same for field cooled (FC) below 50 K. Interestingly, below temperatures, ⁓ 10 K, a sharp increase in ZFC and FC magnetization can be seen. A temperature dependent resistivity reveals insulating behavior followed by power law mechanism. The sintering of sample in air leads to the very low value of resistivity is likely related to Sr or oxygen vacancies.

Electron diffraction study of the sillenites Bi12SiO20, Bi25FeO39 and Bi25InO39: Evidence of short-range ordering of oxygen-vacancies in the trivalent sillenites

Directory of Open Access Journals (Sweden)

Craig A. Scurti

2014-08-01

Full Text Available We present an electron diffraction study of three sillenites, Bi12SiO20, Bi25FeO39, and Bi25InO39 synthesized using the solid-state method. We explore a hypothesis, inspired by optical studies in the literature, that suggests that trivalent sillenites have additional disorder not present in the tetravalent compounds. Electron diffraction patterns of Bi25FeO39 and Bi25InO39 show streaks that confirm deviations from the ideal sillenite structure. Multi-slice simulations of electron-diffraction patterns are presented for different perturbations to the sillenite structure - partial substitution of the M site by Bi3+, random and ordered oxygen-vacancies, and a frozen-phonon model. Although comparison of experimental data to simulations cannot be conclusive, we consider the streaks as evidence of short-range ordered oxygen-vacancies.

Hexagonal perovskites with cationic vacancies. 29. Structure of Ba/sub 4/ScReWvacantO/sub 12/ - on the function of octahedral cationic vacancies in perovskite stacking polytypes

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S; Herrmann, M [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1981-09-01

The hexagonal perovskite stacking polytype Ba/sub 4/ScReWvacantO/sub 12/ crystallizes in a rhombohedral 12 L structure (space group R-3m; sequence (hhcc)/sub 3/). The refined, intensity related R' value is 6.6%. The octahedral net consists of blocks of three face connected octahedra with a central vacancy, in the two outer positions the rhenium and tungsten atoms are located; these units are linked via common corners by single octahedra, occupied with scandium. The construction principles of hexagonal oxygen perovskites with octahedral, cationic vacancies are reported.

Characterization of oxygen vacancies and their migration in Ba-doped Pb(Zr0.52Ti0.48)O3 ferroelectrics

Science.gov (United States)

Zhang, M. F.; Wang, Y.; Wang, K. F.; Zhu, J. S.; Liu, J.-M.

2009-03-01

We investigate in detail the migration kinetics of oxygen vacancies (OVs) in Ba-doped Pb(Zr0.52Ti0.48)O3 (PZT) ferroelectrics by complex impedance spectroscopy. The temperature dependent dc-electrical conductivity σdc suggests that Ba doping into PZT can lower significantly the density of OVs, leading to the distinctly decreased σdc and slightly enhanced activation energy U for the migration of OVs, thus benefiting the polarization fatigue resistance. Furthermore, the polarization fluctuation induced by the relaxation of OVs is reduced by the Ba doping. The Cole-Cole fitting to the dielectric loss manifests strong correlation among OVs, and the migration of OVs appears to be a collective behavior.

A first-principles study of oxygen vacancy induced changes in structural, electronic and magnetic properties of La{sub 2/3}Sr{sub 1/3}MnO{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Li, Jia [Division of Materials Science, Nanyang Technological University, Singapore, 639798 (Singapore); Sun, Lizhong [Division of Materials Science, Nanyang Technological University, Singapore, 639798 (Singapore); Laboratory for Quantum Engineering and Micro-Nano Energy Technology, Xiangtan University, Xiangtan, Hunan, 411105 (China); Shenai, Prathamesh M.; Wang, Junling [Division of Materials Science, Nanyang Technological University, Singapore, 639798 (Singapore); Zheng, Hang [Department of Physics, Shanghai Jiao Tong University, 800 Dong Chuan Road, Shanghai, 200240 (China); Zhao, Yang, E-mail: YZhao@ntu.edu.sg [Division of Materials Science, Nanyang Technological University, Singapore, 639798 (Singapore)

2015-11-15

We have systematically assessed the influence of oxygen vacancy defects on the structural, electronic and magnetic properties of La{sub 2/3}Sr{sub 1/3}MnO{sub 3} via first-principles calculations using the bare GGA as well as the GGA + U formalism. The on-site Coulombic repulsion parameter U for Mn 3d orbital in the latter has been determined by the linear response theory. It is revealed that the introduction of the vacancy defects causes prominent structural changes in the microenvironment of a defect including the distortions of MnO{sub 6} octahedra. In contrast to the general notion, the GGA + U formalism is found to yield significantly more prominent structural changes than the bare GGA method. The octahedral distortion leads to a strengthening or weakening of the hybridization between Mn 3d and O 2p orbitals depending upon an increase or decrease, respectively, in the Mn–O distances as compared to the pristine system. The magnetic moments of the Mn atoms located in three typical sites of the vacancy-containing supercell are all larger than those in the pristine system. This enhancement for the Mn atoms located in the first- and third-nearest neighboring MnO{sub 6} octahedra of the vacancy defect originates from the electron transfer from 4s/3p to 3d orbitals. On the other hand, for the Mn atom located in the first-nearest neighboring site of the vacancy it is attributed to the increased total number of electrons in 3d orbitals due to the absence of one Mn–O bond. Furthermore, we have characterized the O-vacancy defect as a hole-type defect that forms a negative charge center, attracting electrons. - Highlights: • GGA + U calculations reveal effect of O-vacancy on properties of La{sub 1−1/3}Sr{sub 1/3}MnO{sub 3.} • Value of U = 5.9 eV calculated for Mn 3d orbitals from the linear response theory. • O-vacancy causes prominent distortions of MnO{sub 6} octahedra. • Octahedral distortions modulate electronic and magnetic properties of LSMO. �

Methanol Formation via Oxygen Insertion Chemistry in Ices

Science.gov (United States)

Bergner, Jennifer B.; Öberg, Karin I.; Rajappan, Mahesh

2017-08-01

We present experimental constraints on the insertion of oxygen atoms into methane to form methanol in astrophysical ice analogs. In gas-phase and theoretical studies this process has previously been demonstrated to have a very low or nonexistent energy barrier, but the energetics and mechanisms have not yet been characterized in the solid state. We use a deuterium UV lamp filtered by a sapphire window to selectively dissociate O2 within a mixture of O2:CH4 and observe efficient production of CH3OH via O(1D) insertion. CH3OH growth curves are fit with a kinetic model, and we observe no temperature dependence of the reaction rate constant at temperatures below the oxygen desorption temperature of 25 K. Through an analysis of side products we determine the branching ratio of ice-phase oxygen insertion into CH4: ˜65% of insertions lead to CH3OH, with the remainder leading instead to H2CO formation. There is no evidence for CH3 or OH radical formation, indicating that the fragmentation is not an important channel and that insertions typically lead to increased chemical complexity. CH3OH formation from O2 and CH4 diluted in a CO-dominated ice similarly shows no temperature dependence, consistent with expectations that insertion proceeds with a small or nonexistent barrier. Oxygen insertion chemistry in ices should therefore be efficient under low-temperature ISM-like conditions and could provide an important channel to complex organic molecule formation on grain surfaces in cold interstellar regions such as cloud cores and protoplanetary disk midplanes.

Methanol Formation via Oxygen Insertion Chemistry in Ices

Energy Technology Data Exchange (ETDEWEB)

Bergner, Jennifer B. [Harvard University Department of Chemistry and Chemical Biology, 10 Oxford Street, Cambridge, MA 02138 (United States); Öberg, Karin I.; Rajappan, Mahesh [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States)

2017-08-10

We present experimental constraints on the insertion of oxygen atoms into methane to form methanol in astrophysical ice analogs. In gas-phase and theoretical studies this process has previously been demonstrated to have a very low or nonexistent energy barrier, but the energetics and mechanisms have not yet been characterized in the solid state. We use a deuterium UV lamp filtered by a sapphire window to selectively dissociate O{sub 2} within a mixture of O{sub 2}:CH{sub 4} and observe efficient production of CH{sub 3}OH via O({sup 1}D) insertion. CH{sub 3}OH growth curves are fit with a kinetic model, and we observe no temperature dependence of the reaction rate constant at temperatures below the oxygen desorption temperature of 25 K. Through an analysis of side products we determine the branching ratio of ice-phase oxygen insertion into CH{sub 4}: ∼65% of insertions lead to CH{sub 3}OH, with the remainder leading instead to H{sub 2}CO formation. There is no evidence for CH{sub 3} or OH radical formation, indicating that the fragmentation is not an important channel and that insertions typically lead to increased chemical complexity. CH{sub 3}OH formation from O{sub 2} and CH{sub 4} diluted in a CO-dominated ice similarly shows no temperature dependence, consistent with expectations that insertion proceeds with a small or nonexistent barrier. Oxygen insertion chemistry in ices should therefore be efficient under low-temperature ISM-like conditions and could provide an important channel to complex organic molecule formation on grain surfaces in cold interstellar regions such as cloud cores and protoplanetary disk midplanes.

Superabundant vacancies in fcc metals: A combination of ab-initio, thermodynamic and kinetics approaches

Energy Technology Data Exchange (ETDEWEB)

Nazarov, Roman; Hickel, Tilmann; Neugebauer, Joerg [Max-Planck-Institut fuer Eisenforschung, Duesseldorf (Germany)

2011-07-01

A dramatic increase of the vacancy concentration in a H-rich atmosphere, the so called superabundant vacancy formation, has been experimentally observed in several metals and alloys. In order to study this phenomenon we systematically applied density functional theory to a large set of fcc metals. We found that a large amount of H can be trapped by a monovacancy with, e.g., up to 15 H atoms in an Al vacancy, up to 12 H atoms in the case of Pd and more than 17 H atoms for Pb. Based on the defect formation energies from DFT calculations, we have constructed a thermodynamic model that determines the equilibrium concentration of point defects as a function of temperature and H chemical potential. By applying this approach we revealed that the vacancy concentration can indeed strongly increase if H is added. To understand the phenomenon of accelerated self-diffusion in a H-rich atmosphere we coupled the information on the number of vacancies from the thermodynamic treatment with self-diffusion barriers obtained from DFT calculations. Using this approach we found that the self-diffusion coefficient is reduced not only due to the increased vacancy concentration, but also as a result of a H-induced lubricant effect.

Temperature dependence of enthalpies and entropies of formation and migration of mono-vacancy in BCC iron

Energy Technology Data Exchange (ETDEWEB)

Wen, Haohua; Woo, C.H., E-mail: chungho@cityu.edu.hk

2014-12-15

Entropies and enthalpies of vacancy formation and diffusion in BCC iron are calculated for each temperature directly from free-energies using phase-space trajectories obtained from spin–lattice dynamics simulations. Magnon contributions are found to be particularly substantial in the temperature regime near the α−β (ferro/para-magnetic) transition. Strong temperature dependence and singular behavior can be seen in this temperature regime, reflecting magnon softening effects. Temperature dependence of the lattice component in this regime is also much more significant compared to previous estimations based on Arrhenius-type fitting. Similar effects on activation processes involving other irradiation-produced defects in magnetic materials are expected.

Physical properties and band structure of reactive molecular beam epitaxy grown oxygen engineered HfO{sub 2{+-}x}

Energy Technology Data Exchange (ETDEWEB)

Hildebrandt, Erwin; Kurian, Jose; Alff, Lambert [Institute of Materials Science, Technische Universitaet Darmstadt, 64287 Darmstadt (Germany)

2012-12-01

We have conducted a detailed thin film growth structure of oxygen engineered monoclinic HfO{sub 2{+-}x} grown by reactive molecular beam epitaxy. The oxidation conditions induce a switching between (111) and (002) texture of hafnium oxide. The band gap of oxygen deficient hafnia decreases with increasing amount of oxygen vacancies by more than 1 eV. For high oxygen vacancy concentrations, defect bands form inside the band gap that induce optical transitions and p-type conductivity. The resistivity changes by several orders of magnitude as a function of oxidation conditions. Oxygen vacancies do not give rise to ferromagnetic behavior.

Energy Characteristics of Small Metal Clusters Containing Vacancies

Science.gov (United States)

Reva, V. I.; Pogosov, V. V.

2018-02-01

Self-consistent calculations of spatial distributions of electrons, potentials, and energies of dissociation, cohesion, vacancy formation, and electron attachment, as well as the ionization potential of solid Al N , Na N clusters ( N ≥ 254), and clusters containing a vacancy ( N ≥ 12) have been performed using a model of stable jellium. The contribution of a monovacancy to the energy of the cluster, the size dependences of the characteristics, and their asymptotic forms have been considered. The calculations have been performed on the SKIT-3 cluster at the Glushkov Institute of Cybernetics, National Academy of Sciences of Ukraine (Rpeak = 7.4 Tflops).

Vacancy defects in electron-irradiated ZnO studied by Doppler broadening of annihilation radiation

Science.gov (United States)

Chen, Z. Q.; Betsuyaku, K.; Kawasuso, A.

2008-03-01

Vacancy defects in ZnO induced by electron irradiation were characterized by the Doppler broadening of annihilation radiation measurements together with the local density approximation calculations. Zinc vacancies (VZn) are responsible for positron trapping in the as-irradiated state. These are annealed out below 200°C . The further annealing at 400°C results in the formation of secondary defects attributed to the complexes composed of zinc vacancies and zinc antisites (VZn-ZnO) .

Magnetoresistance Versus Oxygen Deficiency in Epi-stabilized SrRu1 - x Fe x O3 - δ Thin Films

Science.gov (United States)

Dash, Umasankar; Acharya, Susant Kumar; Lee, Bo Wha; Jung, Chang Uk

2017-03-01

Oxygen vacancies have a profound effect on the magnetic, electronic, and transport properties of transition metal oxide materials. Here, we studied the influence of oxygen vacancies on the magnetoresistance (MR) properties of SrRu1 - x Fe x O3 - δ epitaxial thin films ( x = 0.10, 0.20, and 0.30). For this purpose, we synthesized highly strained epitaxial SrRu1 - x Fe x O3 - δ thin films with atomically flat surfaces containing different amounts of oxygen vacancies using pulsed laser deposition. Without an applied magnetic field, the films with x = 0.10 and 0.20 showed a metal-insulator transition, while the x = 0.30 thin film showed insulating behavior over the entire temperature range of 2-300 K. Both Fe doping and the concentration of oxygen vacancies had large effects on the negative MR contributions. For the low Fe doping case of x = 0.10, in which both films exhibited metallic behavior, MR was more prominent in the film with fewer oxygen vacancies or equivalently a more metallic film. For semiconducting films, higher MR was observed for more semiconducting films having more oxygen vacancies. A relatively large negative MR ( 36.4%) was observed for the x = 0.30 thin film with a high concentration of oxygen vacancies ( δ = 0.12). The obtained results were compared with MR studies for a polycrystal of (Sr1 - x La x )(Ru1 - x Fe x )O3. These results highlight the crucial role of oxygen stoichiometry in determining the magneto-transport properties in SrRu1 - x Fe x O3 - δ thin films.

Nature of oxygen donors and radiation defects in oxygen-doped germanium

International Nuclear Information System (INIS)

Fukuoka, Noboru; Atobe, Kozo; Honda, Makoto; Matsuda, Koji.

1991-01-01

The nature of oxygen donors and radiation defects in oxygen-doped germanium were studied through measurements of the infrared absorption spectrum, deep level transient spectroscopy spectrum and carrier concentration. It is revealed that a new donor is not formed in oxygen-doped germanium. An A-center (interstitial oxygen-vacancy pair) forms a complex with a thermal donor in its annealing stage at 60degC-140degC. The introduction rate of defects by 1.5 MeV electron irradiation was enhanced in thermal-donor-doped samples. (author)

Modulation of resistive switching characteristics for individual BaTiO3 microfiber by surface oxygen vacancies

Science.gov (United States)

Miao, Zhilei; Chen, Lei; Zhou, Fang; Wang, Qiang

2018-01-01

Different from traditional thin-film BaTiO3 (BTO) RRAM device with planar structure, individual microfiber-shaped RRAM device, showing promising application potentials in the micro-sized non-volatile memory system, has not been investigated so far to demonstrate resistive switching behavior. In this work, individual sol-gel BTO microfiber has been formed using the draw-bench method, followed by annealing in different atmospheres of air and argon, respectively. The resistive switching characteristics of the individual BTO microfiber have been investigated by employing double-probe SEM measurement system, which shows great convenience to test local electrical properties by modulating the contact sites between the W probes and the BTO microfiber. For the sample annealed in air, the average resistive ON/OFF ratio is as high as 108, enhanced about four orders in comparison with the counterpart that annealed in Argon. For the sample annealed in argon ambience, the weakened resistive ON/OFF ratio can be attributed to the increased presence of oxygen vacancies in the surface of BTO fibers, and the underlying electrical conduction mechanisms are also discussed.

Density functional study on the heterogeneous oxidation of NO over α-Fe_2O_3 catalyst by H_2O_2: Effect of oxygen vacancy

International Nuclear Information System (INIS)

Song, Zijian; Wang, Ben; Yu, Jie; Ma, Chuan; Zhou, Changsong; Chen, Tao; Yan, Qianqian; Wang, Ke; Sun, Lushi

2017-01-01

Highlights: • NO and H_2O_2 adsorption on perfect and oxygen defect α-Fe_2O_3 (0 0 1) surface were studied by DFT calculations. • H_2O_2 shows high chemical reactivity for its adsorption on oxygen defect α-Fe_2O_3 (0 0 1) surface. • Oxygen vacancy plays an important role of the catalytic oxidation of NO by H_2O_2 over the α-Fe_2O_3 catalyst surfaces. • Mechanism of NO oxidation over α-Fe_2O_3 (0 0 1) surface by H_2O_2 was explained. - Abstract: Catalytic oxidation with H_2O_2 is a promising method for NOx emission control in coal-fired power plants. Hematite-based catalysts are attracting increased attention because of their surface redox reactivity. To elucidate the NO oxidation mechanism on α-Fe_2O_3 surfaces, density functional theory (DFT) calculations were conducted by investigating the adsorption characteristics of nitric oxide (NO) and hydrogen peroxide (H_2O_2) on perfect and oxygen defect α-Fe_2O_3 (0 0 1) surfaces. Results show that NO was molecularly adsorbed on two kinds of surfaces. H_2O_2 adsorption on perfect surface was also in a molecular form; however, H_2O_2 dissociation occurred on oxygen defect α-Fe_2O_3 (0 0 1) surface. The adsorption intensities of the two gas molecules in perfect α-Fe_2O_3 (0 0 1) surface followed the order NO > H_2O_2, and the opposite was true for the oxygen defect α-Fe_2O_3 (0 0 1). Oxygen vacancy remarkably enhanced the adsorption intensities of NO and H_2O_2 and promoted H_2O_2 decomposition on catalyst surface. As an oxidative product of NO, HNO_2 was synthesized when NO and H_2O_2 co-adsorbed on the oxygen defect α-Fe_2O_3 (0 0 1) surface. Analyses of Mulliken population, electron density difference, and partial density of states showed that H_2O_2 decomposition followed the Haber–Weiss mechanism. The trends of equilibrium constants suggested that NO adsorption on α-Fe_2O_3 (0 0 1) surface was more favorable at low than at high temperatures, whereas H_2O_2 adsorption was favorable between 375 and

Efficacy of surface error corrections to density functional theory calculations of vacancy formation energy in transition metals.

Science.gov (United States)

Nandi, Prithwish Kumar; Valsakumar, M C; Chandra, Sharat; Sahu, H K; Sundar, C S

2010-09-01

We calculate properties like equilibrium lattice parameter, bulk modulus and monovacancy formation energy for nickel (Ni), iron (Fe) and chromium (Cr) using Kohn-Sham density functional theory (DFT). We compare the relative performance of local density approximation (LDA) and generalized gradient approximation (GGA) for predicting such physical properties for these metals. We also make a relative study between two different flavors of GGA exchange correlation functional, namely PW91 and PBE. These calculations show that there is a discrepancy between DFT calculations and experimental data. In order to understand this discrepancy in the calculation of vacancy formation energy, we introduce a correction for the surface intrinsic error corresponding to an exchange correlation functional using the scheme implemented by Mattsson et al (2006 Phys. Rev. B 73 195123) and compare the effectiveness of the correction scheme for Al and the 3d transition metals.

Thickness independent reduced forming voltage in oxygen engineered HfO{sub 2} based resistive switching memories

Energy Technology Data Exchange (ETDEWEB)

Sharath, S. U., E-mail: sharath@oxide.tu-darmstadt.de; Kurian, J.; Komissinskiy, P.; Hildebrandt, E.; Alff, L. [Institute of Materials Science, Technische Universität Darmstadt, 64287 Darmstadt (Germany); Bertaud, T.; Walczyk, C.; Calka, P. [IHP, Im Technologiepark 25, 15236 Frankfurt Oder (Germany); Schroeder, T. [IHP, Im Technologiepark 25, 15236 Frankfurt Oder (Germany); Brandenburgische Technische Universität, Konrad-Zuse-Strasse 1, 03046 Cottbus (Germany)

2014-08-18

The conducting filament forming voltage of stoichiometric hafnium oxide based resistive switching layers increases linearly with layer thickness. Using strongly reduced oxygen deficient hafnium oxide thin films grown on polycrystalline TiN/Si(001) substrates, the thickness dependence of the forming voltage is strongly suppressed. Instead, an almost constant forming voltage of about 3 V is observed up to 200 nm layer thickness. This effect suggests that filament formation and switching occurs for all samples in an oxidized HfO{sub 2} surface layer of a few nanometer thickness while the highly oxygen deficient thin film itself merely serves as a oxygen vacancy reservoir.

Tuning the electronic structure of SrTiO3/SrFeO3−x superlattices via composition and vacancy control

Directory of Open Access Journals (Sweden)

Robert F. Berger

2014-04-01

Full Text Available Using density functional theory-based calculations, we explore the effects of oxygen vacancies and epitaxial layering on the atomic, magnetic, and electronic structure of (SrTiO3n(SrFeO3−x1 superlattices. While structures without oxygen vacancies (x = 0 possess small or non-existent band gaps and ferromagnetic ordering in their iron layers, those with large vacancy concentrations (x = 0.5 have much larger gaps and antiferromagnetic ordering. Though the computed gaps depend numerically on the delicate energetic balance of vacancy ordering and on the value of Hubbard U eff used in the calculations, we demonstrate that changes in layering can tune the band gaps of these superlattices below that of SrTiO3 (3.2 eV by raising their valence band maxima. This suggests the possibility that these superlattices could absorb in the solar spectrum, and could serve as water-splitting photocatalysts.

Application of Electron Structure Calculations to the Migration of Oxygen through a Perovskite Membrane

Science.gov (United States)

Wood, Douglas A.

The focus of this thesis is the application of electron structure calculations, particularly density functional theory, to the analysis of the process by which oxygen is able to migrate through a perovskite crystal. This property creates the possibility of using perovskite membranes to separate oxygen from air. This could be applied to the generation of syngas directly from natural gas without the need for a separate air separation unit. A perovskite has the nominal formula ABO3 where A is a rare earth type cation and B is a transition type cation. The structure consists of the B cations arranged in a cube with the A cation in the center. The oxygen ions are located at the midpoint of each B-B cube edge and form an octahedron centered on each B cation. Any real perovskite crystal will contain a certain fraction of vacancies at the oxygen sites. Oxygen migrates through the crystal by jumping from a neighboring site to the vacancy. The permeability of the crystal is thus a function of the concentration of vacancies and the activation energy of the jump from a neighboring site to the vacancy. These properties can be modified by adding dopants for the A and B cations. The literature contains a substantial amount of experimental work on the effect of such dopants. The overall migration process can be divided into components (i) the concentration of oxygen vacancies, (ii) the activation energy for a neighboring on-site oxygen atom to jump to the vacant site, (iii) the concentration of surface vacancies, and (iv) the processes by which oxygen ions transfer back and forth between the perovskite surface and the contiguous vapor space. Using SrTiO3 and LaCoO3 as model compounds, DFT calculations have been used to (i) calculate various properties of the perovskite crystal, (ii) estimate the activation energy of a jump between an occupied oxygen site and an adjacent vacant oxygen site, (iii) predict the effects of various dopants at the A and B site and (iv) analyze the

Vacancy formation energies in close-packed crystals correlated with melting temperature via thermodynamics and liquid structure

International Nuclear Information System (INIS)

Rashid, R.I.M.A.; March, N.H.

1988-08-01

In earlier work, the vacancy formation energy E v in close-packed crystals, in units of the thermal energy k B T m at the melting temperature T m , has been connected with compressibility and specific heats, plus terms dependent on the liquid structure at T m . Here, this connection has been examined quantitatively for (a) the insulating condensed rare gases Ne, Ar and Kr, and (b) a variety of close-packed metals. For case (a), E v /k B T m can be calculated directly from thermodynamic data to obtain agreement with experiment for Ar and Kr, though not for Ne. A 'residual' contribution is estimated for Ar and Kr from diffraction and computer experiments on the density dependence of the liquid pair correlation function and is shown to be very small. Agreement is less impressive for case (b) for the eight close-packed metals for which all data required is known, the thermodynamic formula giving an average value E v /k B T m =7.8+-1.1 whereas experiment yields 9.4+-1.8. However, for the body-centred cubic alkalis the thermodynamic average value of 4.5+-0.5 is much lower than the experimental value 11.5+-2.0 consistent with the known role of ionic relaxation round the vacancy in such open structures. (author). 16 refs, 2 tabs

Electrochemical transformations of oxygen and the defect structure of solid solutions on the basis of alkaline earth metal ortho-vanadates

International Nuclear Information System (INIS)

Khodos, M.Ya.; Belysheva, G.M.; Brajnina, Kh.Z.

1986-01-01

Effect of iso- and heterovalent substitution in the structure of alkaline earth metal ortho-vanadates and synthesis conditions, simulating the definite type of their crystal lattice disordering, on the character of potentiodynamic anodic-cathodic curves has been investigated by the method of cyclic voltammetry. Correlation between signals observed and the defect structure of oxide compounds is refined. Oxygen chemisorption is shown to be determined by concentration of nonequilibrium oxygen vacancies, which formation is accompanied by appearance of quasi-free electrons

Vacancy-Mediated Magnetism in Pure Copper Oxide Nanoparticles

Science.gov (United States)

2010-01-01

Room temperature ferromagnetism (RTF) is observed in pure copper oxide (CuO) nanoparticles which were prepared by precipitation method with the post-annealing in air without any ferromagnetic dopant. X-ray photoelectron spectroscopy (XPS) result indicates that the mixture valence states of Cu1+ and Cu2+ ions exist at the surface of the particles. Vacuum annealing enhances the ferromagnetism (FM) of CuO nanoparticles, while oxygen atmosphere annealing reduces it. The origin of FM is suggested to the oxygen vacancies at the surface/or interface of the particles. Such a ferromagnet without the presence of any transition metal could be a very good option for a class of spintronics. PMID:20671775

Absolute quantum yield measurements for the formation of oxygen ...

Indian Academy of Sciences (India)

Unknown

Abstract. The dynamics of formation of oxygen atoms after UV photoexcitation of .... The SO2 pressure in the cell was typically 30–55 mTorr (monitored by an MKS .... With this value the quantum yield for O(3P) formation could be calculated to.

The effect of electron localization on the electronic structure and migration barrier of oxygen vacancies in rutile.

Science.gov (United States)

Zhu, Linggang; Hu, Qing-Miao; Yang, Rui

2014-02-05

By applying the on-site Coulomb interaction (Hubbard term U) to the Ti d orbital, the influence of electron localization on the electronic structure as well as the transport of oxygen vacancies (VO) in rutile was investigated. With U = 4.5 eV, the positions of defect states in the bandgap were correctly reproduced. The unbonded electrons generated by taking out one neutral oxygen atom are spin parallel and mainly localized on the Ti atoms near VO, giving rise to a magnetic moment of 2 μB, in agreement with the experimental finding. With regard to the migration barrier of VO, surprisingly, we found that U = 4.5 eV only changed the value of the energy barrier by ±0.15 eV, depending on the diffusion path. The most probable diffusion path (along [110]) is the same as that calculated by using the traditional GGA functional. To validate the GGA + U method itself, a hybrid functional with a smaller supercell was used, and the trend of the more probable diffusion path was not changed. In this regard, the traditional GGA functional might still be reliable in the study of intrinsic-defect transportation in rutile. Analyzing the atomic distortion and density of states of the transition states for different diffusion paths, we found that the anisotropy of the diffusion could be rationalized according to the various atomic relaxations and the different positions of the valence bands relative to the Fermi level of the transition states.

Vibrational properties of vacancy in bcc transition metals using ...

Indian Academy of Sciences (India)

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.

Diffusion of oxygen in uranium dioxide: A first-principles investigation

International Nuclear Information System (INIS)

Gupta, Florence; Brillant, Guillaume; Pasturel, Alain

2010-01-01

Results of ab initio density-functional theory calculations of the migration energies of oxygen vacancies and interstitials in stoichiometric UO 2 are reported. The diffusion of oxygen vacancies in UO 2 is found to be highly anisotropic, and the [1 0 0] direction is energetically favored. The atomic relaxations play an important role in reducing the migration barriers. Within the generalized gradient approximation (GGA), we find that the migration energies of the preferred vacancies and interstitials paths are, respectively, 1.18 and 1.09 eV. With the inclusion of the Hubbard U parameter to account for the 5f electron correlations in GGA+U, the vacancy migration energy is lowered to 1.01 eV while the interstitial migration energy increases slightly to 1.13 eV. We find, however, that the correlation effects have a drastic influence on the mechanism of interstitial migration through the stabilization of Willis-type clusters. Indeed, in contrast to GGA, in GGA+U there is an inversion of the migration path with the so-called 'saddle-point' position being lower in energy than the usual starting position. Thus while the migration barriers are nearly the same in GGA and GGA+U, the mechanisms are completely different. Our results clearly indicate that both vacancies and interstitials contribute almost equally to the diffusion of oxygen in UO 2 .

Understanding the presence of vacancy clusters in ZnO from a kinetic perspective

Science.gov (United States)

Bang, Junhyeok; Kim, Youg-Sung; Park, C. H.; Gao, F.; Zhang, S. B.

2014-06-01

Vacancy clusters have been observed in ZnO by positron-annihilation spectroscopy (PAS), but detailed mechanisms are unclear. This is because the clustering happens in non-equilibrium conditions, for which theoretical method has not been well established. Combining first-principles calculation and kinetic Monte Carlo simulation, we determine the roles of non-equilibrium kinetics on the vacancies clustering. We find that clustering starts with the formation of Zn and O vacancy pairs (VZn - Vo), which further grow by attracting additional mono-vacancies. At this stage, vacancy diffusivity becomes crucial: due to the larger diffusivity of VZn compared to VO, more VZn-abundant clusters are formed than VO-abundant clusters. The large dissociation energy barriers, e.g., over 2.5 eV for (VZn - Vo), suggest that, once formed, it is difficult for the clusters to dissociate. By promoting mono-vacancy diffusion, thermal annealing will increase the size of the clusters. As the PAS is insensitive to VO donor defects, our results suggest an interpretation of the experimental data that could not have been made without the in-depth calculations.

Insight into the effect of screw dislocations and oxygen vacancy defects on the optical nonlinear refraction response in chemically grown ZnO/Al2O3 films

Science.gov (United States)

Agrawal, Arpana; Saroj, Rajendra K.; Dar, Tanveer A.; Baraskar, Priyanka; Sen, Pratima; Dhar, Subhabrata

2017-11-01

We report the effect of screw dislocations and oxygen vacancy defects on the optical nonlinear refraction response of ZnO films grown on a sapphire substrate at various oxygen flow rates using the chemical vapor deposition technique. The nonlinear refraction response was investigated in the off-resonant regime using a CW He-Ne laser source to examine the role of the intermediate bandgap states. It has been observed that the structural defects strongly influence the optical nonlinearity in the off-resonant regime. Nonlinearity has been found to improve as the oxygen flow rate is lowered from 2 sccm to 0.3 sccm. From photoluminescence studies, we observe that the enhanced defect density of the electronic defect levels due to the increased concentration of structural defects (with the decrease in the oxygen flow rate) is responsible for this improved optical nonlinearity along with the thermal effect. This suggests that defect engineering is an effective way to tailor the nonlinearity of ZnO films and their utility for optoelectronic device applications.

Band gap effects of hexagonal boron nitride using oxygen plasma

International Nuclear Information System (INIS)

Sevak Singh, Ram; Leong Chow, Wai; Yingjie Tay, Roland; Hon Tsang, Siu; Mallick, Govind; Tong Teo, Edwin Hang

2014-01-01

Tuning of band gap of hexagonal boron nitride (h-BN) has been a challenging problem due to its inherent chemical stability and inertness. In this work, we report the changes in band gaps in a few layers of chemical vapor deposition processed as-grown h-BN using a simple oxygen plasma treatment. Optical absorption spectra show a trend of band gap narrowing monotonically from 6 eV of pristine h-BN to 4.31 eV when exposed to oxygen plasma for 12 s. The narrowing of band gap causes the reduction in electrical resistance by ∼100 fold. The x-ray photoelectron spectroscopy results of plasma treated hexagonal boron nitride surface show the predominant doping of oxygen for the nitrogen vacancy. Energy sub-band formations inside the band gap of h-BN, due to the incorporation of oxygen dopants, cause a red shift in absorption edge corresponding to the band gap narrowing

Band gap effects of hexagonal boron nitride using oxygen plasma

Energy Technology Data Exchange (ETDEWEB)

Sevak Singh, Ram; Leong Chow, Wai [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Yingjie Tay, Roland [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Temasek Laboratories-NTU, 50 Nanyang Avenue, Singapore 639798 (Singapore); Hon Tsang, Siu [Temasek Laboratories-NTU, 50 Nanyang Avenue, Singapore 639798 (Singapore); Mallick, Govind [Temasek Laboratories-NTU, 50 Nanyang Avenue, Singapore 639798 (Singapore); Weapons and Materials Research Directorate, U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005 (United States); Tong Teo, Edwin Hang, E-mail: htteo@ntu.edu.sg [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore)

2014-04-21

Tuning of band gap of hexagonal boron nitride (h-BN) has been a challenging problem due to its inherent chemical stability and inertness. In this work, we report the changes in band gaps in a few layers of chemical vapor deposition processed as-grown h-BN using a simple oxygen plasma treatment. Optical absorption spectra show a trend of band gap narrowing monotonically from 6 eV of pristine h-BN to 4.31 eV when exposed to oxygen plasma for 12 s. The narrowing of band gap causes the reduction in electrical resistance by ∼100 fold. The x-ray photoelectron spectroscopy results of plasma treated hexagonal boron nitride surface show the predominant doping of oxygen for the nitrogen vacancy. Energy sub-band formations inside the band gap of h-BN, due to the incorporation of oxygen dopants, cause a red shift in absorption edge corresponding to the band gap narrowing.

A critical discussion of the vacancy diffusion model of ion beam induced epitaxial crystallization

International Nuclear Information System (INIS)

Heera, V.

1989-01-01

A simple vacancy diffusion model of ion beam induced epitaxial crystallization of silicon including divacancy formation is developed. The model reproduces some of the experimental findings, as e.g. the dose rate dependence of the crystallization rate. However, the measured activation energy of the ion beam induced epitaxial crystallization cannot be accounted for by vacancy diffusion alone. (author)

Energetics of charged metal clusters containing vacancies

Science.gov (United States)

Pogosov, Valentin V.; Reva, Vitalii I.

2018-01-01

We study theoretically large metal clusters containing vacancies. We propose an approach, which combines the Kohn-Sham results for monovacancy in a bulk of metal and analytical expansions in small parameters cv (relative concentration of vacancies) and RN,v -1, RN ,v being cluster radii. We obtain expressions of the ionization potential and electron affinity in the form of corrections to electron work function, which require only the characteristics of 3D defect-free metal. The Kohn-Sham method is used to calculate the electron profiles, ionization potential, electron affinity, electrical capacitance; dissociation, cohesion, and monovacancy-formation energies of the small perfect clusters NaN, MgN, AlN (N ≤ 270) and the clusters containing a monovacancy (N ≥ 12) in the stabilized-jellium model. The quantum-sized dependences for monovacancy-formation energies are calculated for the Schottky scenario and the "bubble blowing" scenario, and their asymptotic behavior is also determined. It is shown that the asymptotical behaviors of size dependences for these two mechanisms differ from each other and weakly depend on the number of atoms in the cluster. The contribution of monovacancy to energetics of charged clusters and the size dependences of their characteristics and asymptotics are discussed. It is shown that the difference between the characteristics for the neutral and charged clusters is entirely determined by size dependences of ionization potential and electron affinity. Obtained analytical dependences may be useful for the analysis of the results of photoionization experiments and for the estimation of the size dependences of the vacancy concentration including the vicinity of the melting point.

Vacancy clustering behavior in hydrogen-charged martensitic steel AISI 410 under tensile deformation

International Nuclear Information System (INIS)

Sugita, K; Mutou, Y; Shirai, Y

2016-01-01

The formation and accumulation of defects under tensile deformation of hydrogen- charged AISI 410 martensitic steels were investigated by using positron lifetime spectroscopy. During the deformation process, dislocations and vacancy-clusters were introduced and increased with increasing strains. Between hydrogen-charged and uncharged samples with the same tensile strains there was no significant difference in the dislocation density and monovacancy equivalent vacancy density. (paper)

Promoted Fixation of Molecular Nitrogen with Surface Oxygen Vacancies on Plasmon-Enhanced TiO2 Photoelectrodes.

Science.gov (United States)

Li, Chengcheng; Wang, Tuo; Zhao, Zhi-Jian; Yang, Weimin; Li, Jian-Feng; Li, Ang; Yang, Zhilin; Ozin, Geoffrey A; Gong, Jinlong

2018-02-19

A hundred years on, the energy-intensive Haber-Bosch process continues to turn the N 2 in air into fertilizer, nourishing billions of people while causing pollution and greenhouse gas emissions. The urgency of mitigating climate change motivates society to progress toward a more sustainable method for fixing N 2 that is based on clean energy. Surface oxygen vacancies (surface O vac ) hold great potential for N 2 adsorption and activation, but introducing O vac on the very surface without affecting bulk properties remains a great challenge. Fine tuning of the surface O vac by atomic layer deposition is described, forming a thin amorphous TiO 2 layer on plasmon-enhanced rutile TiO 2 /Au nanorods. Surface O vac in the outer amorphous TiO 2 thin layer promote the adsorption and activation of N 2 , which facilitates N 2 reduction to ammonia by excited electrons from ultraviolet-light-driven TiO 2 and visible-light-driven Au surface plasmons. The findings offer a new approach to N 2 photofixation under ambient conditions (that is, room temperature and atmospheric pressure). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen permeation modelling of perovskites

NARCIS (Netherlands)

van Hassel, Bart A.; van Hassel, B.A.; Kawada, Tatsuya; Sakai, Natsuko; Yokokawa, Harumi; Dokiya, Masayuki; Bouwmeester, Henricus J.M.

1993-01-01

A point defect model was used to describe the oxygen nonstoichiometry of the perovskites La0.75Sr0.25CrO3, La0.9Sr0.1FeO3, La0.9Sr0.1CoO3 and La0.8Sr0.2MnO3 as a function of the oxygen partial pressure. Form the oxygen vacancy concentration predicte by the point defect model, the ionic conductivity

Influence of impurities on the evolution of vacancy-type defects in neutron-irradiated nickel

International Nuclear Information System (INIS)

Druzhkov, A.P.; Perminov, D.A.; Arbuzov, V.L.

2012-01-01

Highlights: ► We study, by means of PAS, the effects of purity on damage evolution in neutron-irradiated Ni at 330 K. ► Impurity carbon atoms in solution decrease the cascade efficiency during irradiation. ► C–V complexes are formed on the recovery stage III in impure Ni irradiated with 10 −4 dpa. ► The formation of V-loops and SFTs dominate on stage III with increasing dose level. ► The thermal stability of SFTs in impure Ni is similar to that in pure Ni. - Abstract: In order to investigate the effect of impurities on vacancy defect evolution in nickel, specimens with high (5N) and technical (3N) purity were neutron-irradiated at ∼330 K in the IVV-2M reactor (Russia) to fluencies in the range of 1 × 10 21 –1 × 10 23 n/m 2 (E > 0.1 MeV) corresponding to displacement dose levels in the range of about 0.0001–0.01 dpa and subsequently stepwise annealed to about 900 K. The specimens of Ni with different purities were characterized both in as-irradiated state as well as after post-irradiation annealing by positron annihilation spectroscopy. The formation of three-dimensional vacancy clusters (3D-VCs) in cascades was observed under neutron irradiation. The density and size of 3D-VCs depended not only on dose level, but also on purity. The population of 3D-VCs in the technical Ni is lower than that in the high-purity Ni. 3D-VCs collapse into secondary-type clusters (stacking fault tetrahedra (SFTs) and vacancy loops) during stepwise annealing at 350–450 K (stage III in Ni). The suppression of secondary cluster formation in 3N Ni is attributed to an effective vacancy interaction with impurity carbon atoms, which based on a relatively large vacancy–carbon atom binding energy (0.32–0.35 eV). The trapping of vacancies released at the collapse of 3D-VCs by the interstitial impurity atoms dominates at low irradiation dose level (10 −4 dpa). Thus, we found that carbon impurity atoms have strong effects both on the primary vacancy-type defect

Magnesium Vacancy Segregation and Fast Pipe Diffusion for the ½{110} Edge Dislocation in MgO

Science.gov (United States)

Walker, A. M.; Zhang, F.; Wright, K.; Gale, J. D.

2009-12-01

The movement of point defects in minerals plays a key role in determining their rheological properties, both by permitting diffusional creep and by allowing recovery by dislocation climb. Point defect diffusion can also control the kinetics of phase transitions and grain growth, and can determine the rate of chemical equilibration between phases. Because of this, and the difficulties associated with experimental studies of diffusion, the simulation of point defect formation and migration has been a subject of considerable interest in computational mineral physics. So far, studies have concentrated on point defects moving through otherwise perfect crystals. In this work we examine the behavior of magnesium vacancies close to the core of an edge dislocation in MgO and find that the dislocation dramatically changes the behavior of the point defect. An atomic scale model of the ½{110} edge dislocation in MgO was constructed by applying the anisotropic linear elastic displacement field to the crystal structure and subsequently minimizing the energy of the crystal close to the dislocation core using a parameterized potential model. This process yielded the structure of an isolated edge dislocation in an otherwise perfect crystal. The energy cost associated with introducing magnesium vacancies around the dislocation was then mapped and compared to the formation energy of an isolated magnesium vacancy in bulk MgO. We find that the formation energy of magnesium vacancies around the dislocation mirrors the elastic strain field. Above the dislocation line σxx and σyy are negative and the strain field is compressional. Atoms are squeezed together to make room for the extra half plane effectively increasing the pressure in this region. Below the dislocation line σxx and σyy are positive and the strain field is dilatational. Planes of atoms are pulled apart to avoid a discontinuity across the glide plane and the effective pressure is decreased. In the region with a

Phase equilibrium of PuO2-x - Pu2O3 based on first-principles calculations and configurational entropy change

International Nuclear Information System (INIS)

Minamoto, Satoshi; Kato, Masato; Konashi, Kenji

2011-01-01

Combination of an oxygen vacancy formation energy calculated using first-principles approach and the configurational entropy change treated within the framework of statistical mechanics gives an expression of the Gibbs free energy at large deviation from stoichiometry of plutonium oxide PuO 2 . An oxygen vacancy formation energy 4.20 eV derived from our previously first-principles calculation was used to evaluate the Gibbs free energy change due to oxygen vacancies in the crystal. The oxygen partial pressures then can be evaluated from the change of the free energy with two fitting parameters (a vacancy-vacancy interaction energy and vibration entropy change due to induced vacancies). Derived thermodynamic expression for the free energy based on the SGTE thermodynamic data for the stoichiometric PuO 2 and the Pu 2 O 3 compounds was further incorporated into the CALPHAD modeling, then phase equilibrium between the stoichiometric Pu 2 O 3 and non-stoichiometric PuO 2-x were reproduced.

Phase equilibrium of PuO{sub 2-x} - Pu{sub 2}O{sub 3} based on first-principles calculations and configurational entropy change

Energy Technology Data Exchange (ETDEWEB)

Minamoto, Satoshi, E-mail: satoshi.minamoto@ctc-g.co.jp [ITOCHU Techno-Solutions Corporation, Kasumigaseki, 2-5, Kasumigaseki 3-chome, Chiyoda-ku, Tokyo 100-6080 (Japan); Kato, Masato [Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki (Japan); Konashi, Kenji [Institute for Materials Research, Tohoku University, Oarai-chou, Ibaraki (Japan)

2011-05-31

Combination of an oxygen vacancy formation energy calculated using first-principles approach and the configurational entropy change treated within the framework of statistical mechanics gives an expression of the Gibbs free energy at large deviation from stoichiometry of plutonium oxide PuO{sub 2}. An oxygen vacancy formation energy 4.20 eV derived from our previously first-principles calculation was used to evaluate the Gibbs free energy change due to oxygen vacancies in the crystal. The oxygen partial pressures then can be evaluated from the change of the free energy with two fitting parameters (a vacancy-vacancy interaction energy and vibration entropy change due to induced vacancies). Derived thermodynamic expression for the free energy based on the SGTE thermodynamic data for the stoichiometric PuO{sub 2} and the Pu{sub 2}O{sub 3} compounds was further incorporated into the CALPHAD modeling, then phase equilibrium between the stoichiometric Pu{sub 2}O{sub 3} and non-stoichiometric PuO{sub 2-x} were reproduced.

Chemisorption of oxygen and subsequent reactions on low index surfaces of β-Mo₂C

DEFF Research Database (Denmark)

Shi, Xue Rong; Wang, Shengguang; Wang, Jianguo

2016-01-01

to the carbon vacancy were identified. We examined the effect of oxygen coverage on the morphology of β-Mo2C by plotting the equilibrium crystal shape. Thermodynamic effect of temperature and reactant or product pressure on the CO/CO2 desorption were investigated. The CO/CO2 desorption is more favorable...... at the saturated oxygen coverage than the low oxygen coverage thermodynamically. The subsequent oxygen diffusion to the carbon vacancy after CO/CO2 desorption may happen depending on the surfaces and oxygen coverage....

Vacancy-indium clusters in implanted germanium

KAUST Repository

Chroneos, Alexander I.

2010-04-01

Secondary ion mass spectroscopy measurements of heavily indium doped germanium samples revealed that a significant proportion of the indium dose is immobile. Using electronic structure calculations we address the possibility of indium clustering with point defects by predicting the stability of indium-vacancy clusters, InnVm. We find that the formation of large clusters is energetically favorable, which can explain the immobility of the indium ions. © 2010 Elsevier B.V. All rights reserved.

Vacancy-indium clusters in implanted germanium

KAUST Repository

Chroneos, Alexander I.; Kube, R.; Bracht, Hartmut A.; Grimes, Robin W.; Schwingenschlö gl, Udo

2010-01-01

Secondary ion mass spectroscopy measurements of heavily indium doped germanium samples revealed that a significant proportion of the indium dose is immobile. Using electronic structure calculations we address the possibility of indium clustering with point defects by predicting the stability of indium-vacancy clusters, InnVm. We find that the formation of large clusters is energetically favorable, which can explain the immobility of the indium ions. © 2010 Elsevier B.V. All rights reserved.

Oxygen defects in amorphous Al{sub 2}O{sub 3}: A hybrid functional study

Energy Technology Data Exchange (ETDEWEB)

Guo, Zhendong, E-mail: zhendong.guo@epfl.ch; Ambrosio, Francesco; Pasquarello, Alfredo [Chaire de Simulation à l' Echelle Atomique (CSEA), Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland)

2016-08-08

The electronic properties of the oxygen vacancy and interstitial in amorphous Al{sub 2}O{sub 3} are studied via ab initio molecular dynamics simulations and hybrid functional calculations. Our results indicate that these defects do not occur in amorphous Al{sub 2}O{sub 3}, due to structural rearrangements which assimilate the defect structure and cause a delocalization of the associated defect levels. The imbalance of oxygen leads to a nonstoichiometric compound in which the oxygen occurs in the form of O{sup 2–} ions. Intrinsic oxygen defects are found to be unable to trap excess electrons. For low Fermi energies, the formation of peroxy linkages is found to be favored leading to the capture of holes. The relative +2/0 defect levels occur at 2.5 eV from the valence band.

Understanding the presence of vacancy clusters in ZnO from a kinetic perspective

International Nuclear Information System (INIS)

Bang, Junhyeok; Zhang, S. B.; Kim, Youg-Sung; Park, C. H.; Gao, F.

2014-01-01

Vacancy clusters have been observed in ZnO by positron-annihilation spectroscopy (PAS), but detailed mechanisms are unclear. This is because the clustering happens in non-equilibrium conditions, for which theoretical method has not been well established. Combining first-principles calculation and kinetic Monte Carlo simulation, we determine the roles of non-equilibrium kinetics on the vacancies clustering. We find that clustering starts with the formation of Zn and O vacancy pairs (V Zn  − Vo), which further grow by attracting additional mono-vacancies. At this stage, vacancy diffusivity becomes crucial: due to the larger diffusivity of V Zn compared to V O , more V Zn -abundant clusters are formed than V O -abundant clusters. The large dissociation energy barriers, e.g., over 2.5 eV for (V Zn  − Vo), suggest that, once formed, it is difficult for the clusters to dissociate. By promoting mono-vacancy diffusion, thermal annealing will increase the size of the clusters. As the PAS is insensitive to V O donor defects, our results suggest an interpretation of the experimental data that could not have been made without the in-depth calculations.

Radiation-induced defects in LiAlO{sub 2} crystals: Holes trapped by lithium vacancies and their role in thermoluminescence

Energy Technology Data Exchange (ETDEWEB)

Holston, M.S.; McClory, J.W.; Giles, N.C. [Department of Engineering Physics, Air Force Institute of Technology, Wright-Patterson Air Force Base, OH 45433 (United States); Halliburton, L.E., E-mail: Larry.Halliburton@mail.wvu.edu [Department of Physics and Astronomy, West Virginia University, Morgantown, WV 26506 (United States)

2015-04-15

Electron paramagnetic resonance (EPR) is used to identify the primary hole trap in undoped lithium aluminate (LiAlO{sub 2}) crystals. Our interest in this material arises because it is a candidate for radiation detection applications involving either optically stimulated luminescence (OSL) or thermoluminescence (TL). During an x-ray irradiation at room temperature, holes are trapped at oxygen ions adjacent to lithium vacancies. Large concentrations of these lithium vacancies are introduced into the crystal during growth. With the magnetic field along the [001] direction, the EPR spectrum from these trapped-hole centers consists of eleven lines, evenly spaced but with varying intensities, caused by nearly equal hyperfine interactions with two {sup 27}Al nuclei (I=5/2, 100% abundant). The g matrix is determined from the angular dependence of the EPR spectrum and has principal values of 2.0130, 2.0675, and 2.0015. These g shifts strongly support the model of a hole in a p orbital on an oxygen ion. The adjacent lithium vacancy stabilizes the hole on the oxygen ion. A sequence of pulsed thermal anneals above room temperature shows that the EPR spectrum from the holes trapped adjacent to the lithium vacancies disappears in the 90–120 °C range. The thermal decay of these hole centers directly correlates with an intense TL peak near 105 °C. Signals at lower magnetic field in the 9.4 GHz EPR spectra suggest that the electron trap associated with this TL peak at 105 °C may be a transition-metal-ion impurity, most likely Fe, located at a cation site. Additional less intense TL peaks are observed near 138, 176, and 278 °C. - Highlights: • Undoped LiAlO{sub 2} crystals are irradiated at room temperature with x-rays. • EPR is used to identify holes trapped at oxygen ions adjacent to lithium vacancies. • Thermal decay of the EPR spectrum correlates with an intense TL peak at 105 °C.

Memristive behaviour of Si-Al oxynitride thin films: the role of oxygen and nitrogen vacancies in the electroforming process

Science.gov (United States)

Blázquez, O.; Martín, G.; Camps, I.; Mariscal, A.; López-Vidrier, J.; Ramírez, J. M.; Hernández, S.; Estradé, S.; Peiró, F.; Serna, R.; Garrido, B.

2018-06-01

The resistive switching properties of silicon-aluminium oxynitride (SiAlON) based devices have been studied. Electrical transport mechanisms in both resistance states were determined, exhibiting an ohmic behaviour at low resistance and a defect-related Poole‑Frenkel mechanism at high resistance. Nevertheless, some features of the Al top-electrode are generated during the initial electroforming, suggesting some material modifications. An in-depth microscopic study at the nanoscale has been performed after the electroforming process, by acquiring scanning electron microscopy and transmission electron microscopy images. The direct observation of the devices confirmed features on the top electrode with bubble-like appearance, as well as some precipitates within the SiAlON. Chemical analysis by electron energy loss spectroscopy has demonstrated that there is an out-diffusion of oxygen and nitrogen ions from the SiAlON layer towards the electrode, thus forming silicon-rich paths within the dielectric layer and indicating vacancy change to be the main mechanism in the resistive switching.

Magnetoresistance Versus Oxygen Deficiency in Epi-stabilized SrRu1 - x Fe x O3 - δ Thin Films.

Science.gov (United States)

Dash, Umasankar; Acharya, Susant Kumar; Lee, Bo Wha; Jung, Chang Uk

2017-12-01

Oxygen vacancies have a profound effect on the magnetic, electronic, and transport properties of transition metal oxide materials. Here, we studied the influence of oxygen vacancies on the magnetoresistance (MR) properties of SrRu 1 - x Fe x O 3 - δ epitaxial thin films (x = 0.10, 0.20, and 0.30). For this purpose, we synthesized highly strained epitaxial SrRu 1 - x Fe x O 3 - δ thin films with atomically flat surfaces containing different amounts of oxygen vacancies using pulsed laser deposition. Without an applied magnetic field, the films with x = 0.10 and 0.20 showed a metal-insulator transition, while the x = 0.30 thin film showed insulating behavior over the entire temperature range of 2-300 K. Both Fe doping and the concentration of oxygen vacancies had large effects on the negative MR contributions. For the low Fe doping case of x = 0.10, in which both films exhibited metallic behavior, MR was more prominent in the film with fewer oxygen vacancies or equivalently a more metallic film. For semiconducting films, higher MR was observed for more semiconducting films having more oxygen vacancies. A relatively large negative MR (~36.4%) was observed for the x = 0.30 thin film with a high concentration of oxygen vacancies (δ = 0.12). The obtained results were compared with MR studies for a polycrystal of (Sr 1 - x La x )(Ru 1 - x Fe x )O 3 . These results highlight the crucial role of oxygen stoichiometry in determining the magneto-transport properties in SrRu 1 - x Fe x O 3 - δ thin films.

Synthesis of surface oxygen-deficient BiPO{sub 4} nanocubes with enhanced visible light induced photocatalytic activity

Energy Technology Data Exchange (ETDEWEB)

Shi, Bingtao; Yin, Haoyong; Li, Tao; Gong, Jianying; Lv, Shumei; Nie, Qiulin, E-mail: yhy@hdu.edu.cn [College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou (China)

2017-05-15

The visible light driven BiPO{sub 4} nanocubes with sufficient surface oxygen deficiency were fabricated by a hydrothermal process and subsequently ultrasonic assistant Fe reduction process. The products were characterized by XRD, DRS, XPS, SEM and TEM which showed that the BiPO{sub 4} had cuboid-like shape with a smooth surface and clear edges and the oxygen vacancies were successfully introduced on the surface of the BiPO{sub 4} nanocubes. The as prepared oxygen-deficient BiPO{sub 4} nanocubes showed greatly enhanced visible light induced photocatalytic activity in degradation of Rhodamine B. The enhanced photocatalytic performance and expanded visible light response of BiPO{sub 4} may be due to the introduction of surface oxygen vacancies which can generate the oxygen vacancies mid-gap states lower to the conduction band of BiPO{sub 4}. (author)

Cation vacancies and electrical compensation in Sb-doped thin-film SnO2 and ZnO

International Nuclear Information System (INIS)

Korhonen, E; Prozheeva, V; Tuomisto, F; Bierwagen, O; Speck, J S; White, M E; Galazka, Z; Liu, H; Izyumskaya, N; Avrutin, V; Özgür, Ü; Morkoç, H

2015-01-01

We present positron annihilation results on Sb-doped SnO 2 and ZnO thin films. The vacancy types and the effect of vacancies on the electrical properties of these intrinsically n-type transparent semiconducting oxides are studied. We find that in both materials low and moderate Sb-doping leads to formation of vacancy clusters of variable sizes. However, at high doping levels cation vacancy defects dominate the positron annihilation signal. These defects, when at sufficient concentrations, can efficiently compensate the n-type doping produced by Sb. This is the case in ZnO, but in SnO 2 the concentrations appear too low to cause significant compensation. (invited article)

Cation vacancies and electrical compensation in Sb-doped thin-film SnO2 and ZnO

Science.gov (United States)

Korhonen, E.; Prozheeva, V.; Tuomisto, F.; Bierwagen, O.; Speck, J. S.; White, M. E.; Galazka, Z.; Liu, H.; Izyumskaya, N.; Avrutin, V.; Özgür, Ü.; Morkoç, H.

2015-02-01

We present positron annihilation results on Sb-doped SnO2 and ZnO thin films. The vacancy types and the effect of vacancies on the electrical properties of these intrinsically n-type transparent semiconducting oxides are studied. We find that in both materials low and moderate Sb-doping leads to formation of vacancy clusters of variable sizes. However, at high doping levels cation vacancy defects dominate the positron annihilation signal. These defects, when at sufficient concentrations, can efficiently compensate the n-type doping produced by Sb. This is the case in ZnO, but in SnO2 the concentrations appear too low to cause significant compensation.

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

Energy Technology Data Exchange (ETDEWEB)

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.

Stratigraphy on Oxygen and Carbon Isotope of Paciran Formation East Java

International Nuclear Information System (INIS)

Premonowati; R P Koesoemadinata; Harsono-Pringgoprawiro; Wahyoe-S-Hantoro

2004-01-01

Paleotemperature fluctuation in tropical zone (centennial and decad al scale) has been known. It's based on stable isotopic analysis from each of unconformity zones. Those boundaries have derived on reef units of shallows marine reef complex of Paciran Formation, Tuban area in Northeast Java Basin. From 25 samples have been choosen on undeformed calcite and analyzed by oxygen and carbon stable isotope. It used to validizing a sea level changes during the formation to Reef 1 to Reef 17 from Paciran formation with sea surface temperature (SST) since 4 Ma until now. On early forming of Reef 1 to Reef 3 (since 4 Ma - 2,88 Ma), sea level occurred marine flooding surface. Since the formation of reef 4 (2,59 Ma) to Reef 8 (1,4 Ma) occurred stagnant temperature and almost to warmer condition. Then, δ 18 O have arise up drastically to 5 0/00 and shows warmer condition to Reef 8 formation, in contrary, the sea level have been arised to Reef 10 formation (0,7 Ma). The temperature have been fluctuated between 0,5 o and 1 o C until the formation of Reef 17 (Early Holocene) and continued to Reef 17 formation at 2 o C based on the rapidity sampling of Po rites sp. Wholly, in centennial scale, since the formation of Reef 4 (2,59 Ma) to Reef 17 (1 Ma), the curve of oxygen stable isotope shows decrease or cooler condition. Those condition have conducted to sea level drop since the formation to Reef 7 and Reef 8. There are 4 periods of interglacial since the formation of Reef 4. The warmer condition indicated since the formation of Reef 9, Reef 11 and Reef 17. Recently, a curve of oxygen isotopes reveals warmer drastically or sea level have been arisen. (author)

Origin and enhancement of spin polarized current in diluted magnetic oxides by oxygen vacancies

Energy Technology Data Exchange (ETDEWEB)

Chou, Hsiung, E-mail: hchou@mail.nsysu.edu.tw; Yang, Kung-Shang; Tsao, Yao-Chung; Dwivedi, G. D.; Lin, Cheng-Pang [Department of Physics, National Sun Yat-Sen University, 70, Lienhai Road, Gushan District, Kaohsiung 804, Taiwan (China); Sun, Shih-Jye [Department of Applied Physics, National Kaohsiung University, 700, Gaoxiongdaxue Rd., Nanzi District, Kaohsiung 811, Taiwan (China); Lin, L. K.; Lee, S. F. [Institute of Physics, Academia Sinica, 128 Academia Road, Section 2, Nankang, Taipei 115, Taiwan (China)

2016-04-04

Spin polarized current (SPC) is a crucial characteristic of diluted magnetic oxides due to the potential application of oxides in spintronic devices. However, most research has been focused on ferromagnetic properties rather than polarization of electric current, because direct measurements are difficult and the origin of SPC has yet to be fully understood. The method to increase the SPC percentage is beyond practical consideration at present. To address this problem, we focus on the role of oxygen vacancies (V{sub O}) on SPC, which are controlled by growing the Co-doped ZnO thin-films at room temperature in a reducing atmosphere [Ar + (1%–30%)H{sub 2}]. We found that the conductivity increases with an increase of V{sub O} via two independent channels: the variable range hopping (VRH) within localized states and the itinerant transport in the conduction band. The point contact Andreev reflection measurements at 4.2 K, where the electric conduction is governed only by the VRH mechanism, prove that the current flowing in the VRH hopping channel is SPC. The percentage of SPC increases with the introduction of V{sub O} and increase in its concentration. The transport measurement shows that by manipulating V{sub O}, one can control the percentage of VRH hopping conduction such that it can even dominate room temperature conduction. The highest achieved SPC ratio at room temperature was 80%.

Ab initio atomic thermodynamics investigation on oxygen defects in the anatase TiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Cheng, Zhijun [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Liu, Tingyu, E-mail: liutyyxj@163.com [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Yang, Chenxing; Gan, Haixiu [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Chen, Jianyu [Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China); Zhang, Feiwu [Nanochemistry Research Institute, Curtin University, GPO Box U1987, Perth, WA 6845 (Australia)

2013-01-05

Highlights: Black-Right-Pointing-Pointer Three typical oxygen defects under the different annealing conditions have been studied. Black-Right-Pointing-Pointer The oxygen vacancy is easier to form at the surface than in the bulk. Black-Right-Pointing-Pointer The adsorption of O{sub 2} whose orientation is parallel to the surface should be more favorable. Black-Right-Pointing-Pointer The reduction reaction may firstly undertake at the surface during the annealing treatment. Black-Right-Pointing-Pointer The interstitial oxygen has important contribution to lead to the reduction of the band gap. - Abstract: In the framework of the ab initio atomic thermodynamics, the preliminary analysis of the oxygen defects in anatase TiO{sub 2} has been done by investigating the influence of the annealing treatment under representative conditions on three typical oxygen defects, that is, oxygen vacancy, oxygen adsorption and oxygen interstitial. Our results in this study agree well with the related experimental results. The molecular species of the adsorbed O{sub 2} is subject to the ratio of the number of the O{sub 2} to that of the vacancy, as well as to the initial orientation of O{sub 2} relative to the surface (101). Whatever the annealing condition is, the oxygen vacancy is easier to form at the surface than in the bulk indicating that the reduction reaction may firstly undertake at the surface during the annealing treatment, which is consistent with the phase transformation experiments. The molecular ion, peroxide species, caused by the interstitial oxygen has important contribution to the top of the valence band and lead to the reduction of the band gap.

Ordering of vacancies on Si(001)

NARCIS (Netherlands)

Zandvliet, Henricus J.W.

1997-01-01

Missing dimer vacancies are always present on the clean Si(001) surface. The vacancy density can be increased by ion bombardment (Xe+, Ar+), etching (O2, Br2, I2, etc.) or Ni contamination. The equilibrium shape at low vacancy concentrations (<0.2¿0.3 monolayers) of these vacancy islands is

Oxygen nonstoichiometry and ionic transport properties of La0.4Sr0.6CoO3-delta .

Science.gov (United States)

Sitte, W; Bucher, E; Benisek, A; Preis, W

2001-09-01

Homogeneous samples of La0.4Sr0.6CoO3-delta were obtained by the glycine nitrate process. The oxygen nonstoichiometry was determined from oxygen exchange measurements as a function of oxygen partial pressure (10(-4) bar PO2 PO2-range between 10(-4) and 10(-2) bar to yield D and the ionic conductivity sigma(i) from the long time solution of the diffusion equation. Values for D from polarization measurements at T= 775 degrees C and from oxygen exchange measurements at T= 725 degrees C are in good agreement with each other. D and sigma(1) increase with increasing PO2 (10(-4) to 10(-2) bar). The ionic conductivity shows a maximum at 3-delta approximately 2.82 and decreases with decreasing oxygen content indicating the possible formation of vacancy ordered structures.

O vacancy formation in (Pr/Gd)BaCo2O5.5 and the role of antisite defects

KAUST Repository

Omotayo Akande, Salawu

2017-04-20

In search for materials for intermediate temperature solid oxide fuel cells, (Pr/Gd)BaCo2O5.5 is investigated by first principles calculations. Antisite defects are considered as they may modify the electronic and O diffusion properties but are rarely studied in double perovskite oxides. Octahedrally coordinated Co atoms are shown to realize intermediate and high spin states for PrBaCo2O5.5 and GdBaCo2O5.5, respectively, while pyramidally coordinated Co atoms always have high spin. It turns out that O vacancy formation is significantly easier in PrBaCo2O5.5 than in GdBaCo2O5.5, the difference in formation energy being hardly modified by antisite defects. While pyramidally coordinated Co atoms are not affected, we show that the presence of antisite defects causes parts of the octahedrally coordinated Co atoms to switch from intermediate to high spin.

Electron diffraction study of the sillenites Bi{sub 12}SiO{sub 20}, Bi{sub 25}FeO{sub 39} and Bi{sub 25}InO{sub 39}: Evidence of short-range ordering of oxygen-vacancies in the trivalent sillenites

Energy Technology Data Exchange (ETDEWEB)

Scurti, Craig A.; Arenas, D. J. [Department of Physics, University of North Florida, Jacksonville, FL 32224 (United States); Auvray, Nicolas [Department of Physics, University of North Florida, Jacksonville, FL 32224 (United States); Laboratoire de Nanotechnologie et d’Instrumentation Optique - UMR CNRS 6279, Université Technologie de Troyes, 12 rue Marie Curie, Troyes 10010 (France); Lufaso, Michael W. [Department of Chemistry, University of North Florida, Jacksonville, FL 32224 (United States); Takeda, Seiji [The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Kohno, Hideo [School of Environmental Science and Engineering, Kochi University of Technology, Tosayamada, Kami, Kochi 782-8502 Japan (Japan)

2014-08-15

We present an electron diffraction study of three sillenites, Bi{sub 12}SiO{sub 20}, Bi{sub 25}FeO{sub 39}, and Bi{sub 25}InO{sub 39} synthesized using the solid-state method. We explore a hypothesis, inspired by optical studies in the literature, that suggests that trivalent sillenites have additional disorder not present in the tetravalent compounds. Electron diffraction patterns of Bi{sub 25}FeO{sub 39} and Bi{sub 25}InO{sub 39} show streaks that confirm deviations from the ideal sillenite structure. Multi-slice simulations of electron-diffraction patterns are presented for different perturbations to the sillenite structure - partial substitution of the M site by Bi{sup 3+}, random and ordered oxygen-vacancies, and a frozen-phonon model. Although comparison of experimental data to simulations cannot be conclusive, we consider the streaks as evidence of short-range ordered oxygen-vacancies.

High temperature oxidation of metals: vacancy injection and consequences on the mechanical properties

International Nuclear Information System (INIS)

Perusin, S.

2004-11-01

The aim of this work is to account for the effects of the high temperature oxidation of metals on their microstructure and their mechanical properties. 'Model' materials like pure nickel, pure iron and the Ni-20Cr alloy are studied. Nickel foils have been oxidised at 1000 C on one side only in laboratory air, the other side being protected from oxidation by a reducing atmosphere. After the oxidation treatment, the unoxidized face was carefully examined by using an Atomic Force Microscope (AFM). Grain boundaries grooves were characterised and their depth were compared to the ones obtained on the same sample heat treated in the reducing atmosphere during the same time. They are found to be much deeper in the case of the single side oxidised samples. It is shown that this additional grooving is directly linked to the growth of the oxide scale on the opposite side and that it can be explained by the diffusion of the vacancies produced at the oxide scale - metal interface, across the entire sample through grain boundaries. Moreover, the comparison between single side oxidised samples and samples oxidised on both sides points out that voids in grain boundaries are only observed in this latter case proving the vacancies condensation in the metal when the two faces are oxidised. The role of the carbon content and the sample's geometry on this phenomenon is examined in detail. The diffusion of vacancies is coupled with the transport of oxygen so that a mechanism of oxygen transport by vacancies is suggested. The tensile tests realised at room temperature on nickel foils (bamboo microstructure) show that the oxide scale can constitute a barrier to the emergence of dislocations at the metal surface. Finally, the Ni-20Cr alloy is tested in tensile and creep tests between 25 and 825 C in oxidising or reducing atmospheres. (author)

Oxygen vacancy defect engineering using atomic layer deposited HfAlOx in multi-layered gate stack

Science.gov (United States)

Bhuyian, M. N.; Sengupta, R.; Vurikiti, P.; Misra, D.

2016-05-01

This work evaluates the defects in high quality atomic layer deposited (ALD) HfAlOx with extremely low Al (estimated by the high temperature current voltage measurement shows that the charged oxygen vacancies, V+/V2+, are the primary source of defects in these dielectrics. When Al is added in HfO2, the V+ type defects with a defect activation energy of Ea ˜ 0.2 eV modify to V2+ type to Ea ˜ 0.1 eV with reference to the Si conduction band. When devices were stressed in the gate injection mode for 1000 s, more V+ type defects are generated and Ea reverts back to ˜0.2 eV. Since Al has a less number of valence electrons than do Hf, the change in the co-ordination number due to Al incorporation seems to contribute to the defect level modifications. Additionally, the stress induced leakage current behavior observed at 20 °C and at 125 °C demonstrates that the addition of Al in HfO2 contributed to suppressed trap generation process. This further supports the defect engineering model as reduced flat-band voltage shifts were observed at 20 °C and at 125 °C.

Oxygen vacancy as fatigue evidence of La0.5Sr0.5CoO3/PbZr0.4Ti0.6O3/La0.5Sr0.5CoO3 capacitors

Science.gov (United States)

Liu, B. T.; Chen, J. E.; Sun, J.; Wei, D. Y.; Chen, J. H.; Li, X. H.; Bian, F.; Zhou, Y.; Guo, J. X.; Zhao, Q. X.; Guan, L.; Wang, Y. L.; Guo, Q. L.; Ma, L. X.

2010-09-01

La0.5Sr0.5CoO3 (LSCO) films grown on SrTiO3 substrates, cooled at reduced oxygen pressures, ranging from 8×104 to 1×10-4 Pa, from the depostion temperature, are used as the bottom electrodes of PbZr0.4Ti0.6O3 (PZT) capacitors to study the impact of oxygen stoichiometry of the LSCO bottom electrodes on the structural and physical properties of LSCO/PZT/LSCO capacitors. It is found that the tetragonality, polarization and fatigue-resistance of PZT films decrease with the decrease of the cooling oxygen pressure. Almost 60% polarization degradation occurs for the PZT capacitor with the LSCO bottom electrode cooled in 1×10-4 Pa oxygen up to 1010 switching cycles, indicating that the oxygen vacancy of the bottom electrode can result in fatigue of the LSCO/PZT/LSCO capacitor.

Zn-vacancy related defects in ZnO grown by pulsed laser deposition

Science.gov (United States)

Ling, F. C. C.; Luo, C. Q.; Wang, Z. L.; Anwand, W.; Wagner, A.

2017-02-01

Undoped and Ga-doped ZnO (002) films were grown c-sapphire using the pulsed laser deposition (PLD) method. Znvacancy related defects in the films were studied by different positron annihilation spectroscopy (PAS). These included Doppler broadening spectroscopy (DBS) employing a continuous monenergetic positron beam, and positron lifetime spectroscopy using a pulsed monoenergetic positron beam attached to an electron linear accelerator. Two kinds of Znvacancy related defects namely a monovacancy and a divacancy were identified in the films. In as-grown undoped samples grown with relatively low oxygen pressure P(O2)≤1.3 Pa, monovacancy is the dominant Zn-vacancy related defect. Annealing these samples at 900 oC induced Zn out-diffusion into the substrate and converted the monovacancy to divacancy. For the undoped samples grown with high P(O2)=5 Pa irrespective of the annealing temperature and the as-grown degenerate Ga-doped sample (n=1020 cm-3), divacancy is the dominant Zn-vacancy related defect. The clustering of vacancy will be discussed.

Understanding the presence of vacancy clusters in ZnO from a kinetic perspective

Energy Technology Data Exchange (ETDEWEB)

Bang, Junhyeok; Zhang, S. B., E-mail: zhangs9@rpi.edu, E-mail: kimyongsung@gmail.com [Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute, Troy, New York 12180 (United States); Kim, Youg-Sung, E-mail: zhangs9@rpi.edu, E-mail: kimyongsung@gmail.com [Korea Research Institute of Standards and Science, Daejeon 305-340 (Korea, Republic of); Department of Nano Science, University of Science and Technology, Daejeon 305-350 (Korea, Republic of); Park, C. H. [Research Center for Dielectric and Advanced Matter Physics, Pusan National University, Busan 609-735 (Korea, Republic of); Gao, F. [Pacific Northwest National Laboratory, MS K8-93, P.O. Box 999, Richland, Washington 99352 (United States)

2014-06-23

Vacancy clusters have been observed in ZnO by positron-annihilation spectroscopy (PAS), but detailed mechanisms are unclear. This is because the clustering happens in non-equilibrium conditions, for which theoretical method has not been well established. Combining first-principles calculation and kinetic Monte Carlo simulation, we determine the roles of non-equilibrium kinetics on the vacancies clustering. We find that clustering starts with the formation of Zn and O vacancy pairs (V{sub Zn} − Vo), which further grow by attracting additional mono-vacancies. At this stage, vacancy diffusivity becomes crucial: due to the larger diffusivity of V{sub Zn} compared to V{sub O}, more V{sub Zn}-abundant clusters are formed than V{sub O}-abundant clusters. The large dissociation energy barriers, e.g., over 2.5 eV for (V{sub Zn} − Vo), suggest that, once formed, it is difficult for the clusters to dissociate. By promoting mono-vacancy diffusion, thermal annealing will increase the size of the clusters. As the PAS is insensitive to V{sub O} donor defects, our results suggest an interpretation of the experimental data that could not have been made without the in-depth calculations.

Slow-positron annihilation analysis on optical degradation of ZnO white paint irradiated by protons

International Nuclear Information System (INIS)

Xiao Haiying; Li Chundong; Yang Dezhuang; He Shiyu; Jia Jin; Ye Bangjiao

2009-01-01

The optical degradation in ZnO white paint under low energy proton exposure was investigated in terms of slow-positron annihilation spectroscopy. Experimental results show that with increasing proton fluence, the S-parameter of the Doppler broadening spectrum gradually decreases, and the W-parameter increases.The slope plot of the fitting S-W changes under the proton exposure. The decrease of S-parameter can be attributed to a decrease of zinc vacancy content and the formation of quasi-positronium. The quasi-positronium is viewed as a bounded state of a singly ionized oxygen vacancy (trapping an electron) with a positron, the formation of which could reduce the positron annihilation rate and thus the S-parameter. The decrease of S-parameter demonstrates the amount increase of singly ionized oxygen vacancy of ZnO white paint caused by proton irradiation. The change of the S-Wplot slope is related to the transformation of doubly ionized oxygen vacancies into singly ionized oxygen vacancies under proton irradiation. (authors)

Thermal conductivity reduction in oxygen-deficient strontium titanates

NARCIS (Netherlands)

Yu, Choongho; Scullin, Matthew L.; Huijben, Mark; Ramesh, Ramamoorthy; Majumdar, Arun

2008-01-01

We report significant thermal conductivity reduction in oxygen-deficient lanthanum-doped strontium titanate (Sr1−xLaxTiO3−δ) films as compared to unreduced strontium titanates. Our experimental results suggest that the oxygen vacancies could have played an important role in the reduction. This could

Formation of reactive oxygen species in rat epithelial cells upon ...

Indian Academy of Sciences (India)

In our study, we investigated the influence of fly ash on the promotion of early inflammatory reactions like the formation of reactive oxygen species (ROS) in rat lung epithelial cells (RLE-6TN). Furthermore, we determined the formation of nitric oxide (NO). The cells show a clear dose-response relationship concerning the ...

Radiation accelerated formation of oxygen and carbon related complexes in silicon

International Nuclear Information System (INIS)

Lazrak, A.; Magnea, N.; Pautrat, J.L.

1984-06-01

During the pulling of silicon monocrystals by the Czochralsky method, oxygen is incorporated into the lattice. It is known from early works that low temperature annealings (400-1000 0 C) make this oxygen to precipitate and a number of different defects to be generated. In order to check whether the fast diffusivity of an oxygen silicon interstitial complex has to be taken in consideration it was interesting to examinate the possible role of radiation damage on the formation of oxygen related defects. Experimental results of an experiment are presented and discussed

Phosphorous–vacancy–oxygen defects in silicon

KAUST Repository

Wang, Hao; Chroneos, Alexander; Hall, D.; Schwingenschlö gl, Udo; Sgourou, E. N.

2013-01-01

Electronic structure calculations employing the hybrid functional approach are used to gain fundamental insight in the interaction of phosphorous with oxygen interstitials and vacancies in silicon. It recently has been proposed, based on a binding

Vacancy ordered γ-Fe{sub 2}O{sub 3} nanoparticles functionalized with nanohydroxyapatite: XRD, FTIR, TEM, XPS and Mössbauer studies

Energy Technology Data Exchange (ETDEWEB)

Ramos Guivar, Juan A., E-mail: juan.ramos5@unmsm.edu.pe [Faculty of Physical Sciences, National University of San Marcos, P. O. Box 14- 0149, Lima 14 (Peru); Sanches, Edgar A., E-mail: sanches.ufam@gmail.com [Federal University of Amazonas, Department of Physics, Manaus/AM (Brazil); Bruns, Florian, E-mail: f.bruns@tu-braunschweig.de [Institut für Physik der Kondensierten Materie, Technische Universität Braunschweig, 38110 Braunschweig (Germany); Sadrollahi, Elaheh, E-mail: elahe.sadrollahi@gmail.com [Institut für Physik der Kondensierten Materie, Technische Universität Braunschweig, 38110 Braunschweig (Germany); Morales, M.A., E-mail: marco.moralestorres@gmail.com [Department of Theoretical and Experimental Physics, UFRN, Natal, RN 59078- 970 (Brazil); López, Elvis O., E-mail: lopmezel@gmail.com [Brazilian Center for Research in Physics (CBPF), Rio de Janeiro, RJ 22290-180 (Brazil); Litterst, F. Jochen, E-mail: litterst@cbpf.br [Institut für Physik der Kondensierten Materie, Technische Universität Braunschweig, 38110 Braunschweig (Germany); Brazilian Center for Research in Physics (CBPF), Rio de Janeiro, RJ 22290-180 (Brazil)

2016-12-15

Graphical abstract: Possible bonding configuration in the γ-Fe{sub 2}O{sub 3} nanoparticles functionalized with nanoHAp. - Highlights: • Coprecipitation in alkaline medium for the synthesis of vacancy ordered γ-Fe{sub 2}O{sub 3}@HAp nanocomposite. • Samples were characterized by XRD, FTIR, XPS, TEM, VSM and Mössbauer spectroscopy. • The functionalization is explained with the binding of two oxygens of chemisorbed H{sub 2}O molecules at the common interface of HAp/C{sub 6}H{sub 8}O{sub 7}/γ-Fe{sub 2}O{sub 3}. - Abstract: Vacancy ordered maghemite (γ-Fe{sub 2}O{sub 3}) nanoparticles functionalized with nanohydroxyapatite (HAp – Ca{sub 10}(PO{sub 4}) {sub 6}(OH){sub 2}) have been successfully synthesized using an inexpensive co-precipitation chemical route. Evidence for the presence of vacancy order in maghemite was shown by the superstructure lines observed in X-ray diffraction. The adsorption of carboxyl groups of citric acid (C{sub 6}H{sub 8}O{sub 7}) onto γ-Fe{sub 2}O{sub 3} nanoparticles was investigated by FTIR, XPS and Mössbauer spectroscopy. From XPS surface analysis, two binding energies related to oxygen were attributed to bindings between C{sub 6}H{sub 8}O{sub 7}/γ- Fe{sub 2}O{sub 3} and C{sub 6}H{sub 8}O{sub 7}/HAp from an interfacial reaction promoted by strongly adsorbed H{sub 2}O molecules at the surface of these nanomaterials. Le Bail refinement of the XRD patterns showed the formation of well-crystallized pure tetragonal maghemite before and after functionalization with nanoHAp. The temperature dependence of hyperfine parameters of pure and functionalized γ-Fe{sub 2}O{sub 3} nanoparticles was investigated via Mössbauer spectroscopy. TEM revealed the formation of quasi-spherical γ- Fe{sub 2}O{sub 3} nanoparticles with an average diameter of ca. 12 nm and 16 nm before and after functionalization with nanoHAp in agreement with Le Bail refinement. Magnetometry measurements showed a saturation magnetization of 12 emu/g and a blocking

First-principles study on migration of vacancy in tungsten

International Nuclear Information System (INIS)

Oda, Yasuhiro; Ito, Atsushi M.; Takayama, Arimichi; Nakamura, Hiroaki

2014-03-01

We calculated di-vacancy binding energies and migration energies of mono-vacancy and di-vacancy in tungsten material using DFT calculation. The mono-vacancy diffuses in [111] direction easily rather than in [001] direction. The migration energies of di-vacancies are almost the same value of the mono-vacancy. The migration of di-vacancy is approximately the same as the migration of mono-vacancy. The di-vacancy binding energies are almost zero or negative. The interactions between two vacancies in tungsten material are repulsive from the second to fifth nearest-neighbor. The vacancies are difficult to aggregate since di-vacancy is less stable than mono-vacancy. (author)

Remarkable changes in the photoluminescent properties of Y2Ce2O7:Eu(3+) red phosphors through modification of the cerium oxidation states and oxygen vacancy ordering.

Science.gov (United States)

Raj, Athira K V; Prabhakar Rao, P; Sreena, T S; Sameera, S; James, Vineetha; Renju, U A

2014-11-21

A new series of red phosphors based on Eu(3+)-doped yttrium cerate [Y1.9Ce2O7:0.1Eu(3+), Y2Ce1.9O7:0.1Eu(3+) and Y2Ce2-xO7:xEu(3+) (x = 0.05, 0.10, 0.15, 0.20, 0.25 and 0.50)] was prepared via a conventional solid-state method. The influence of the substitution of Eu(3+) at the aliovalent site on the photoluminescent properties was determined by powder X-ray diffraction, FT Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy with energy-dispersive spectroscopy, UV-visible absorption spectroscopy, photoluminescence spectroscopy and lifetime measurements. The substitution of Eu(3+) at the Ce(4+) site induces a structural transition from a defect fluorite to a C-type structure, which increases the oxygen vacancy ordering and the distortion of the Eu(3+) environment, and decreases the formation of Ce(3+) states. In contrast, phosphors with isovalent substitution at the Y(3+) site exhibit the biphasic nature of defect fluorite and a C-type structure, thereby increasing the number of Ce(3+) oxidation states. These modifications resulted in remarkable changes in the photoluminescent properties of Y2Ce1.9O7:0.1Eu(3+) red phosphors, with emission intensities 3.8 times greater than those of the Ce0.9O2:0.1Eu(3+) and Y1.9Ce2O7:0.1Eu(3+). The photoluminescent properties of Y2Ce2-xO7:xEu(3+) were studied at different Eu(3+) concentrations under excitation with blue light. These phosphors emit intense red light due to the (5)D0-(7)F2 transition under excitation at 466 nm and no concentration quenching is observed with up to 50 mol% Eu(3+). They show increased lifetimes in the range 0.62-0.72 ms at Eu(3+) concentrations. The cation ordering linked to the oxygen vacancy ordering led to the uniform distribution of Eu(3+) ions in the lattice, thus allowing higher doping concentrations without quenching and consequently increasing the lifetime of the (5)D0 states. Our results demonstrate that significant improvements in

Interaction of hydrogen and oxygen with bulk defects and surfaces of metals

International Nuclear Information System (INIS)

Besenbacher, F.

1994-05-01

The thesis deals with the interaction of hydrogen with defects in metals and the interaction of hydrogen and oxygen with metal surfaces studied by ion-beam techniques and scanning tunneling microscopy (STM), respectively. The first part of the thesis discusses the interaction of hydrogen with simple defects in transition metals. The trap-binding enthalpies and the lattice location of hydrogen trapped to vacancies have been determined, and an extremely simple and versatile picture of the hydrogen-metal interaction has evolved, in which the trap strength is mainly determined by the local electron density. Any dilution of the lattice will lead to a trap, vacancies and voids being the strongest trap. It is found that hydrogen trapped to vacancies in fcc metals is quantum-mechanically delocalized, and the excitation energies for the hydrogen in the vacancy potential are a few MeV only. The interaction of hydrogen with metal surfaces is studied by the transmission channeling (TC) technique. It is found that hydrogen chemisorbs in the highest-coordinated sites on the surfaces, and that there is a direct relationship between the hydrogen-metal bond length and the coordination number for the hydrogen. In the final part of the thesis the dynamics of the chemisorption process for oxygen and hydrogen on metal surfaces is studied by STM, a fascinating and powerful technique for exploring the atomic-scale realm of surfaces. It is found that there is a strong coupling between the chemisorption process and the distortion of the metal surface. The adsorbates induce a surface reconstruction, i.e. metal-metal bond breaks and metal-adsorbate bounds form. Whereas hydrogen interacts weakly with the metals and induces reconstructions where only nnn metals bonds are broken, oxygen interacts strongly with the metal, and the driving force for the O-induced reconstructions appears to be the formation of low-coordinated metal-O rows, formed by breaking of nn metal bonds. Finally it is shown

Indium vacancy induced d0 ferromagnetism in Li-doped In2O3 nanoparticles

Science.gov (United States)

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.

Low-power resistive random access memory by confining the formation of conducting filaments

International Nuclear Information System (INIS)

Huang, Yi-Jen; Lee, Si-Chen; Shen, Tzu-Hsien; Lee, Lan-Hsuan; Wen, Cheng-Yen

2016-01-01

Owing to their small physical size and low power consumption, resistive random access memory (RRAM) devices are potential for future memory and logic applications in microelectronics. In this study, a new resistive switching material structure, TiO_x/silver nanoparticles/TiO_x/AlTiO_x, fabricated between the fluorine-doped tin oxide bottom electrode and the indium tin oxide top electrode is demonstrated. The device exhibits excellent memory performances, such as low operation voltage (<±1 V), low operation power, small variation in resistance, reliable data retention, and a large memory window. The current-voltage measurement shows that the conducting mechanism in the device at the high resistance state is via electron hopping between oxygen vacancies in the resistive switching material. When the device is switched to the low resistance state, conducting filaments are formed in the resistive switching material as a result of accumulation of oxygen vacancies. The bottom AlTiO_x layer in the device structure limits the formation of conducting filaments; therefore, the current and power consumption of device operation are significantly reduced.

Effect of tin doping on oxygen- and carbon-related defects in Czochralski silicon

International Nuclear Information System (INIS)

Chroneos, A.; Londos, C. A.; Sgourou, E. N.

2011-01-01

Experimental and theoretical techniques are used to investigate the impact of tin doping on the formation and the thermal stability of oxygen- and carbon-related defects in electron-irradiated Czochralski silicon. The results verify previous reports that Sn doping reduces the formation of the VO defect and suppresses its conversion to the VO 2 defect. Within experimental accuracy, a small delay in the growth of the VO 2 defect is observed. Regarding carbon-related defects, it is determined that Sn doping leads to a reduction in the formation of the C i O i , C i C s , and C i O i (Si I ) defects although an increase in their thermal stability is observed. The impact of strain induced in the lattice by the larger tin substitutional atoms, as well as their association with intrinsic defects and carbon impurities, can be considered as an explanation to account for the above observations. The density functional theory calculations are used to study the interaction of tin with lattice vacancies and oxygen- and carbon-related clusters. Both experimental and theoretical results demonstrate that tin co-doping is an efficient defect engineering strategy to suppress detrimental effects because of the presence of oxygen- and carbon-related defect clusters in devices.

Solute-vacancy binding in aluminum

International Nuclear Information System (INIS)

Wolverton, C.

2007-01-01

Previous efforts to understand solute-vacancy binding in aluminum alloys have been hampered by a scarcity of reliable, quantitative experimental measurements. Here, we report a large database of solute-vacancy binding energies determined from first-principles density functional calculations. The calculated binding energies agree well with accurate measurements where available, and provide an accurate predictor of solute-vacancy binding in other systems. We find: (i) some common solutes in commercial Al alloys (e.g., Cu and Mg) possess either very weak (Cu), or even repulsive (Mg), binding energies. Hence, we assert that some previously reported large binding energies for these solutes are erroneous. (ii) Large binding energies are found for Sn, Cd and In, confirming the proposed mechanism for the reduced natural aging in Al-Cu alloys containing microalloying additions of these solutes. (iii) In addition, we predict that similar reduction in natural aging should occur with additions of Si, Ge and Au. (iv) Even larger binding energies are found for other solutes (e.g., Pb, Bi, Sr, Ba), but these solutes possess essentially no solubility in Al. (v) We have explored the physical effects controlling solute-vacancy binding in Al. We find that there is a strong correlation between binding energy and solute size, with larger solute atoms possessing a stronger binding with vacancies. (vi) Most transition-metal 3d solutes do not bind strongly with vacancies, and some are even energetically strongly repelled from vacancies, particularly for the early 3d solutes, Ti and V

Magnetism and metal-insulator transition in oxygen deficient SrTiO3

Science.gov (United States)

Lopez-Bezanilla, Alejandro; Ganesh, P.; Littlewood, Peter

2015-03-01

We report new findings in the electronic structure and magnetism of oxygen vacancies in SrTiO3. By means of first-principles calculations we show that the appearance of magnetism in oxygen-deficient SrTiO3 is not determined solely by the presence of a single oxygen vacancy but by the density of free carriers and the relative proximity of the vacant sites. While an isolated vacancy behaves as a non-magnetic double donor, manipulation of the doping conditions allows the stability of a single donor state with emergent local moments. Strong local lattice distortions enhance the binding of this state. Consequently we find that the free-carrier density and strain are fundamental components to obtaining trapped spin-polarized electrons in oxygen-deficient SrTiO3, which may have important implications in the design of switchable magneto-optic devices. AL-B and PBL were supported by DOE-BES under Contract No. DE-AC02-06CH11357. PG was sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT- Battelle, LLC, for the US Department of Energy.

Vacancy distribution in nonstoichiometric vanadium monoxide

International Nuclear Information System (INIS)

Gusev, A.I.; Davydov, D.A.; Valeeva, A.A.

2011-01-01

Graphical abstract: Display Omitted Research highlights: → A certain fraction of vanadium atoms in disordered cubic vanadium monoxide VO y and ordered tetragonal phase V 52 O 64 is located in tetrahedral positions of a basic cubic lattice. → These positions are never occupied by any atoms in other strongly nonstoichiometric carbides, nitrides and oxides. → Both disordered and ordered structures of vanadium monoxide are characterized by the presence of short-range order of displacements in the oxygen sublattice and short-range order of substitution in the metal sublattice. → The short-range order of displacement is caused by the local displacements of O atoms from V (t) atoms occupying tetrahedral positions. The short-range order of substitution appears because V (t) atoms in the tetrahedral positions are always in the environment of four vacancies □ of the vanadium sublattice. - Abstract: Structural vacancy distribution in the crystal lattice of the tetragonal V 52 O 64 superstructure which is formed on the basis of disordered superstoichiometric cubic vanadium monoxide VO y ≡V x O z is experimentally determined and the presence of significant local atomic displacements and large local microstrains in a crystal lattice of real ordered phase is established. It is shown that the relaxation of local microstrains takes place owing to the basic disordered cubic phase grain refinement and a formation of ordered phase domains. The ordered phase domains grow in the direction from the boundaries to the centre of grains of the disordered basic cubic phase. Isothermal evolution at 970 K of the average domain size in ordered VO 1.29 vanadium monoxide is established. It is shown that the short-range order presents in a metal sublattice of disordered cubic VO y vanadium monoxide. The character of the short-range order is such that vanadium atoms occupying tetrahedral positions are in the environment of four vacant sites of the vanadium sublattice. This means that the

The formation of non-oxidic oxygen phases on Ru(0001). From the first stages of the oxygen take-up to oxidation

International Nuclear Information System (INIS)

Blume, R.

2005-01-01

The aim of the thesis presented here was the investigation of the formation of non oxidic oxygen phases on the Ru(0001) surface. Smooth and defect rich surfaces were exposed to high oxygen pressures (up to 1 bar) at moderate temperatures (550 K). The characterisation was performed under UHV conditions using Thermal Desorption Spectroscopy (TDS), Scanning Photoemission Microscopy (SPEM), Thermal Energy Atomic Scattering (TEAS), Ultraviolett Photoelectron Spectroscopy (UPS) and Low Energy Electron Diff raction (LEED) as well as In situ by the In Situ X-Ray Photoelectron Spectroscopy (In Situ XPS). The application of this Low Temperature preparation procedure (LT) leads to an Oxygen uptake up to 3 MLE of ''subsurface'' oxygen into a smooth Ru(0001) surface without the typical indications of oxidation (MLE: Monolayer Equivalent). The accumulation of oxygen beneath the surface starts immediatly after the completion of a full chemisorbed layer. Here, the local saturation of the adsorbed oxygen is the decisive step. Diff usion of oxygen directly through the chemisorbed layer only slightly contributes to the overall uptake. Oxygen is mostly accomodated in the vicinity of the surface via surface defects which has been shown on defect rich surfaces created by mild Ar+ sputtering. The maximum oxygen capacity is 10 Atoms/Defect. The uptake is thermally activated with an activation energy of 0.15 eV. The oxygen uptake causes a massive structural change of at least the top two ruthenium layers. Whereas the ruthenium atoms of the first layer are coordinated with up to four, those of the second layer are coordinated with up to two oxygen atoms. These binding condition are metastable and can be changed by annealing the surface. With reaching the desorption temperature two distinct desorption peaks are observed with TDS. For an accumulation of about 0.5 MLE of ''subsurface'' oxygen the desorption proceeds exclusively at the characteristic temperature of the chemisorbed layer at 1040

The importance of dissolved free oxygen during formation of sandstone-type uranium deposits

Science.gov (United States)

Granger, Harry Clifford; Warren, C.G.

1979-01-01

One factor which distinguishes t, he genesis of roll-type uranium deposits from the Uravan Mineral Belt and other sandstone-type uranium deposits may be the presence and concentration of dissolved free oxygen in the ore-forming. solutions. Although dissolved oxygen is a necessary prerequisite for the formation of roll-type deposits, it is proposed that a lack of dissolved oxygen is a prerequisite for the Uravan deposits. Solutions that formed both types of deposits probably had a supergene origin and originated as meteoric water in approximate equilibrium with atmospheric oxygen. Roll-type deposits were formed where the Eh dropped abruptly following consumption of the oxygen by iron sulfide minerals and creation of kinetically active sulfur species that could reduce uranium. The solutions that formed the Uravan deposits, on the other hand, probably first equilibrated with sulfide-free ferrous-ferric detrital minerals and fossil organic matter in the host rock. That is, the uraniferous solutions lost their oxygen without lowering their Eh enough to precipitate uranium. Without oxygen, they then. became incapable of oxidizing iron sulfide minerals. Subsequent localization and formation of ore bodies from these oxygen-depleted solutions, therefore, was not necessarily dependent on large reducing capacities.

Influence of surface vacancy defects on the carburisation of Fe 110 surface by carbon monoxide

Energy Technology Data Exchange (ETDEWEB)

Chakrabarty, Aurab, E-mail: aurab.chakrabarty@qatar.tamu.edu; Bouhali, Othmane [Texas A& M University at Qatar, P.O. Box 23874, Doha (Qatar); Mousseau, Normand [Département de Physique and RQMP, Université de Montréal, Case Postale 6128, Succursale Centre-Ville, Montréal (QC) H3C 3J7 (Canada); Becquart, Charlotte S. [UMET, UMR CNRS 8207, ENSCL, Université Lille I, 59655 Villeneuve d’Ascq cédex (France); El-Mellouhi, Fedwa, E-mail: felmellouhi@qf.org.qa [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 5825 Doha (Qatar)

2016-07-28

Adsorption and dissociation of gaseous carbon monoxide (CO) on metal surfaces is one of the most frequently occurring processes of carburisation, known as primary initiator of metal dusting corrosion. Among the various factors that can significantly influence the carburisation process are the intrinsic surface defects such as single surface vacancies occurring at high concentrations due to their low formation energy. Intuitively, adsorption and dissociation barriers of CO are expected to be lowered in the vicinity of a surface vacancy, due to the strong attractive interaction between the vacancy and the C atom. Here the adsorption energies and dissociation pathways of CO on clean and defective Fe 110 surface are explored by means of density functional theory. Interestingly, we find that the O adatom, resulting from the CO dissociation, is unstable in the electron-deficit neighbourhood of the vacancy due to its large electron affinity, and raises the barrier of the carburisation pathway. Still, a full comparative study between the clean surface and the vacancy-defected surface reveals that the complete process of carburisation, starting from adsorption to subsurface diffusion of C, is more favourable in the vicinity of a vacancy defect.

Effect of germanium doping on the annealing characteristics of oxygen and carbon-related defects in Czochralski silicon

International Nuclear Information System (INIS)

Londos, C. A.; Andrianakis, A.; Sgourou, E. N.; Emtsev, V.; Ohyama, H.

2010-01-01

This paper is devoted to the annealing studies of defects produced in carbon-rich Ge-doped Czochralski-grown Si (Cz-Si) by 2 MeV electron irradiation. The annealing temperature of vacancy-oxygen (VO) complexes, carbon interstitial-oxygen interstitial (C i O i ), and carbon interstitial-carbon substitutional (C i C s ) pairs as well as the formation temperature of vacancy-two oxygen (VO 2 ) complexes are monitored as a function of Ge concentration. It has been established that the annealing of C i O i and C i C s defects remains practically unaffected by the Ge presence, whereas the annealing temperature of VO defects and the formation temperature of VO 2 complexes are substantially lowered at Ge concentrations larger than 1x10 19 cm -3 . The hydrostatic component of elastic strains introduced by Ge atoms in the Si crystal lattice was calculated. It appears to be very small, at least insufficient to exert a pronounced effect upon the annealing behavior of radiation-produced defects. This conclusion is in line with what is observed for the C i O i and C i C s species. In the case of VO, whose annealing process in Cz-Si is concurrently conducted by two reaction paths VO+O i →VO 2 and VO+Si I →O i , we suggest that the latter reaction in Ge-doped Cz-Si is enhanced by emitting self-interstitials (Si I ) from loosely bound self-interstitial clusters predominantly formed around Ge impurity atoms. As a result, the liberation of self-interstitials at lower annealing temperatures leads to an enhanced annealing of VO defects. An enhanced formation of VO 2 complexes at lower temperatures is also discussed in terms of other reactions running in parallel with the reaction VO+Si I →O i .

Hydrogen isotope in erbium oxide: Adsorption, penetration, diffusion, and vacancy trapping

International Nuclear Information System (INIS)

Mao, Wei; Chikada, Takumi; Suzuki, Akihiro; Terai, Takayuki; Matsuzaki, Hiroyuki

2015-01-01

Highlights: • H adsorption on cubic Er 2 O 3 surface results in electron transfer from H to the surface. • The H penetration energy of at least 1.6 eV is required for cubic Er 2 O 3 surface. • The dominated mechanisms of H diffusion in bulk Er 2 O 3 are elucidated. • H diffusion near or at vacancies in Er 2 O 3 is an exothermic reaction. - Abstract: In this study, we report results using first-principles density functional theory calculations for four critical aspects of the interaction: H adsorption on Er 2 O 3 surface, surface-to-subsurface penetration of H into Er 2 O 3 , bulk diffusion of H in Er 2 O 3 , and trapping of H at vacancies. We identify surface stable adsorption positions and find that H prefers to transfer electrons to the surfaces and form covalent bonds with the nearest neighboring four oxygen atoms. For low surface coverage of H as in our case (0.89 × 10 14 H/cm 2 ), a penetration energy of at least 1.60 eV is required for cubic Er 2 O 3 surfaces. Further, the H diffusion barrier between the planes defined by Er 2 O 3 units along the favorable <1 1 1> direction is found to be very small – 0.16 eV – whereas higher barriers of 0.41 eV and 1.64 eV are required for diffusion across the planes, somewhat higher than the diffusion energy barrier of 0.20 eV observed experimentally at 873 K. In addition, we predict that interstitial H is exothermically trapped when it approaches a vacancy with the vacancy defect behaving as an electron trap since the H-vacancy defect is found to be more stable than the intrinsic defect

Mathematical modeling of oxygen transport in solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Svensson, Ann Mari

1997-12-31

This thesis develops mathematical models to describe the electrochemical performance of a solid oxide fuel cell cathode based on electrochemical kinetics and mass transfer. The individual effects of various coupled processes are investigated. A one-dimensional model is developed based on porous electrode theory. Two different mechanisms are investigated for the charge transfer reaction. One of these assumes that intermediately adsorbed oxygen atoms are reduced at the electrode/electrolyte interface, similar to the models proposed for metal electrodes. Simulated polarization curves exhibit limited currents due to depletion of oxygen adsorbates at high cathodic overvoltages. An empirical correlation is confirmed to exist between the limiting current an the oxygen partial pressure, however, a similar correlation often assumed to exist between the measured polarization resistance and the oxygen partial pressure could not be justified. For the other model, oxygen vacancies are assumed to be exchanged directly at the electrode/electrolyte interface. The electrochemical behaviour is improved by reducing the oxygen partial pressure, due to increased vacancy concentration of the electrode material. Simulated polarization curves exhibit Tafel-like slopes in the cathodic direction, which are due to polarization concentration, and not activation polarization in the conventional sense. Anodic limiting currents are predicted due to lack of available free sites for vacancy exchange at the cathode side. The thesis also presents a theoretical treatment of current and potential distributions in simple two-dimensional cell geometries, and a two-dimensional model for a porous electrode-electrolyte system for investigation of the effect of interfacial diffusion of adsorbates along the electrode/electrolyte interface. 172 refs., 60 figs., 11 tabs.

Positron-annihilation study of oxygen-deficient YBa2Cu3Ox (6.3

International Nuclear Information System (INIS)

Tang, C.Q.; Li, B.R.; Chen, A.

1990-01-01

We have measured the positron-lifetime spectra of oxygen-deficient YBa 2 Cu 3 O x for 6.3 m , τ 1 , τ 2 , and I 2 have a significant oxygen-content dependence. It is suggested that there are many kinds of positron states in polycrystalline YBa 2 Cu 3 O x , the disordering of O(1) vacancies strongly affects positron lifetime, and with gradually decreasing x the average electronic density decreases and the configuration and/or the charge states of the oxygen vacancies change in the region containing Cu(1)-O(1) chains

Probing of O2 vacancy defects and correlated magnetic, electrical and photoresponse properties in indium-tin oxide nanostructures by spectroscopic techniques

Science.gov (United States)

Ghosh, Shyamsundar; Dev, Bhupendra Nath

2018-05-01

Indium-tin oxide (ITO) 1D nanostructures with tunable morphologies i.e. nanorods, nanocombs and nanowires are grown on c-axis (0 0 0 1) sapphire (Al2O3) substrate in oxygen deficient atmosphere through pulsed laser deposition (PLD) technique and the effect of oxygen vacancies on optical, electrical, magnetic and photoresponse properties is investigated using spectroscopic methods. ITO nanostructures are found to be enriched with significant oxygen vacancy defects as evident from X-ray photoelectron and Raman spectroscopic analysis. Photoluminescence spectra exhibited intense mid-band blue emission at wavelength of region of 400-450 nm due to the electronic transition from conduction band maxima (CBM) to the singly ionized oxygen-vacancy (VO+) defect level within the band-gap. Interestingly, ITO nanostructures exhibited significant room-temperature ferromagnetism (RTFM) and the magnetic moment found proportional to concentration of VO+ defects which indicates VO+ defects are mainly responsible for the observed RTFM in nanostructures. ITO nanowires being enriched with more VO+ defects exhibited strongest RTFM as compared to other morphologies. Current voltage (I-V) characteristics of ITO nanostructures showed an enhancement of current under UV light as compared to dark which indicates such 1D nanostructure can be used as photovoltaic material. Hence, the study shows that there is ample opportunity to tailor the properties of ITOs through proper defect engineering's and such photosensitive ferromagnetic semiconductors might be promising for spintronic and photovoltaic applications.

Defect formation in LaGa(Mg,Ni)O3-δ : A statistical thermodynamic analysis validated by mixed conductivity and magnetic susceptibility measurements

Science.gov (United States)

Naumovich, E. N.; Kharton, V. V.; Yaremchenko, A. A.; Patrakeev, M. V.; Kellerman, D. G.; Logvinovich, D. I.; Kozhevnikov, V. L.

2006-08-01

A statistical thermodynamic approach to analyze defect thermodynamics in strongly nonideal solid solutions was proposed and validated by a case study focused on the oxygen intercalation processes in mixed-conducting LaGa0.65Mg0.15Ni0.20O3-δ perovskite. The oxygen nonstoichiometry of Ni-doped lanthanum gallate, measured by coulometric titration and thermogravimetric analysis at 923-1223K in the oxygen partial pressure range 5×10-5to0.9atm , indicates the coexistence of Ni2+ , Ni3+ , and Ni4+ oxidation states. The formation of tetravalent nickel was also confirmed by the magnetic susceptibility data at 77-600K , and by the analysis of p -type electronic conductivity and Seebeck coefficient as function of the oxygen pressure at 1023-1223K . The oxygen thermodynamics and the partial ionic and hole conductivities are strongly affected by the point-defect interactions, primarily the Coulombic repulsion between oxygen vacancies and/or electron holes and the vacancy association with Mg2+ cations. These factors can be analyzed by introducing the defect interaction energy in the concentration-dependent part of defect chemical potentials expressed by the discrete Fermi-Dirac distribution, and taking into account the probabilities of local configurations calculated via binomial distributions.

Vacancy clustering and acceptor activation in nitrogen-implanted ZnO

Science.gov (United States)

Børseth, Thomas Moe; Tuomisto, Filip; Christensen, Jens S.; Monakhov, Edouard V.; Svensson, Bengt G.; Kuznetsov, Andrej Yu.

2008-01-01

The role of vacancy clustering and acceptor activation on resistivity evolution in N ion-implanted n -type hydrothermally grown bulk ZnO has been investigated by positron annihilation spectroscopy, resistivity measurements, and chemical profiling. Room temperature 220keV N implantation using doses in the low 1015cm-2 range induces small and big vacancy clusters containing at least 2 and 3-4 Zn vacancies, respectively. The small clusters are present already in as-implanted samples and remain stable up to 1000°C with no significant effect on the resistivity evolution. In contrast, formation of the big clusters at 600°C is associated with a significant increase in the free electron concentration attributed to gettering of amphoteric Li impurities by these clusters. Further annealing at 800°C results in a dramatic decrease in the free electron concentration correlated with activation of 1016-1017cm-3 acceptors likely to be N and/or Li related. The samples remain n type, however, and further annealing at 1000°C results in passivation of the acceptor states while the big clusters dissociate.

Enhanced tunability of electrical and magnetic properties in (La,Sr)MnO3 thin films via field-assisted oxygen vacancy modulation

Science.gov (United States)

Wong, Hon Fai; Ng, Sheung Mei; Cheng, Wang Fai; Liu, Yukuai; Chen, Xinxin; von Nordheim, Danny; Mak, Chee Leung; Dai, Jiyan; Ploss, Bernd; Leung, Chi Wah

2017-12-01

We investigated the tunability of the transport and magnetic properties in 7.5 nm La0.7Sr0.3MnO3 (LSMO) epitaxial films in a field effect geometry with the ferroelectric copolymer P(VDF-TrFE) as the gate insulator. Two different switching behaviors were observed upon application of gate voltages with either high or low magnitudes. The application of single voltage pulses of alternating polarity with an amplitude high enough to switch the remanent polarization of the ferroelectric copolymer led to a 15% change of the resistance of the LSMO channel at temperature 300 K (but less than 1% change at 20 K). A minimal shift of the peak in the resistance-temperature plot was observed, implying that the Curie temperature TC of the manganite layer is not changed. Alternatively, the application of a chain of low voltage pulses was found to shift TC by more than 16 K, and a change of the channel resistance by a 45% was obtained. We attribute this effect to the field-assisted injection and removal of oxygen vacancies in the LSMO layer, which can occur across the thickness of the oxide film. By controlling the oxygen migration, the low-field switching route offers a simple method for modulating the electric and magnetic properties of manganite films.

Density functional study on the heterogeneous oxidation of NO over α-Fe{sub 2}O{sub 3} catalyst by H{sub 2}O{sub 2}: Effect of oxygen vacancy

Energy Technology Data Exchange (ETDEWEB)

Song, Zijian, E-mail: szj22zc15@163.com [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Wang, Ben, E-mail: benwang@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Yu, Jie, E-mail: yujie@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Ma, Chuan, E-mail: machuan628@163.com [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Zhou, Changsong, E-mail: zhouchangsong@hust.edu.cn [School of Energy and Mechanical Engineering, Nanjing Normal University, 210042, Nanjing (China); Chen, Tao, E-mail: chentao_hust@foxmail.com [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Yan, Qianqian [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Wang, Ke, E-mail: m201570959@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Sun, Lushi, E-mail: sunlushi@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China)

2017-08-15

Highlights: • NO and H{sub 2}O{sub 2} adsorption on perfect and oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface were studied by DFT calculations. • H{sub 2}O{sub 2} shows high chemical reactivity for its adsorption on oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface. • Oxygen vacancy plays an important role of the catalytic oxidation of NO by H{sub 2}O{sub 2} over the α-Fe{sub 2}O{sub 3} catalyst surfaces. • Mechanism of NO oxidation over α-Fe{sub 2}O{sub 3} (0 0 1) surface by H{sub 2}O{sub 2} was explained. - Abstract: Catalytic oxidation with H{sub 2}O{sub 2} is a promising method for NOx emission control in coal-fired power plants. Hematite-based catalysts are attracting increased attention because of their surface redox reactivity. To elucidate the NO oxidation mechanism on α-Fe{sub 2}O{sub 3} surfaces, density functional theory (DFT) calculations were conducted by investigating the adsorption characteristics of nitric oxide (NO) and hydrogen peroxide (H{sub 2}O{sub 2}) on perfect and oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surfaces. Results show that NO was molecularly adsorbed on two kinds of surfaces. H{sub 2}O{sub 2} adsorption on perfect surface was also in a molecular form; however, H{sub 2}O{sub 2} dissociation occurred on oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface. The adsorption intensities of the two gas molecules in perfect α-Fe{sub 2}O{sub 3} (0 0 1) surface followed the order NO > H{sub 2}O{sub 2}, and the opposite was true for the oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1). Oxygen vacancy remarkably enhanced the adsorption intensities of NO and H{sub 2}O{sub 2} and promoted H{sub 2}O{sub 2} decomposition on catalyst surface. As an oxidative product of NO, HNO{sub 2} was synthesized when NO and H{sub 2}O{sub 2} co-adsorbed on the oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface. Analyses of Mulliken population, electron density difference, and partial density of states showed that H{sub 2}O{sub 2} decomposition

Effect on hydrogen adsorption due to a lonely or a pair of carbon vacancies on the graphene layer

International Nuclear Information System (INIS)

Arellano, J S

2017-01-01

The influence on the hydrogen molecule adsorption on a pristine and a defective graphene layer is compared. The different lengths for the C-C bonds on the graphene layer with one vacancy are visualized and compared respect to pristine graphene. The energy of formation of one vacancy is calculated and a comparison of the binding energy for the hydrogen molecule is presented when the molecule is adsorbed on pristine graphene or on the defective graphene layer. The adsorption is studied for a single vacancy and at least for two different pairs of carbon vacancies. The qualitative general result, and contrary to the expected effect of the carbon vacancies on the hydrogen adsorption is that the rearrangement of the carbon atoms on the defective graphene layer allows only a relatively small increase in the magnitude of the binding energy for the hydrogen molecule. (paper)

OXYGEN TRANSPORT CERAMIC MEMBRANES

Energy Technology Data Exchange (ETDEWEB)

Dr. Sukumar Bandopadhyay; Dr. Nagendra Nagabhushana

2000-10-01

This is the third quarterly report on oxygen Transport Ceramic Membranes. In the following, the report describes the progress made by our university partners in Tasks 1 through 6, experimental apparatus that was designed and built for various tasks of this project, thermodynamic calculations, where applicable and work planned for the future. (Task 1) Design, fabricate and evaluate ceramic to metal seals based on graded ceramic powder/metal braze joints. (Task 2) Evaluate the effect of defect configuration on ceramic membrane conductivity and long term chemical and structural stability. (Task 3) Determine materials mechanical properties under conditions of high temperatures and reactive atmospheres. (Task 4) Evaluate phase stability and thermal expansion of candidate perovskite membranes and develop techniques to support these materials on porous metal structures. (Task 5) Assess the microstructure of membrane materials to evaluate the effects of vacancy-impurity association, defect clusters, and vacancy-dopant association on the membrane performance and stability. (Task 6) Measure kinetics of oxygen uptake and transport in ceramic membrane materials under commercially relevant conditions using isotope labeling techniques.

In situ observation of thermal relaxation of interstitial-vacancy pair defects in a graphite gap.

Science.gov (United States)

Urita, Koki; Suenaga, Kazu; Sugai, Toshiki; Shinohara, Hisanori; Iijima, Sumio

2005-04-22

Direct observation of individual defects during formation and annihilation in the interlayer gap of double-wall carbon nanotubes (DWNT) is demonstrated by high-resolution transmission electron microscopy. The interlayer defects that bridge two adjacent graphen layers in DWNT are stable for a macroscopic time at the temperature below 450 K. These defects are assigned to a cluster of one or two interstitial-vacancy pairs (I-V pairs) and often disappear just after their formation at higher temperatures due to an instantaneous recombination of the interstitial atom with vacancy. Systematic observations performed at the elevated temperatures find a threshold for the defect annihilation at 450-500 K, which, indeed, corresponds to the known temperature for the Wigner energy release.

In situ observation of thermal relaxation of interstitial-vacancy pair defects in a graphite gap

International Nuclear Information System (INIS)

Urita, Koki; Suenaga, Kazu; Iijima, Sumio; Sugai, Toshiki; Shinohara, Hisanori

2005-01-01

Direct observation of individual defects during formation and annihilation in the interlayer gap of double-wall carbon nanotubes (DWNT) is demonstrated by high-resolution transmission electron microscopy. The interlayer defects that bridge two adjacent graphen layers in DWNT are stable for a macroscopic time at the temperature below 450 K. These defects are assigned to a cluster of one or two interstitial-vacancy pairs (I-V pairs) and often disappear just after their formation at higher temperatures due to an instantaneous recombination of the interstitial atom with vacancy. Systematic observations performed at the elevated temperatures find a threshold for the defect annihilation at 450-500 K, which, indeed, corresponds to the known temperature for the Wigner energy release

Density functional study of NO adsorption on undefected and oxygen defective Au–BaO(1 0 0) surfaces

Energy Technology Data Exchange (ETDEWEB)

Añez, Rafael, E-mail: ranez@ivic.gob.ve [Laboratorio de Química Física y Catálisis Computacional, Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado, 21827 Caracas (Venezuela, Bolivarian Republic of); Sierraalta, Aníbal; Bastardo, Anelisse [Laboratorio de Química Física y Catálisis Computacional, Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado, 21827 Caracas (Venezuela, Bolivarian Republic of); Coll, David [Laboratorio de Físico Química Teórica de Materiales, Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado, 21827 Caracas (Venezuela, Bolivarian Republic of); Garcia, Belkis [Instituto Universitario de Tecnología de Valencia IUTVAL, Valencia, Edo. Carabobo (Venezuela, Bolivarian Republic of)

2014-07-01

A periodic density functional approach has been used in order to explore the interaction of NO with undoped and Au doped BaO(1 0 0) surface. Due to oxygen vacancies increase the interaction between the doping metal and the surface, F{sub S} and F{sub S}{sup +} vacancies were studied and compared with the results obtained on the undefected doped BaO(1 0 0). Our results indicate that the high basicity of the BaO surface, besides the electron density changes produced by the oxygen vacancies, modify considerably how the Au atom interacts with the surface increasing the ionic character of the interaction. F{sub S} vacancy shows to be a promise center to activate de NO bond on the BaO(1 0 0) surface.

Origin of unbalanced reaction of vacancies and interstitials during irradiation with cascades and influence on microstructural evolution

International Nuclear Information System (INIS)

Kiritani, M.; Yoshiie, T.; Kojima, S.; Satoh, Y.

1993-01-01

Based upon the underlying premise that all the microstructure evolution during irradiation results from the asymetrical reaction between vacancies and interstitials, the origin of the asymetry is sought and categorized, and the mechanism of defect structure evolution for each source of asymetry is investigated. The role of neutral sinks and the influence of dislocations are examined for the cases of irradiation with and without cascade damage. Vacancy cluster formation directly from cascades is found to favor the generation of freely migrating interstitials. Stochastic fluctuations of the point defect reactions under the balanced condition of vacancy and interstitial is experimentally detected, and the important role of the fluctuations is found in the determination of the fate of small interstitial cluster embryos produced by cascade damage. The influence of the unbalanced point defect reaction starting from difference in spacial distribution between vacancies and interstitials formed by cascade collisions is discussed as one of the important origins of vacancy dominant reactions. (orig.)

Oxygen and disorder effect in the magnetic properties of manganite films

Energy Technology Data Exchange (ETDEWEB)

Sirena, M. E-mail: sirenam@ib.cnea.gov.ar; Haberkorn, N.; Granada, M.; Steren, L.B.; Guimpel, J

2004-05-01

We have made a systematic study of the magnetic properties of low doped manganite films submitted to different oxygenation treatments. We have found that oxygenation dynamics depends critically of the strain field in the sample. The T{sub C} and the Mr increase as the oxygen content is increased. A decrease of the coercive field of the LSMO-STO films was observed, indicating that annealing treatments increase the oxygen content reducing oxygen vacancies.

Oxygen and disorder effect in the magnetic properties of manganite films

International Nuclear Information System (INIS)

Sirena, M.; Haberkorn, N.; Granada, M.; Steren, L.B.; Guimpel, J.

2004-01-01

We have made a systematic study of the magnetic properties of low doped manganite films submitted to different oxygenation treatments. We have found that oxygenation dynamics depends critically of the strain field in the sample. The T C and the Mr increase as the oxygen content is increased. A decrease of the coercive field of the LSMO-STO films was observed, indicating that annealing treatments increase the oxygen content reducing oxygen vacancies

Formation of p-type ZnO thin film through co-implantation

Science.gov (United States)

Chuang, Yao-Teng; Liou, Jhe-Wei; Woon, Wei-Yen

2017-01-01

We present a study on the formation of p-type ZnO thin film through ion implantation. Group V dopants (N, P) with different ionic radii are implanted into chemical vapor deposition grown ZnO thin film on GaN/sapphire substrates prior to thermal activation. It is found that mono-doped ZnO by N+ implantation results in n-type conductivity under thermal activation. Dual-doped ZnO film with a N:P ion implantation dose ratio of 4:1 is found to be p-type under certain thermal activation conditions. Higher p-type activation levels (1019 cm-3) under a wider thermal activation range are found for the N/P dual-doped ZnO film co-implanted by additional oxygen ions. From high resolution x-ray diffraction and x-ray photoelectron spectroscopy it is concluded that the observed p-type conductivities are a result of the promoted formation of PZn-4NO complex defects via the concurrent substitution of nitrogen at oxygen sites and phosphorus at zinc sites. The enhanced solubility and stability of acceptor defects in oxygen co-implanted dual-doped ZnO film are related to the reduction of oxygen vacancy defects at the surface. Our study demonstrates the prospect of the formation of stable p-type ZnO film through co-implantation.

Nucleation of voids in materials supersaturated with mobile interstitials, vacancies and divacancies

International Nuclear Information System (INIS)

Wolfer, W.G.; Si-Ahmed, A.

1982-01-01

In previous void nucleation theories, the void size has been allowed to change only by one atomic volume through vacancy or interstitial absorption or through vacancy emission. To include the absorption of divacancies, the classical nucleation theory is here extended to include double-step transitions between clusters. The new nucleation theory is applied to study the effect of divacancies on void formation. It is found that the steady-state void nucleation rate is enhanced by several orders of magnitude as compared to results with previous void nucleation theories. However, to obtain void nucleation rates comparable to measured ones, the effect of impurities, segregation and insoluble gases must still be invoked. (author)

The influence of excess vacancy generation on the diffusion of ion implanted phosphorus into silicon

International Nuclear Information System (INIS)

Bakowski, A.

1985-01-01

The diffusion of ion implanted phosphorus in silicon has been studied. It was found that the diffusion coefficient is not only dependent on the phosphorus surface concentration (the concentration effect) but also on the conditions at the silicon surface (the surface effect). The phosphorus diffusion coefficient is considerably lower when the silicon surface during annealing is covered with a CVD oxide layer. It is suggested that excess vacancies generated at the surface are reponsible for both the concentration and surface effects. Enhanced phosphorus diffusion is attributed to the disturbance of thermodynamic equilibrium in the crystal through phosphorus-vacancy part formation by vacancies introduced into silicon at the surface. On the basis of the data presented, it can be concluded that two mechanisms for excess vacancy generation are involved. Assuming that phosphorus diffuses via E-centers, calculations of the concentration profiles and the diffusion coefficient were performed for different concentrations and surface conditions. (orig.)

7 CFR 1221.105 - Vacancies.

Science.gov (United States)

2010-01-01

... Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (MARKETING AGREEMENTS... INFORMATION ORDER Sorghum Promotion, Research, and Information Order Sorghum Promotion, Research, and Information Board § 1221.105 Vacancies. To fill any vacancy occasioned by the death, removal, resignation, or...

Formation of radiation induced precipitates in VVER RPV materials

International Nuclear Information System (INIS)

Platonov, P.A.; Chernobaeva, A.A.

2016-01-01

This paper presents an analysis of experimental results received in course of research of copper-enriched precipitates (Cu-precipitates) and nickel-manganese-silicon clusters (Ni-Mn-Si clusters), which are formed in steels of VVER-type reactor pressure vessels (RPVs) under neutron irradiation. Based on this analysis, a hypothetical model is suggested for cluster formation in course of evolution of a cascade region. The model presumes cluster formation in two stages. At the first stage, in course of cascade region crystallization, a stable cluster is formed in the center of the cascade region, which consists of vacancies and Cu atoms following the mechanism of the inverse Kirkendall effect. At the second stage, diffusion of Ni, Mn and P atoms with a flow of vacancies from the matrix takes place to form a cluster. The size of a cluster is limited by a balance of vacancies' flows entering and leaving the cluster. The paper also considers a possibility of stabilization of atomic-vacancy cluster due to uneven distribution of Ni, Mn and P atoms, which explains dependence of cluster density on the content of these elements. Kinetics of cluster formation and evolution presumed by suggested model is analyzed. It is demonstrated that a fall in cluster density and an increase in their size under high irradiation doses may be caused by a decrease of matrix supersaturation with vacancies resulting from high density of dislocation loops. - Highlights: • The analysis of the mechanism of formation of radiation-induced clusters in RPV steels has been done. • Radiation-induced clusters are formed after the mechanism based on the inverse Kirkendall effect in two stages. • At post-dynamic stage a flow of vacancies moving to the center of the cascade entrains Cu atoms contained and forms a stable atom-vacancies cluster. • At the 2nd stage Cu, Ni, Mn, Si atoms forming complexes with vacancies diffuse into a cluster driving out Fe and Cr atoms from the cluster. • The cluster

Effect of solute atom concentration on vacancy cluster formation in neutron-irradiated Ni alloys

Science.gov (United States)

Sato, Koichi; Itoh, Daiki; Yoshiie, Toshimasa; Xu, Qiu; Taniguchi, Akihiro; Toyama, Takeshi

2011-10-01

The dependence of microstructural evolution on solute atom concentration in Ni alloys was investigated by positron annihilation lifetime measurements. The positron annihilation lifetimes in pure Ni, Ni-0.05 at.%Si, Ni-0.05 at.%Sn, Ni-Cu, and Ni-Ge alloys were about 400 ps even at a low irradiation dose of 3 × 10 -4 dpa, indicating the presence of microvoids in these alloys. The size of vacancy clusters in Ni-Si and Ni-Sn alloys decreased with an increase in the solute atom concentration at irradiation doses less than 0.1 dpa; vacancy clusters started to grow at an irradiation dose of about 0.1 dpa. In Ni-2 at.%Si, irradiation-induced segregation was detected by positron annihilation coincidence Doppler broadening measurements. This segregation suppressed one-dimensional (1-D) motion of the interstitial clusters and promoted mutual annihilation of point defects. The frequency and mean free path of the 1-D motion depended on the solute atom concentration and the amount of segregation.

Enhanced native acceptor-related blue emission of ZnO thin films annealed in an oxygen ambient

International Nuclear Information System (INIS)

Shim, Eunhee; Lee, Choeun; Jung, Eiwhan; Lee, Jinyong; Kim, Doosoo; Lee, Youngmin; Kim, Deukyoung; Lee, Sejoon

2012-01-01

The thermodynamic behaviors of charged point defects in unintentionally-doped ZnO thin films were investigated. The as-grown sample displayed two different types of blue-emission bands: one at ∼2.95 eV from native-donor zinc interstitial (Zn i ) and the other at ∼3.17 eV from native acceptor zinc vacancies (V Zn ). In the samples annealed at oxygen ambience, V Zn -related emission was dramatically enhanced, and Zn i -related emission was drastically reduced. The behavior was observed to become more apparent when the annealing temperature was increased. The results can be explained by both the increased generation probability and the lowered formation enthalpy of V Zn in an oxygen-rich environment, particularly at higher temperatures.

Enhanced native acceptor-related blue emission of ZnO thin films annealed in an oxygen ambient

Energy Technology Data Exchange (ETDEWEB)

Shim, Eunhee; Lee, Choeun; Jung, Eiwhan; Lee, Jinyong; Kim, Doosoo; Lee, Youngmin; Kim, Deukyoung; Lee, Sejoon [Dongguk University, Seoul (Korea, Republic of)

2012-06-15

The thermodynamic behaviors of charged point defects in unintentionally-doped ZnO thin films were investigated. The as-grown sample displayed two different types of blue-emission bands: one at ∼2.95 eV from native-donor zinc interstitial (Zn{sub i}) and the other at ∼3.17 eV from native acceptor zinc vacancies (V{sub Zn}). In the samples annealed at oxygen ambience, V{sub Zn}-related emission was dramatically enhanced, and Zn{sub i}-related emission was drastically reduced. The behavior was observed to become more apparent when the annealing temperature was increased. The results can be explained by both the increased generation probability and the lowered formation enthalpy of V{sub Zn} in an oxygen-rich environment, particularly at higher temperatures.

Suppression of oxygen diffusion by thin Al2O3 films grown on SrTiO3 studied using a monoenergetic positron beam

International Nuclear Information System (INIS)

Uedono, A.; Kiyohara, M.; Yasui, N.; Yamabe, K.

2005-01-01

The annealing behaviors of oxygen vacancies introduced by the epitaxial growth of thin SrTiO 3 and Al 2 O 3 films on SrTiO 3 substrates were studied by using a monoenergetic positron beam. The films were grown by molecular-beam epitaxy without using an oxidant. The Doppler broadening spectra of the annihilation radiation were measured as a function of the incident positron energy for samples fabricated under various growth conditions. The line-shape parameter S, corresponding to the annihilation of positrons in the substrate, was increased by the film growth, suggesting diffusion of oxygen from the substrate into the film and a resultant introduction of vacancies (mainly oxygen vacancies). A clear correlation between the value of S and the substrate conductivity was obtained. From isochronal annealing experiments, the Al 2 O 3 thin film was found to suppress the penetration of oxygen from the atmosphere for annealing temperatures below 600 deg. C. Degradation of the film's oxygen blocking property occurred due to the annealing at 700 deg. C, and this was attributed to the oxidation of the Al 2 O 3 by the atmosphere and the resultant introduction of vacancy-type defects

Vacancy-type defects in TiO2/SiO2/SiC dielectric stacks

Science.gov (United States)

Coleman, P. G.; Burrows, C. P.; Mahapatra, R.; Wright, N. G.

2007-07-01

Open-volume (vacancy-type) point defects have been observed in ˜80-nm-thick titanium dioxide films grown on silicon dioxide/4H silicon carbide substrates as stacks with high dielectric constant for power device applications, using variable-energy positron annihilation spectroscopy. The concentration of vacancies decreases as the titanium dioxide growth temperature is increased in the range from 700to1000°C, whereas grain boundaries form in the polycrystalline material at the highest growth temperatures. It is proposed that the optimal electrical performance for films grown at 800°C reflects a balance between decreasing vacancy concentration and increasing grain boundary formation. The concentration of vacancies at the silicon dioxide/silicon carbide interface appears to saturate after 2.5h oxidation at 1150°C. A supplementary result suggests that the quality of the 10-μm-thick deposited silicon carbide epilayer is compromised at depths of about 2μm and beyond, possibly by the migration of impurities and/or other defects from the standard-grade highly doped 4H silicon carbide wafer beneath the epilayer during oxidation.

Phosphorous–vacancy–oxygen defects in silicon

KAUST Repository

Wang, Hao

2013-07-30

Electronic structure calculations employing the hybrid functional approach are used to gain fundamental insight in the interaction of phosphorous with oxygen interstitials and vacancies in silicon. It recently has been proposed, based on a binding energy analysis, that phosphorous–vacancy–oxygen defects may form. In the present study we investigate the stability of this defect as a function of the Fermi energy for the possible charge states. Spin polarization is found to be essential for the charge neutral defect.

Changing vacancy balance in ZnO by tuning synthesis between zinc/oxygen lean conditions

Science.gov (United States)

Venkatachalapathy, Vishnukanthan; Galeckas, Augustinas; Zubiaga, Asier; Tuomisto, Filip; Kuznetsov, Andrej Yu.

2010-08-01

The nature of intrinsic defects in ZnO films grown by metal organic vapor phase epitaxy was studied by positron annihilation and photoluminescence spectroscopy techniques. The supply of Zn and O during the film synthesis was varied by applying different growth temperatures (325-485 °C), affecting decomposition of the metal organic precursors. The microscopic identification of vacancy complexes was derived from a systematic variation in the defect balance in accordance with Zn/O supply trends.

Surface oxygen vacancy and oxygen permeation flux limits of perovskite ion transport membranes

KAUST Repository

Hunt, Anton; Dimitrakopoulos, Georgios; Ghoniem, Ahmed F.

2015-01-01

© 2015 Elsevier B.V. The mechanisms and quantitative models for how oxygen is separated from air using ion transport membranes (ITMs) are not well understood, largely due to the experimental complexity for determining surface exchange reactions

Hydrogen isotope in erbium oxide: Adsorption, penetration, diffusion, and vacancy trapping

Energy Technology Data Exchange (ETDEWEB)

Mao, Wei, E-mail: mao@nuclear.jp [Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-8656 (Japan); The University Museum, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan); Chikada, Takumi [Department of Chemistry, Graduate School of Science, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka 422-8529 (Japan); Suzuki, Akihiro [Nuclear Professional School, School of Engineering, The University of Tokyo, 2-22, Shirakata-shirane, Tokai, Naka 319-1188, Ibaraki (Japan); Terai, Takayuki [Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-8656 (Japan); Matsuzaki, Hiroyuki [The University Museum, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan)

2015-03-15

Highlights: • H adsorption on cubic Er{sub 2}O{sub 3} surface results in electron transfer from H to the surface. • The H penetration energy of at least 1.6 eV is required for cubic Er{sub 2}O{sub 3} surface. • The dominated mechanisms of H diffusion in bulk Er{sub 2}O{sub 3} are elucidated. • H diffusion near or at vacancies in Er{sub 2}O{sub 3} is an exothermic reaction. - Abstract: In this study, we report results using first-principles density functional theory calculations for four critical aspects of the interaction: H adsorption on Er{sub 2}O{sub 3} surface, surface-to-subsurface penetration of H into Er{sub 2}O{sub 3}, bulk diffusion of H in Er{sub 2}O{sub 3}, and trapping of H at vacancies. We identify surface stable adsorption positions and find that H prefers to transfer electrons to the surfaces and form covalent bonds with the nearest neighboring four oxygen atoms. For low surface coverage of H as in our case (0.89 × 10{sup 14} H/cm{sup 2}), a penetration energy of at least 1.60 eV is required for cubic Er{sub 2}O{sub 3} surfaces. Further, the H diffusion barrier between the planes defined by Er{sub 2}O{sub 3} units along the favorable <1 1 1> direction is found to be very small – 0.16 eV – whereas higher barriers of 0.41 eV and 1.64 eV are required for diffusion across the planes, somewhat higher than the diffusion energy barrier of 0.20 eV observed experimentally at 873 K. In addition, we predict that interstitial H is exothermically trapped when it approaches a vacancy with the vacancy defect behaving as an electron trap since the H-vacancy defect is found to be more stable than the intrinsic defect.

Diffusion in a pure, high-vacancy-content crystal

International Nuclear Information System (INIS)

McKee, R.A.

1981-01-01

The idea that vacancies can follow a nonrandom walk in a solid has been developed and put into a quantitative form for diffusion in a pure, high-vacancy-content crystal. Intrinsic and tracer diffusion in a metal have been analyzed, and the electrical mobility in an ionic solid has been expressed in terms of the tracer diffusion coefficient and the separate correlation factors for atoms and vacancies. The description uses classical methods of diffusion theory, and generalized results that account for nonrandom vacancy walk have been shown to reduce to those obtained by Howard and Lidiard in a system where the vacancy moves randomly as an isolated point defect. Experimental data for carbon diffusion in fcc iron have been examined to illustrate an interstitial-vacancy analogy that was used in this analysis, and the general result has been applied specifically to discuss vacancy diffusion in Fe/sub 1-x/S

Synthesis, Single Crystal Growth, and Properties of Cobalt Deficient Double Perovskite EuBaCo2−xO6−δ (x = 0–0.1

Directory of Open Access Journals (Sweden)

S. V. Telegin

2017-01-01

Full Text Available The cobalt deficient double perovskites EuBaCo2−xO6−δ with x=0–0.1 were obtained both as powders and as single crystal. Formation of cobalt vacancies in their crystal lattice was shown to be accompanied by the formation of oxygen ones. Chemical lattice strain caused by this cooperative disordering of cobalt and oxygen sublattices was found to be isotropic contrary to that caused by the formation of oxygen vacancies only. Cobalt deficiency was also shown to lead to lowering overall conductivity and Seebeck coefficient of EuBaCo2−xO6−δ double perovskites as a result of simultaneous decrease of charge carriers’ concentration and their mobility as well as number of sites available for electrons and holes transfer. Strong anisotropy of the overall conductivity of the single crystal double perovskites EuBaCo2−xO6−δ was found and explained on the basis of preferential location of oxygen vacancies in the rare-earth-oxygen- (REO- planes.

Invariance of the mobility edge in anodic titanium oxides

International Nuclear Information System (INIS)

Tit, N.; Halley, J.W.; Shore, H.B.

1992-05-01

We present a theoretical investigation to explain the electronic and optical properties of anodic rutile TiO 2 thin films of different thicknesses (ranging from 5nm to 20nm). There is experimental evidence that the observed gap state at 0.7eV below the edge of conduction-band is due to an oxygen vacancy. For this reason, oxygen vacancies are used as defects in our model. A comparison of the calculated bulk-photoconductivity to photospectroscopy experiment reveals that the films have bulk-like transport properties with a bandgap E g =3.0eV. On the other hand, a fit of the surface density of states to the scanning tunneling microscopy (STM) experiment on the (001) surfaces has suggested a surface defect density of 5% of oxygen vacancies. To resolve this discrepancy, we calculated the dc-conductivity where localization effects are included. Our results show an impurity band formation at about p c =9% of oxygen vacancies. We concluded that the studied films have defect densities below the threshold of impurity band formation. As a consequence the gap states seen in STM are localized (i.e. the oxygen vacancies are playing the role of trapping centers, deep levels) and the mobility edge is invariant. (author). 11 refs, 3 figs

HYDROGEN VACANCY INTERACTION IN TUNGSTEN

NARCIS (Netherlands)

FRANSENS, [No Value; ELKERIEM, MSA; PLEITER, F

1991-01-01

Hydrogen-vacancy interaction in tungsten was investigated by means of the perturbed angular correlation technique, using the isotope In-111 as a probe. Hydrogen trapping at an In-111-vacancy cluster manifests itself as a change of the local electric field gradient, which gives rise to an observable

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

International Nuclear Information System (INIS)

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.

Strontium-free rare earth perovskite ferrites with fast oxygen exchange kinetics: Experiment and theory

Science.gov (United States)

Berger, Christian; Bucher, Edith; Windischbacher, Andreas; Boese, A. Daniel; Sitte, Werner

2018-03-01

The Sr-free mixed ionic electronic conducting perovskites La0.8Ca0.2FeO3-δ (LCF82) and Pr0.8Ca0.2FeO3-δ (PCF82) were synthesized via a glycine-nitrate process. Crystal structure, phase purity, and lattice constants were determined by XRD and Rietveld analysis. The oxygen exchange kinetics and the electronic conductivity were obtained from in-situ dc-conductivity relaxation experiments at 600-800 °C and 1×10-3≤pO2/bar≤0.1. Both LCF82 and PCF82 show exceptionally fast chemical surface exchange coefficients and chemical diffusion coefficients of oxygen. The oxygen nonstochiometry of LCF82 and PCF82 was determined by precision thermogravimetry. A point defect model was used to calculate the thermodynamic factors of oxygen and to estimate self-diffusion coefficients and ionic conductivities. Density Functional Theory (DFT) calculations on the crystal structure, oxygen vacancy formation as well as oxygen migration energies are in excellent agreement with the experimental values. Due to their favourable properties both LCF82 and PCF82 are of interest for applications in solid oxide fuel cell cathodes, solid oxide electrolyser cell anodes, oxygen separation membranes, catalysts, or electrochemical sensors.

The electronic structure and bonding of a H-H pair in the vicinity of a BCC Fe bulk vacancy

Energy Technology Data Exchange (ETDEWEB)

Juan, A.; Pistonesi, C.; Brizuela, G. [Universidad Nacional del Sur, Bahia Blanca (Argentina). Departamento de Fisica; Garcia, A.J. [Universidad Nacional del Sur, Bahia Blanca (Argentina). Departamento de Ciencias de la Computacion

2003-09-01

The H-Fe interaction near a bcc Fe vacancy is analysed using a semi-empirical theoretical method. Calculations were performed using a Fe{sub 86} cluster with a vacancy. Hydrogen atoms are positioned in their local energy minima configurations. Changes in the electronic structure of Fe atoms near a vacancy were analysed for the system without H, with one H and with two H atoms. Fe atoms surrounding the vacancy weaken their bond when hydrogen is present. This is due to the formation of H-Fe bonds. Hydrogen influences only its nearest-neighbour Fe atoms. The H-H interaction was also analysed. For H-H distance of 0.82 Angstrom an H-H association is formed, while H-Fe interaction and Fe-Fe weakening is markedly reduced, when compared with other H-H interactions. (author)

Vacancy decay in endohedral atoms

International Nuclear Information System (INIS)

Amusia, M. Ya.; Baltenkov, A. S.

2006-01-01

It is demonstrated that the fullerene shell dramatically affects the radiative and Auger vacancy decay of an endohedral atom A-C 60 . The collectivized electrons of the C 60 shell add new possibilities for radiative and nonradiative decays similar to that in ordinary atoms where the vacancies in the initial and final state almost always belong to different subshells. It is shown that the smallness of the atomic shell radii as compared to that of the fullerene shell provides an opportunity to derive the simple formulas for the probabilities of the electron transitions. It is shown that the radiative and Auger (or Koster-Kronig) widths of the vacancy decay due to electron transition in the atom A in A-C 60 acquire an additional factor that can be expressed via the polarizability of the C 60 at transition energy. It is demonstrated that due to an opening of the nonradiative decay channel for vacancies in subvalent subshells the decay probability increases by five to six orders of magnitude

Theoretical study on magnetism induced by H vacancy in isolated Alq3 and Gaq3 molecules

Science.gov (United States)

Ju, Lin; Xu, Tongshuai; Zhang, Yongjia; Sun, Li

2017-10-01

The magnetism induced by H vacancy in isolated Alq3 and Gaq3 molecules has been studied based on density functional theory. The isolated stoichiometric Alq3 and Gaq3 molecules are non-magnetic. With an H vacancy, both Alq3 and Gaq3 molecules could show magnetism, which are mainly due to the polarization of the C 2p electrons and the magnetic moments are mainly distributed at most nearby C atoms of H vacancies. This is because the unpaired electron on the C atom appears, when the H atom nearby is removed. Six cases of the H vacancy introduced in the Alq3 and Gaq3 molecules are considered, respectively. By comparing the relative defect formation energy, the V H3 vacancy is most likely to appear in the two kinds of molecules. In addition, for the ground state configuration of isolated Alq3 and Gaq3 molecules with two H vacancies, the energy of the ferromagnetic state is lower than that of the antiferromagnetic state, which means that the ferromagnetic state is stable. The ferromagnetic mechanism can be explained by the Heisenberg direct exchange interaction between two the polarized C atoms. Our work opens a new way to synthesize organic magnetic materials and perfects the theory of organic ferromagnetism by introducing the d 0 ferromagnetism.

Remarkable changes in interface O vacancy and metal-oxide bonds in amorphous indium-gallium-zinc-oxide thin-film transistors by long time annealing at 250 °C

International Nuclear Information System (INIS)

Chowdhury, Md Delwar Hossain; Um, Jae Gwang; Jang, Jin

2014-01-01

We have studied the effect of long time post-fabrication annealing on negative bias illumination stress (NBIS) of amorphous indium-gallium-zinc-oxide (a-IGZO) thin-film-transistors. Annealing for 100 h at 250 °C increased the field effect mobility from 14.7 cm 2 /V s to 17.9 cm 2 /V s and reduced the NBIS instability remarkably. Using X-ray photoelectron spectroscopy, the oxygen vacancy and OH were found to exist at the interfaces of a-IGZO with top and bottom SiO 2 . Long time annealing helps to decrease the vacancy concentration and increase the metal-oxygen bonds at the interfaces; this leads to increase in the free carrier concentrations in a-IGZO and field-effect mobility. X-ray reflectivity measurement indicated the increment of a-IGZO film density of 5.63 g cm −3 to 5.83 g cm −3 (3.4% increase) by 100 h annealing at 250 °C. The increase in film density reveals the decrease of O vacancy concentration and reduction of weak metal-oxygen bonds in a-IGZO, which substantially helps to improve the NBIS stability

Theoretical study on the magnetic moments formation in Ta-doped anatase TiO2

Science.gov (United States)

Bupu, A.; Majidi, M. A.; Rusydi, A.

2017-04-01

We present a theoretical study on Ti-vacancy induced ferromagnetism in Ta-doped anatase TiO2. Experimental study of Ti1-x Ta x O2 thin film has shown that Ti-vacancies (assisted by Ta doping) induce the formation of localized magnetic moment around it, then, the observed ferromagnetism is caused by the alignment of localized magnetic moments through Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction. In this study, we focus on the formation of the localized magnetic moments in this system. We hypothesize that on a unit cell, Ti-vacancy has caused four electrons from the surrounding oxygen atoms to become unpaired. These unpaired electrons then arrange themselves into a configuration with a non-zero net magnetic moment. To examine our hypothesis, we construct a Hamiltonian of the four unpaired electrons, incorporating the Coulomb intra- and inter-orbital interactions, in matrix form. Using a set of chosen parameter values, we diagonalize the Hamiltonian to get the eigenstates and eigenvalues, then, with the resulting eigenstates, we calculate the magnetic moment, μ, by obtaining the expectation value of the square of total spin operator. Our calculation results show that in the ground state, provided that the ratio of parameters satisfies some criterion, μ ≈ 4μ B , corresponding to the four electron spins being almost perfectly aligned, can be achieved. Further, as long as we keep the Coulomb intra-orbital interaction between 0.5 and 1 eV, we find that μ ≈ 4μ B is robust up to far above room temperature. Our results demonstrate that Ti vacancies in anatase TiO2 can form very stable localized magnetic moments.

Drift forces on vacancies and interstitials in alloys with radiation-induced segregation

International Nuclear Information System (INIS)

Wolfer, W.G.

1983-01-01

Radiation-induced segregation in alloys leads to compositional gradients around point defect sinks such as voids and dislocations. These compositional gradients in turn affect the drift forces on both interstitials and vacancies and thereby modify the bias. Linear irreversible thermodynamics is employed to derive the total drift force on interstitials and vacancies in substitutional binary alloys. The obtained results are evaluated for binary Fe-Ni alloys. It is shown that radiation-induced segregation produces new drift forces which can be of the same order of magnitude as the stress-induced drift force produced by edge dislocations in an alloy with uniform composition. Hence, segregation results in a significant modification of the bias for void nucleation and swelling. The additional drift forces on interstitials and vacancies are due to the compositional dependence of the formation and migration energies; due to the dependence of the point defect's strain energy on the local elastic properties; due to a coherency strain field caused by lattice parameter variations; and finally due to the Kirkendall force produced by the difference in tracer mobilities. Estimates of these forces given for Fe-Ni alloys indicate that the Kirkendall force is small compared to the other segregation-induced forces on interstitials. In contrast, the Kirkendall force seems to be the dominant one for vacancies. (orig.)

Direct observation of hopping induced spin polarization current in oxygen deficient Co-doped ZnO by Andreev reflection technique

Energy Technology Data Exchange (ETDEWEB)

Yang, Kung-Shang; Huang, Tzu-Yu; Dwivedi, G.D. [Department of Physics, National Sun Yat-sen University, Kaohsiung, Taiwan (China); Lin, Lu-Kuei; Lee, Shang-Fan [Taiwan Institute of Physics, Academia Sinica, Taipei, Taiwan (China); Sun, Shih-Jye [Department of Applied Physics, National Kaohsiung University, Kaohsiung, Taiwan (China); Chou, Hsiung, E-mail: hchou@mail.nsysu.edu.tw [Department of Physics, National Sun Yat-sen University, Kaohsiung, Taiwan (China)

2017-07-01

Highlights: • Co-doped ZnO thin-films were grown with varying V{sub O} concentartion. • PCAR measurements were done to study the SPC. • High spin polarization was observed above a certain V{sub O} concentartion. • High V{sub O} samples provide a high density of completed percolation path. • This complete percolation path gives rise to high SPC. - Abstract: Oxygen vacancy induced ferromagnetic coupling in diluted magnetic oxide (DMO) semiconductors have been reported in several studies, but technologically more crucial spin-polarized current (SPC) is still under-developed in DMOs. Few studies have claimed that VRH mechanism can originate the SPC, but, how VRH mechanism associated with percolation path, is not clearly understood. We used Point-contact Andreev reflection (PCAR) technique to probe the SPC in Co-doped ZnO (CZO) films. Since the high resistance samples cause broadening in conductance(G)-voltage(V) curves, which may result in an unreliable evaluation of spin polarization, we include two extra parameters, (i) effective temperature and (ii) spreading resistance, for the simulation to avoid the uncertainty in extracting spin polarization. The effective G-V curves and higher spin polarization can be obtained above a certain oxygen vacancy concentration. The number of completed and fragmentary percolation paths is proportional to the concentration of oxygen vacancies. For low oxygen vacancy samples, the Pb-tip has a higher probability of covering fragmentary percolation paths than the complete ones, due to its small contact size. The completed paths may remain independent of one another and get polarized in different directions, resulting in lower spin-polarization value. High oxygen vacancy samples provide a high density of completed path, most of them link to one another by crossing over, and gives rise to high spin-polarization value.

First-principles study of intrinsic defects in CdO

Science.gov (United States)

Zhukov, V. P.; Medvedeva, N. I.; Krasilnikov, V. N.

2018-03-01

Using the density functional theory (DFT) in the GGA and LSDA + U approximations, we studied the effect of cadmium atoms in the interstitial sites and vacancies in the oxygen and cadmium sublattices on the electronic structure of rock-salt cadmium oxide (CdO). Migration of cadmium atoms into interstitial sites was shown to be unlikely. In the presence of oxygen vacancies, the behavior of CdO remains semiconducting and nonmagnetic. Cadmium vacancies induce d0 ferromagnetism and spin-dependent conductivity, which is semiconducting for spin-up electrons and is p-type metallic for spin-down electrons. The formation energies and free energies were calculated for oxygen vacancies and metallic cadmium phase, which allowed an explanation to be offered for the large number of vacancies and the metallic phase formed during reduction in hydrogen atmosphere.

Vacancy-mediated fcc/bcc phase separation in Fe1 -xNix ultrathin films

Science.gov (United States)

Menteş, T. O.; Stojić, N.; Vescovo, E.; Ablett, J. M.; Niño, M. A.; Locatelli, A.

2016-08-01

The phase separation occurring in Fe-Ni thin films near the Invar composition is studied by using high-resolution spectromicroscopy techniques and density functional theory calculations. Annealed at temperatures around 300 ∘C ,Fe0.70Ni0.30 films on W(110) break into micron-sized bcc and fcc domains with compositions in agreement with the bulk Fe-Ni phase diagram. Ni is found to be the diffusing species in forming the chemical heterogeneity. The experimentally determined energy barrier of 1.59 ±0.09 eV is identified as the vacancy formation energy via density functional theory calculations. Thus, the principal role of the surface in the phase separation process is attributed to vacancy creation without interstitials.

Nanocrystalline SnO2 formation by oxygen ion implantation in tin thin films

Science.gov (United States)

Kondkar, Vidya; Rukade, Deepti; Kanjilal, Dinakar; Bhattacharyya, Varsha

2018-03-01

Metallic tin thin films of thickness 100 nm are deposited on fused silica substrates by thermal evaporation technique. These films are implanted with 45 keV oxygen ions at fluences ranging from 5 × 1015 to 5 × 1016 ions cm-2. The energy of the oxygen ions is calculated using SRIM in order to form embedded phases at the film-substrate interface. Post-implantation, films are annealed using a tube furnace for nanocrystalline tin oxide formation. These films are characterized using x-ray diffraction, Raman spectroscopy, UV-vis spectroscopy and photoluminescence spectroscopy. XRD and Raman spectroscopy studies reveal the formation of single rutile phase of SnO2. The size of the nanocrystallites formed decreases with an increase in the ion fluence. The nanocrystalline SnO2 formation is also confirmed by UV-vis and photoluminescence spectroscopy.

The effect of oxygen on segregation-induced redistribution of rare-earth elements in silicon layers amorphized by ion implantation

International Nuclear Information System (INIS)

Aleksandrov, O. V.

2006-01-01

A model of segregation-induced redistribution of impurities of rare-earth elements during solid-phase epitaxial crystallization of silicon layers amorphized by ion implantation is developed. This model is based on the assumption that a transition layer with a high mobility of atoms is formed at the interphase boundary on the side of a-Si; the thickness of this layer is governed by the diffusion length of vacancies in a-Si. The Er concentration profiles in Si implanted with both erbium and oxygen ions are analyzed in the context of the model. It shown that, in the case of high doses of implantation of rare-earth ions, it is necessary to take into account the formation of R m clusters (m = 4), where R denotes the atom of a rare-earth element, whereas, if oxygen ions are also implanted, formation of the complexes RO n (n = 3-6) should be taken into account; these complexes affect the transition-layer thickness and segregation coefficient

AB initio energetics of lanthanum substitution in ferroelectric bismuth titanate

International Nuclear Information System (INIS)

Shah, S.H.

2012-01-01

Density functional theory based electronic structure calculations play a vital role in understanding, controlling and optimizing physical properties of materials at microscopic level. In present study system of interest is bismuth titanate (Bi/sub 4/Ti/sub 3/O/sub 12/)/(BIT) which has wide range of applications such as a high temperature piezoelectric and one of the best material for memory devices. However, it also suffers from serious issues such as oxygen vacancies which degrade its performance as a memory element and piezoelectric material. In this context, the bulk and defect properties of orthorhombic bismuth titanate (Bi/sub 4/Ti/sub 3/O/sub 12/) and bismuth lanthanum titanate (Bi/sub 3.25/La/sub 0.75/Ti/sub 3/O/sub 12/)/(BLT, x=0.75) were investigated by using first principles calculations and atomistic thermodynamics. Heats of formation, valid chemical conditions for synthesis, lanthanum substitution energies and oxygen and bismuth vacancy formation energies were computed. The study improves understanding of how native point defects and substitutional impurities influence the ferroelectric properties of these layered perovskite materials. It was found that lanthanum incorporation could occur on either of the two distinct bismuth sites in the structure and that the effect of substitution is to increase the formation energy of nearby native oxygen vacancies. The results provide direct atomistic evidence over a range of chemical conditions for the suggestion that lanthanum incorporation reduces the oxygen vacancy concentration. Oxygen vacancies contribute to ferroelectric fatigue by interacting strongly with domain walls and therefore a decrease in their concentration is beneficial. (orig./A.B.)

Mechanisms of defect complex formation and environmental-assisted fracture behavior of iron aluminides

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