Sample records for lanio3 lani1-xfexo3 andlani1-xcoxo3

  1. Preparation and characterization of LaNiO3 films grown by metal ...

    Indian Academy of Sciences (India)


    Keywords. Conductive films; LaNiO3; metal–organic deposition; texture. 1. Introduction ... films on Si (111) and quartz substrates were first prepared with the 2-ethyl hexanotes of ..... Li A, Ge C, Lü P and Ming N 1996a Appl. Phys. Lett. 68. 1347.

  2. Orientation control of chemical solution deposited LaNiO3 thin films

    International Nuclear Information System (INIS)

    Ueno, Kengo; Yamaguchi, Toshiaki; Sakamoto, Wataru; Yogo, Toshinobu; Kikuta, Koichi; Hirano, Shin-ichi


    High quality LaNiO 3 (LNO) thin films with preferred orientation could be synthesized on Pt/Ti/SiO 2 /Si substrates at 700 deg. C using the chemical solution deposition method. The homogeneous and stable LNO precursor solutions were prepared using lanthanum isopropoxide and nickel (II) acetylacetonate in a mixed solvent of absolute ethanol and 2-methoxyethanol. The oriented LNO thin films exhibit metallic electro-conduction, and their resistivity at room temperature is sufficiently low for making them an alternative electrode material for functional ceramic thin films

  3. Dry etching of LaNiO3 thin films using inductively coupled plasma

    International Nuclear Information System (INIS)

    Kim, Gwan-Ha; Kim, Dong-Pyo; Kim, Kyoung-Tae; Kim, Chang-Il; Lee, Cheol-In; Kim, Tae-Hyung


    The etching characteristics of LaNiO 3 (LNO) thin films and SiO 2 in Cl 2 /Ar plasma were investigated. LNO etch rates decreased with increasing Cl 2 fraction in Ar plasma and the working pressure. Langmuir probe measurement showed a noticeable influence of Cl 2 /Ar mixing ratio on electron temperature, electron density, and ion current density. The modeling of volume kinetics for charged particles and OES measurements for neutral atoms indicated monotonous changes of both densities and fluxes of active species such as chlorine atoms and positive ions. The LNO etch rate behavior may be explained by physical mechanisms

  4. Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution (United States)

    Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios


    The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

  5. A First Principles Study of H2 Adsorption on LaNiO3(001 Surfaces

    Directory of Open Access Journals (Sweden)

    Changchang Pan


    Full Text Available The adsorption of H2 on LaNiO3 was investigated using density functional theory (DFT calculations. The adsorption sites, adsorption energy, and electronic structure of LaNiO3(001/H2 systems were calculated and indicated through the calculated surface energy that the (001 surface was the most stable surface. By looking at optimized structure, adsorption energy and dissociation energy, we found that there were three types of adsorption on the surface. First, H2 molecules completely dissociate and then tend to bind with the O atoms, forming two –OH bonds. Second, H2 molecules partially dissociate with the H atoms bonding to the same O atom to form one H2O molecule. These two types are chemical adsorption modes; however, the physical adsorption of H2 molecules can also occur. When analyzing the electron structure of the H2O molecule formed by the partial dissociation of the H2 molecule and the surface O atom, we found that the interaction between H2O and the (001 surface was weaker, thus, H2O was easier to separate from the surface to create an O vacancy. On the (001 surface, a supercell was constructed to accurately study the most stable adsorption site. The results from analyses of the charge population; electron localization function; and density of the states indicated that the dissociated H and O atoms form a typical covalent bond and that the interaction between the H2 molecule and surface is mainly due to the overlap-hybridization among the H 1s, O 2s, and O 2p states. Therefore, the conductivity of LaNiO3(001/H2 is stronger after adsorption and furthermore, the conductivity of the LaNiO3 surface is better than that of the LaFeO3 surface.

  6. Characterization of LaNiO3 prepared by sol–gel: Application to hydrogen evolution under visible light

    International Nuclear Information System (INIS)

    Khettab, M.; Omeiri, S.; Sellam, D.; Ladjouzi, M.A.; Trari, M.


    Highlights: ► Photoactive LaNiO 3 was prepared by sol–gel. ► LaNiO 3 exhibits n type conductivity it due to slight oxygen deficiency. ► LaNiO 3 was successfully for hydrogen evolution upon visible light. - Abstract: The semi conducting properties of LaNiO 3 , elaborated by sol–gel, have been investigated for the first time by the photocurrent technique and capacitance measurements. The oxide crystallizes in a distorted perovskite structure and the transport properties indicate degenerate conductivity with activation energy of 18 meV. The infrared spectrum allowed us to evaluate the band gap at 88 meV. The electrochemical behaviour has been studied in alkaline electrolyte (KOH, 0.5 M). The corrosion potential (−0.204 V SCE ) and the exchange current density (0.103 mA cm −2 ), determined from the semi logarithmic plot, indicate long lived oxide. The slope and the intercept to C −2 = 0 of the Mott Schottky plot, characteristic of n type behaviour, gave respectively an electron density (N D ) of 2.3 × 10 19 cm −3 and a flat band potential (V fb ) of −0.61 V SCE . The nature of the Nyquist plot, measured over a wide frequency range (10 −3 –10 5 Hz), shows the predominance of the bulk contribution. The arc is not centred on the real axis (−6.3°), an evidence of a constant phase element. The straight line at low frequencies is due to Warburg diffusion and the data are interpreted thanks to the Randles model. The absorption of light promotes electrons into LaNiO 3 –CB with a potential (−0.62 V SCE ) sufficient to reduce water (−0.50 V SCE ). As application, the oxide has been tested successfully for hydrogen evolution upon visible light with a rate evolution of 1.73 μmol min −1 (g catalyst) −1 and a quantum efficiency of 0.042% under full light (29 mW cm −2 ).

  7. Synthesis of LaNiO3 perovskite type by chelating precursor method using EDTA: optimization of chelating content

    International Nuclear Information System (INIS)

    Santos, Jose Carlos dos; Pedrosa, Anne Michelle Garrido; Mesquita, Maria Eliane; Souza, Marcelo Jose Barros de


    The perovskites are strategic materials due their catalytic, electronic and magnetic properties. These properties are influenced by the calcination and synthesis conditions. In this work was carried out the synthesis of LaNiO 3 perovskite type by chelating precursor method using EDTA and also was studied the optimization of the EDTA content in the synthesis. The synthesized materials were characterized by X-ray diffraction (XRD), thermal gravimetric analysis (TG) and Infrared Spectroscopy (FTIR). In the optimization of the EDTA content the lowest ratio of metal / EDTA used was 1.0 / 0.1, where it was possible to obtain monophasic perovskite. (author)

  8. Comparative study of LaNiO$_3$/LaAlO$_3$ heterostructures grown by pulsed laser deposition and oxide molecular beam epitaxy


    Wrobel, F.; Mark, A. F.; Christiani, G.; Sigle, W.; Habermeier, H. -U.; van Aken, P. A.; Logvenov, G.; Keimer, B.; Benckiser, E.


    Variations in growth conditions associated with different deposition techniques can greatly affect the phase stability and defect structure of complex oxide heterostructures. We synthesized superlattices of the paramagnetic metal LaNiO3 and the large band gap insulator LaAlO3 by atomic layer-by-layer molecular beam epitaxy (MBE) and pulsed laser deposition (PLD) and compared their crystallinity, microstructure as revealed by high-resolution transmission electron microscopy images and resistiv...

  9. Generalizable, Electroless, Template-Assisted Synthesis and Electrocatalytic Mechanistic Understanding of Perovskite LaNiO3 Nanorods as Viable, Supportless Oxygen Evolution Reaction Catalysts in Alkaline Media. (United States)

    McBean, Coray L; Liu, Haiqing; Scofield, Megan E; Li, Luyao; Wang, Lei; Bernstein, Ashley; Wong, Stanislaus S


    The oxygen evolution reaction (OER) is a key reaction for water electrolysis cells and air-powered battery applications. However, conventional metal oxide catalysts, used for high-performing OER, tend to incorporate comparatively expensive and less abundant precious metals such as Ru and Ir, and, moreover, suffer from poor stability. To attempt to mitigate for all of these issues, we have prepared one-dimensional (1D) OER-active perovskite nanorods using a unique, simple, generalizable, and robust method. Significantly, our work demonstrates the feasibility of a novel electroless, seedless, surfactant-free, wet solution-based protocol for fabricating "high aspect ratio" LaNiO 3 and LaMnO 3 nanostructures. As the main focus of our demonstration of principle, we prepared as-synthesized LaNiO 3 rods and correlated the various temperatures at which these materials were annealed with their resulting OER performance. We observed generally better OER performance for samples prepared with lower annealing temperatures. Specifically, when annealed at 600 °C, in the absence of a conventional conductive carbon support, our as-synthesized LaNiO 3 rods not only evinced (i) a reasonable level of activity toward OER but also displayed (ii) an improved stability, as demonstrated by chronoamperometric measurements, especially when compared with a control sample of commercially available (and more expensive) RuO 2 .

  10. Low Fatigue in Epitaxial Pb(Zr0.2Ti0.8)O3 on Si Substrates with LaNiO3 Electrodes by RF Sputtering (United States)

    Wang, Chun; Kryder, Mark H.


    Epitaxial PZT (001) thin films with a LaNiO3 bottom electrode were deposited by radio-frequency (RF) sputtering onto Si(001) single-crystal substrates with SrTiO3/TiN buffer layers. Pb(Zr0.2Ti0.8)O3 (PZT) samples were shown to consist of a single perovskite phase and to have an (001) orientation. The orientation relationship was determined to be PZT(001)[110]∥LaNiO3(001)[110]∥SrTiO3 (001)[110]∥TiN(001)[110]∥Si(001)[110]. Atomic force microscope (AFM) measurements showed the PZT films to have smooth surfaces with a roughness of 1.15 nm. The microstructure of the multilayer was studied using transmission electron microscopy (TEM). Electrical measurements were conducted using both Pt and LaNiO3 as top electrodes. The measured remanent polarization P r and coercive field E c of the PZT thin film with Pt top electrodes were 23 μC/cm2 and 75 kV/cm, and were 25 μC/cm2 and 60 kV/cm for the PZT film with LaNiO3 top electrodes. No obvious fatigue after 1010 switching cycles indicated good electrical endurance of the PZT films using LaNiO3 electrodes, compared with the PZT film with Pt top electrodes showing a significant polarization loss after 108 cycles. These PZT films with LaNiO3 electrodes could be potential recording media for probe-based high-density data storage.

  11. Crystallization of Sr0.5Ba0.5Nb2O6 Thin Films on LaNiO3 Electrodes by RF Magnetron Reactive Sputtering (United States)

    Jong, Chao-An; Gan, Jon-Yiew


    Strontium barium niobium (Sr0.5Ba0.5Nb2O6) (SBN) thin films are prepared on conductive-oxide LNO (LaNiO3) electrodes by the rf magnetron sputtering system. Instead of conventional furnace annealing, SBN thin films are crystallized by rapid thermal annealing (RTA) above 700°C for 5 min. The textured SBN films are crystallized with two orientations: one is the (001) or (310) direction, and the other is the (002) or (620) direction. Films compositions measured by the electron spectroscopy of chemical analysis (ESCA) quantitative analysis method show nearly the same stoichiometric ratio as the target. The depth profiles of SBN films and the target are examined by secondary ion mass spectrometer (SIMS). The concentrations of the films are quite uniform. After being heat treated at 800°C for 5 min by RTA, La and Ni diffuse into the SBN film. The diffusion coefficient of La in SBN films is also calculated.

  12. Annealing effect on the bipolar resistive switching behaviors of BiFeO3 thin films on LaNiO3-buffered Si substrates

    International Nuclear Information System (INIS)

    Chen Xinman; Zhang Hu; Ruan Kaibin; Shi Wangzhou


    Highlights: ► Annealing effect on the bipolar resistive switching behaviors of BiFeO 3 thin films with Pt/BiFeO 3 /LNO was reported. ► Rectification property was explained from the asymmetrical contact between top and bottom interfaces and the distinct oxygen vacancy density. ► The modification of Schottky-like barrier was suggested to be responsible for the resistance switching behaviors of Pt/BiFeO 3 /LNO devices. - Abstract: We reported the annealing effect on the electrical behaviors of BiFeO 3 thin films integrated on LaNiO 3 (LNO) layers buffered Si substrates by sol–gel spin-coating technique. All the BiFeO 3 thin films exhibit the reversible bipolar resistive switching behaviors with Pt/BiFeO 3 /LNO configuration. The electrical conduction mechanism of the devices was dominated by the Ohmic conduction in the low resistance state and trap-controlled space charged limited current in the high resistance state. Good diode-like rectification property was observed in device with BiFeO 3 film annealed at 500 °C, but vanished in device with BiFeO 3 film annealed at 600 °C. This was attributed to the asymmetrical contact between top and bottom interfaces as well as the distinct oxygen vacancy density verified by XPS. Furthermore, the modification of Schottky-like barrier due to the drift of oxygen vacancies was suggested to be responsible for the resistance switching behaviors of Pt/BiFeO 3 /LNO devices.

  13. A Study on Production of Carbon Nanotubes by CH4 Decomposition over LaNiO3, La4Ni3O10, La3Ni2O7 and La2NiO4

    Institute of Scientific and Technical Information of China (English)


    Carbon nanotubes (CNTs) of narrow size distribution can be abundantly produced in the catalytic decomposition of CH4 over pre-reduced LaNiO3, La4Ni3O10, La3Ni2O7 and La2NiO4.The CNTs obtained were characterized by means of transmission electron microscopy (TEM).Thermal oxidation of CNTs in air was monitored thermogravimetrically (TG). The resultsrevealed that a lower La/Ni ratio of the catalysts would lead to a wider diameter distribution and a higher degree of graphitic nature.

  14. LaNiO3 buffer layers for high critical current density YBa2Cu3O7-δ and Tl2Ba2CaCu2O8-δ films

    International Nuclear Information System (INIS)

    Carlson, C.M.; Parilla, P.A.; Siegal, M.P.; Ginley, D.S.; Wang, Y.; Blaugher, R.D.; Price, J.C.; Overmyer, D.L.; Venturini, E.L.


    We demonstrate high critical current density superconducting films of YBa 2 Cu 3 O 7-δ (YBCO) and Tl 2 Ba 2 CaCu 2 O 8-δ (Tl-2212) using LaNiO 3 (LNO) buffer layers. YBCO films grown on an LNO buffer layer have only a slightly lower J c (5 K, H=0) than films grown directly on a bare LaAlO 3 substrate. YBCO films grown on LNO buffer layers exhibit minor microstructural disorder and enhanced flux pinning. LNO-buffered Tl-2212 samples show large reductions in J c at all temperatures and fields compared to those grown on bare LaAlO 3 , correlating to both a-axis grain and nonsuperconducting phase formation. LNO could be a promising buffer layer for both YBCO and Tl-based superconducting films in coated conductor applications. copyright 1999 American Institute of Physics

  15. LaNiO3 Buffer Layers for High Critical Current Density YBa2Cu3O7δ and Tl2Ba2CaCu2O8δ Films

    International Nuclear Information System (INIS)

    Carlson, C.M.; Parilla, P.A.; Siegal, M.P.; Ginley, D.S.; Wang, Y.-T.; Blaugher, R.D.; Price, J.C.; Overmyer, D.L.; Venturini, E.L.


    We demonstrate high critical current density superconducting films of YBa 2 Cu 3 O 7-δ (YBCO) and Tl 2 Ba 2 CaCu 2 O 8-δ (Tl-2212) using LaNiO 3 (LNO) buffer layers. YBCO films grown on an LNO buffer layer have only a slightly lower J c (5K, H=0) than films grown directly on a bare LaAlO 3 substrate. It is noteworthy that YBCO films grown on LNO buffer layers exhibit minor microstructural disorder and enhanced flux pinning. LNO-buffered Tl-2212 samples show large reductions in J c at all temperatures and fields compared to those grown on bare LaAlO 3 , correlating to both a-axis grain and nonsuperconducting phase formation. With additional optimization, LNO could be a promising buffer layer for both YBCO and Tl-based superconducting films, perhaps ideally suited for coated conductor applications

  16. Effect of thermal strain on structure and polarization fatigue of CSD-derived PbZr0.53Ti0.47O3/LaNiO3 hetero-structures

    International Nuclear Information System (INIS)

    Wang, G.S.; Remiens, D.; Dogheche, E.; Dong, X.L.


    PbZr 0.53 Ti 0.47 O 3 /LaNiO 3 (PZT/LNO) hetero-structures have been successfully deposited on MgO, SrTiO 3 , Al 2 O 3 and Si substrate by chemical solution routes, respectively. The X-ray diffraction measurements show that out-of-plane lattice parameters of PZT increase as increase of thermal expansion coefficient of substrate. Polarization fatigues of Pt/PZT/LNO capacitors are strongly affected by the thermal strain caused by difference of thermal expansion coefficient between PZT and substrate materials. High fatigue resistance of Pt/PZT/LNO can be obtained by using substrate with similar thermal expansion coefficient as PZT. (orig.)

  17. Comparative study between traditional and modified Pechini synthesis methods in the preparation of LaNiO_3 and LaNi_0_,_8Co_0_,_2O_3 catalysts

    International Nuclear Information System (INIS)

    Silva, F.E.F.; Aquino, F.M.; Silva, M.C.M.F.


    One of the ways of obtaining hydrogen is from the methane reforming reaction, which is an endothermic and non-spontaneous reaction. In order to minimize this energy, nickel catalysts are used. This work aims to synthesize and characterize the catalysts LaNiO_3 and LaNi_0_,_8Co_0_,_2O_3 using the Pechini method, making use of citric acid and ethylene glycol and modified Pechini, using the edible gelatin as a chelating and polymerizing agent. The obtained materials were characterized by X-Ray Diffraction (XRD), where the formation of peaks characteristic of perovskite and monophasic structures was observed. Scanning Electron Microscopy (SEM) showed that porosity and powders with few agglomerates were observed by both methods. In the analysis of determination of the specific surface area (BET) the materials were shown with areas that are according to the literature

  18. Study of Ni2-Mn-Ga phase formation by magnetron sputtering film deposition at low temperature onto Si substrates and LaNiO3/Pb(Ti,Zr)O3 buffer

    International Nuclear Information System (INIS)

    Figueiras, F.; Rauwel, E.; Amaral, V. S.; Vyshatko, N.; Kholkin, A. L.; Soyer, C.; Remiens, D.; Shvartsman, V. V.; Borisov, P.; Kleemann, W.


    Film deposition of Ni 2 MnGa phaselike alloy by radio frequency (rf) magnetron sputtering was performed onto bare Si(100) substrates and LaNiO 3 /Pb(Ti,Zr)O 3 (LNO/PZT) ferroelectric buffer layer near room temperature. The prepared samples were characterized using conventional x-ray diffraction (XRD), superconducting quantum interference device, and electron dispersive x-ray spectroscopy from scanning electron microscope observations. The optimized films deposited under high rf power and low argon pressure present good surface quality and highly textured phase crystallization. The positioning distance between the substrate and the target-holder axis has some limited effect on the film's composition due to the specific diffusion behavior of each element in the sputtering plasma. Extended four pole high resolution XRD analysis allowed one to discriminate the intended Ni-Mn-Ga tetragonal martensitic phase induced by the (100) LNO/PZT oriented buffer. This low temperature process appears to be very promising, allowing separate control of the functional layer's properties, while trying to achieve high electromagnetoelastic coupling.

  19. LaNiO(3) Buffer Layers for High Critical Current Density YBa(2)Cu(3)O(7-delta) and Tl(2)Ba(2)CaCu(2)O(8-delta) Films

    Energy Technology Data Exchange (ETDEWEB)

    Carlson, C.M.; Parilla, P.A.; Siegal, M.P.; Ginley, D.S.; Wang, Y.-T.; Blaugher, R.D.; Price, J.C.; Overmyer, D.L.; Venturini, E.L.


    We demonstrate high critical current density superconducting films of YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} (YBCO) and Tl{sub 2}Ba{sub 2}CaCu{sub 2}O{sub 8{minus}{delta}} (Tl-2212) using LaNiO{sub 3} (LNO) buffer layers. YBCO films grown on an LNO buffer layer have only a slightly lower J{sub c} (5K, H=0) than films grown directly on a bare LaAlO{sub 3} substrate. It is noteworthy that YBCO films grown on LNO buffer layers exhibit minor microstructural disorder and enhanced flux pinning. LNO-buffered Tl-2212 samples show large reductions in J{sub c} at all temperatures and fields compared to those grown on bare LaAlO{sub 3}, correlating to both a-axis grain and nonsuperconducting phase formation. With additional optimization, LNO could be a promising buffer layer for both YBCO and Tl-based superconducting films, perhaps ideally suited for coated conductor applications.

  20. Filmes finos de LaNiO3 e PZT preparados pelo métodos das soluções precursoras poliméricas e depositados em substratos de silício


    Souza, Éder Carlos Ferreira de [UNESP


    Nesta tese estudou-se a preparação de filmes finos de PZT não dopados e dopados com Nióbio, depositados sobre substratos de Pt/Ti/SiO2/Si para aplicações em memórias não voláteis de acesso randômico (NVRAM) e memórias ferroelétricas de acesso randômico (FeRAM). A dopagem dos filmes de PZT com Nióbio foi realizada visando obter valores ótimos nas propriedades ferroelétricas para a aplicação destes filmes como memórias ferroelétricas. Todavia, problemas como imprint, corrente de fuga e fadiga n...

  1. Large piezoelectric strain with ultra-low strain hysteresis in highly c-axis oriented Pb(Zr0.52Ti0.48)O3 films with columnar growth on amorphous glass substrates

    NARCIS (Netherlands)

    Nguyen, Minh D.; Houwman, Evert P.; Rijnders, Guus


    Thin films of PbZr0.52Ti0.48O3 (PZT) with largely detached columnar grains, deposited by pulsed laser deposition (PLD) on amorphous glass substrates covered with Ca2Nb3O10 nanosheets as growth template and using LaNiO3 electrode layers, are shown to exhibit very high unipolar piezoelectric strain

  2. Gaps and pseudogaps in perovskite rare earth nickelates

    Directory of Open Access Journals (Sweden)

    S. James Allen


    Full Text Available We report on tunneling measurements that reveal the evolution of the quasiparticle state density in two rare earth perovskite nickelates, NdNiO3 and LaNiO3, that are close to a bandwidth controlled metal to insulator transition. We measure the opening of a sharp gap of ∼30 meV in NdNiO3 in its insulating ground state. LaNiO3, which remains a correlated metal at all practical temperatures, exhibits a pseudogap of the same order. The results point to both types of gaps arising from a common origin, namely, a quantum critical point associated with the T = 0 K metal-insulator transition. The results support theoretical models of the quantum phase transition in terms of spin and charge instabilities of an itinerant Fermi surface.

  3. 2016 CEC Annual Workshop on Electrochemistry (United States)


    rate constant ever recorded in electrochemical experiments. 12 Poster Session Caleb Alexander & Will Hardin Synthesis of...Growth with TOF-SIMS Paul DeGregory Quantitative Electrochemical Metalloimmunoassay for TFF3 in Urine using a Paper Analytical Device Jeffrey Dick...Robin Forslund Nanostructured LaNiO3 Perovskite Electrocatalyst for Enhanced Urea Oxidation Jerzy Gazda Advances in Energy Storage: Lithium-ion

  4. The exploration of Lanthanum based perovskites and their complementary electrolytes for the supercapacitor applications

    Directory of Open Access Journals (Sweden)

    Nadarajan Arjun

    Full Text Available In this study, four different kinds of perovskite powders (LaMnO3, LaFeO3, LaCrO3, and LaNiO3 were prepared and investigated as anode materials for supercapacitor. The as-prepared powders were blended with active carbon and subsequently coated on the nickel plates as the collector layer of the supercapacitors. Three different types of the aqueous solutions (3 M KCl, 1 M LiOH, and 3 M LiOH were respectively served as the electrolytes for the supercapacitor. The morphology and crystalline phase were characterized by transmission electron microscopy and XRD. The electrical capacity and impedance were measured by the electrochemical capacitance voltage analyzer and impedance spectroscopy. The profiles of specific capacitance of the four different anodic electrodes and three different electrolytes were implemented. The impedance results indicated that four asymmetric pseudocapacitors didn’t show any Warburg-type line and semi-circle line in the low-frequency region. According to the CV profiles, the intrinsic LaNiO3 exhibits the highest specific capacitance of 106.58 F/g in 3 M LiOH. Furthermore, the 98% of the initial capacitance of LaNiO3 was retained after 500 charge-discharge life cycles at the maximum current density of 1 A/g. The efficient charge storage of LaNiO3 was attributed by the anion intercalated redox reactions along with the suitability of electrode-electrolyte interactions. Keywords: Perovskite, Lanthanum nickel oxide, Pseudocapacitance, Asymmetric supercapacitor, Oxygen de-intercalation

  5. Manufacturing of a LaNiO3 composite electrode for oxygen evolution in commercial alkaline water electrolysis

    DEFF Research Database (Denmark)

    Egelund, Sune; Caspersen, Michael; Nikiforov, Aleksey Valerievich


    results were compared to a non-catalysed Watts nickel reference sample and the electrochemical measurements confirmed that the coating decreased the OER overpotential by 70 mV. XRD furthermore revealed that a LaNiO3 + Ni composite structure was obtained. Conventional alkaline water electrolysis...... was carried out at a temperature of 120 °C and a current densities of 0.2 and 0.8 A cm-2. Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS) and X-ray Diffraction (XRD) were used for characterization of the morphology....

  6. Polarization recovery in lead zirconate titanate thin films deposited on nanosheets-buffered Si (001)


    Anuj Chopra; Muharrem Bayraktar; Maarten Nijland; Johan E. ten Elshof; Fred Bijkerk; Guus Rijnders


    Fatigue behavior of Pb(Zr,Ti)O3 (PZT) films is one of the deterrent factors that limits the use of these films in technological applications. Thus, understanding and minimization of the fatigue behavior is highly beneficial for fabricating reliable devices using PZT films. We have investigated the fatigue behavior of preferentially oriented PZT films deposited on nanosheets-buffered Si substrates using LaNiO3 bottom and top electrodes. The films show fatigue of up to 10% at 100 kHz, whereas n...

  7. Emergent Phenomena at Mott Interfaces (United States)


    thickness for electron liquid formation in SrTiO3 embedded in GdTiO3, and standing-wave soft- and hard - x-ray photoemission to determine the energetic...Transition in VO2 by Electric Field-Induced Oxygen Vacancy Formation , Science, (03 2013): 1402. doi: 10.1126/science.1230512 L. Feigl, B.D. Schultz, S...S. Fadley. Band offsets in complex-oxide thin films and heterostructures ofSrTiO3/LaNiO3 and SrTiO3/GdTiO3 by soft and hard X-ray

  8. Comparison of reduction agents in the synthesis of infinite-layer LaNiO2 films

    International Nuclear Information System (INIS)

    Ikeda, Ai; Manabe, Takaaki; Naito, Michio


    Highlights: • Reduction agents were compared from a viewpoint of the facility for topotactic reduction of LaNiO 3 to LaNiO 2 films. • TiH 2 and CaH 2 yielded infinite-layer LaNiO 2 with low and metallic resistivity. • H 2 released from metal hydrides plays a dominant role in the topotactic reduction. - Abstract: Reduction agents, such as activated carbon, TiH 2 , and CaH 2 , were compared from a viewpoint of the facility for the topotactic reduction of LaNiO 3 to LaNiO 2 films. Activated carbon did not yield infinite-layer LaNiO 2 whereas both of TiH 2 and CaH 2 yielded infinite-layer LaNiO 2 with low resistivity (∼1 mΩ cm at 300 K) as well as metallic behavior down to 70 K. Thermal desorption spectroscopy indicated that H 2 released from metal hydrides plays a dominant role in the topotactic reduction

  9. Thermochemical characteristics of La n+1Ni nO3n+1 oxides

    International Nuclear Information System (INIS)

    Bannikov, D.O.; Safronov, A.P.; Cherepanov, V.A.


    Lanthanum nickelates: La 2 NiO 4+δ , La 3 Ni 2 O 7-δ , La 4 Ni 3 O 10-δ and LaNiO 3-δ the members of Ruddlesden-Popper series La n+1 Ni n O 3n+1 were prepared using citrate route. Dissolution enthalpies of complex oxides as well as a number of subsidiary substances were measured by means of Calvet calorimeter in 1 M solution of hydrochloric acid at 25 deg. C. The dissolution scheme of complex oxides in hydrochloric acid was proposed and enthalpies of formation of the complex oxides from binary oxides were calculated considering oxygen nonstoichiometry of these substances. Enthalpies of step-by-step oxidation were evaluated. Partial enthalpy contribution of LaO layers was calculated endothermic equals to 30.9 J/mol while partial enthalpy contribution of perovskite LaNiO 3 layers was negative equals to -97.0 J/mol. Enthalpy of formation of any complex oxide of Ruddlesden-Popper series fits very well to the linear regression based on these values

  10. Avoiding polar catastrophe in the growth of polarly orientated nickel perovskite thin films by reactive oxide molecular beam epitaxy

    International Nuclear Information System (INIS)

    Yang, H. F.; Liu, Z. T.; Fan, C. C.; Xiang, P.; Zhang, K. L.; Li, M. Y.; Liu, J. S.; Yao, Q.; Shen, D. W.


    By means of the state-of-the-art reactive oxide molecular beam epitaxy, we synthesized (001)- and (111)-orientated polar LaNiO 3 thin films. In order to avoid the interfacial reconstructions induced by polar catastrophe, screening metallic Nb-doped SrTiO 3 and iso-polarity LaAlO 3 substrates were chosen to achieve high-quality (001)-orientated films in a layer-by-layer growth mode. For largely polar (111)-orientated films, we showed that iso-polarity LaAlO 3 (111) substrate was more suitable than Nb-doped SrTiO 3 . In situ reflection high-energy electron diffraction, ex situ high-resolution X-ray diffraction, and atomic force microscopy were used to characterize these films. Our results show that special attentions need to be paid to grow high-quality oxide films with polar orientations, which can prompt the explorations of all-oxide electronics and artificial interfacial engineering to pursue intriguing emergent physics like proposed interfacial superconductivity and topological phases in LaNiO 3 based superlattices.

  11. Controlling the properties of ferroelectric-nickelate interfaces (United States)

    Marshall, Matthew S. J.; Malashevich, Andrei; Disa, Ankit; Han, Myung-Geun; Zhu, Yimei; Ismail-Beigi, Sohrab; Walker, Frederick; Ahn, Charles


    Ferroelectrics are a class of materials that exhibit a stable, reversible polarization making them useful for non-volatile electronic devices. In devices consisting of thin film ferroelectric PZT acting as a gate and a thin film of the conductive oxide LaNiO3 grown on LaAlO3(001) acting as a channel, we have realized a large change in room temperature channel resistance by switching the ferroelectric polarization. The effect of switching the polarization of the ferroelectric is to modify the electronic structure of the interface between the gate and channel, resulting in conduction in the otherwise insulating ferroelectric. Here, we discuss how changing the epitaxial strain and interface termination of LaNiO3 can result in larger changes in resistivity. The epitaxial strain is varied by growing the devices on LaAlO3 for tensile strain and SrTiO3 for compressive strain. An interface termination of either an atomic layer of NiO2 or LaO is achieved via atomic layering using oxygen plasma assisted molecular beam epitaxy (MBE).

  12. Formation of Two-Dimensional Homologous Faults and Oxygen Electrocatalytic Activities in a Perovskite Nickelate. (United States)

    Bak, Jumi; Bae, Hyung Bin; Kim, Jaehoon; Oh, Jihun; Chung, Sung-Yoon


    Atomic-scale direct probing of active sites and subsequent elucidation of the structure-activity relationship are important issues involving oxide-based electrocatalysts to achieve better electrochemical conversion efficiency. By generating Ruddlesden-Popper (RP) two-dimensional homologous faults via simple control of the cation nonstoichiometry in LaNiO 3 thin films, we demonstrate that strong tetragonal distortion of [NiO 6 ] octahedra is induced by more than 20% elongation of Ni-O bonds in the faults. In addition to direct visualization of the elongation by scanning transmission electron microscopy, we identify that the distorted [NiO 6 ] octahedra in the faults show considerably higher electrocatalytic activities than other surface sites during the electrochemical oxygen evolution reaction. This unequivocal evidence of the octahedral distortion and its impact on electrocatalysis in LaNiO 3 suggests that the formation of RP-type faults can provide an efficient way to control the octahedral geometry and thereby remarkably enhance the oxygen catalytic performance of perovskite oxides.

  13. Resolution of the crystal structure of the deficient perovskite LaNiO2.5 from neutron powder diffraction data

    International Nuclear Information System (INIS)

    Alonso, J.A.; Martinez-Lope, M.J.


    The oxygen-deficient perovskite LaNiO 2.5 has been prepared by controlled reduction of LaNiO 3 with Zr metal. The XRD pattern could be indexed in a monoclinic unit-cell with dimensions a 0 xa 0 xa 0 (a 0 : lattice parameter of the ideal cubic perovskite). The indexing of the neutron powder diffraction pattern needed a doubled cell to account for the superstructure reflections originated by the oxygen vacancy ordering and the tilting of the Ni coordination polyhedra. The structure was solved and refined from the neutron powder data. The oxygen vacancies are ordered in such a way that square planar NiO 4 and NiO 6 octahedra alternate in the ab plane along the [110] direction. Both kinds of Ni polyhedra are fairly distorted and tilted in order to optimize the La-O distances, giving rise to a highly strained structure of metastable character. In fact, the compound readily takes oxygen, above 175 C in air, to give the much more stable LaNiO 3 perovskite. (orig.)

  14. Comparison of reduction agents in the synthesis of infinite-layer LaNiO2 films (United States)

    Ikeda, Ai; Manabe, Takaaki; Naito, Michio


    Reduction agents, such as activated carbon, TiH2, and CaH2, were compared from a viewpoint of the facility for the topotactic reduction of LaNiO3 to LaNiO2 films. Activated carbon did not yield infinite-layer LaNiO2 whereas both of TiH2 and CaH2 yielded infinite-layer LaNiO2 with low resistivity (∼1 mΩ cm at 300 K) as well as metallic behavior down to 70 K. Thermal desorption spectroscopy indicated that H2 released from metal hydrides plays a dominant role in the topotactic reduction.


    Directory of Open Access Journals (Sweden)

    P. P. Silva


    Full Text Available AbstractThe objective of this paper was to use a thermodynamic analysis to find operational conditions that favor the production of hydrogen from steam and oxidative reforming of liquefied petroleum gas (LPG. We also analyzed the performance of a catalyst precursor, LaNiO3, in order to compare the performance of the obtained catalyst with the thermodynamic equilibrium predictions. The results showed that it is possible to produce high concentrations of hydrogen from LPG reforming. The gradual increase of temperature and the use of high water concentrations decrease the production of coke and increase the formation of H2. The reaction of oxidative reforming of LPG was more suitable for the production of hydrogen and lower coke formation. Furthermore the use of an excess of water (H2O/LPG =7.0 and intermediate temperatures (973 K are the most suitable conditions for the process.

  16. Comparative study of effects of Mo and W dopants on the ferroelectric property of Pb(Zr0.3Ti0.7) thin films

    International Nuclear Information System (INIS)

    Zhang Zhen; Wang Shijie; Lu Li; Shu Chang; Song Wendong; Wu Ping


    Pb(Zr 0.3 Ti 0.7 )O 3 thin films, respectively, doped with 1 mol% W and 1 mol% Mo have been deposited on the LaNiO 3 bottom electrodes using pulse laser deposition. The x-ray diffraction analyses revealed that both dopants induced (1 1 0) orientation of the perovskite structures. Compared with the undoped PZT films, the doped PZT films showed smoother and denser surfaces. The XPS measurements indicated that W possessed a valence state of +6 in the PZTW films, but Mo showed mixed valence states of +4 and +6. The hysteresis loops and fatigue results of the undoped, the W-doped (PZTW) and the Mo-doped PZT (PZTM) films were obtained. While both the two doped films revealed better fatigue behaviour than undoped PZT, the PZTW film had a slow fatigue rate in comparison with the PZTM film, which is consistent with our previous theoretical predictions

  17. A flexible, high-performance magnetoelectric heterostructure of (001) oriented Pb(Zr0.52Ti0.48)O3 film grown on Ni foil (United States)

    Palneedi, Haribabu; Yeo, Hong Goo; Hwang, Geon-Tae; Annapureddy, Venkateswarlu; Kim, Jong-Woo; Choi, Jong-Jin; Trolier-McKinstry, Susan; Ryu, Jungho


    In this study, a flexible magnetoelectric (ME) heterostructure of PZT/Ni was fabricated by depositing a (001) oriented Pb(Zr0.52Ti0.48)O3 (PZT) film on a thin, flexible Ni foil buffered with LaNiO3/HfO2. Excellent ferroelectric properties and large ME voltage coefficient of 3.2 V/cmṡOe were realized from the PZT/Ni heterostructure. The PZT/Ni composite's high performance was attributed to strong texturing of the PZT film, coupled with the compressive stress in the piezoelectric film. Besides, reduced substrate clamping in the PZT film due to the film on the foil structure and strong interfacial bonding in the PZT/LaNiO3/HfO2/Ni heterostructure could also have contributed to the high ME performance of PZT/Ni.

  18. Low-temperature synthesis of the infinite-layer compound LaNiO2 by soft-chemical techniques

    International Nuclear Information System (INIS)

    Takamatsu, Tomohisa; Kato, Masatsune; Noji, Takashi; Koike, Yoji


    Bulk samples of LaNiO 2 with the so-called infinite-layer structure have successfully been synthesized. First, polycrystalline samples of LaNiO 3 with the perovskite structure were prepared using molten KOH at a temperature of 400-450degC. Then, they were finely ground with a double stoichiometric excess of reductant CaH 2 and sealed in an evacuated Pyrex tube. The sealed ampoule was then heated at 300degC for 24 h. Powder X-ray diffraction analysis has revealed that the product obtained after removing the residual CaH 2 and the byproduct CaO is of almost single phase with tetragonal symmetry, indicating the formation of the infinite-layer compound LaNiO 2 . (author)

  19. Process for obtaining cobalt and lanthanum nickelate

    International Nuclear Information System (INIS)

    Tapcov, V.; Samusi, N.; Gulea, A.; Horosun, I.; Stasiuc, V.; Petrenco, P.


    The invention relates to the process for obtaining polycrystalline ceramics of cobalt and lanthanum nickelate with the perovskite structure from coordinative hetero metallic compounds. The obtained products can be utilized in the industry in the capacity of catalysts. Summary of the invention consists in obtaining polycrystalline ceramics LaCoO 3 and LaNiO 3 with the perovskite structure by pyrolysis of the parent compounds, namely, the coordinative hetero metallic compounds of the lanthanum cobalt or lanthanum nickel. The pyrolysis of the parent compound runs during one hour at 800 C. The technical result of the invention consists in lowering the temperature of the parent compound pyrolysis containing the precise ratio of metals necessary for ceramics obtaining

  20. Oxidation states of Fe in LaNi1-xFexO3

    International Nuclear Information System (INIS)

    Goeta, A.E.; Falcon, H.; Carbonio, R.


    The distribution of oxidation states in perovskites of the type LaA 1-x B x O 3 (A and B transition metal ions) can be ''tailored'' by x variation. In particular, in LaNiO 3 it has been shown that Fe substitution for Ni foces some Ni 3+ into Ni 2+ , while some Fe 3+ changes into the unusual Fe 4+ state. In addition, the existence of mixed oxidation states of Fe and/or Ni in LaNi 1-x Fe x O 3 has been related to its catalytic activity in hydrogen peroxide decomposition. The Fe 4+ population, obtained using Moessbauer spectroscopy, was found to be constant for all the analyzed annealing temperatures for x = 0.25 concentration, where the isomer shift difference for both states is the highest and the catalytic activity is maximum. (orig.)

  1. Infrared reflectivity of the solid solutions LaNi1-xFexO3 (0.00≤x≤1.00)

    International Nuclear Information System (INIS)

    Massa, N.E.; Falcon, H.; Salva, H.; Carbonio, R.E.


    We report temperature-dependent far- and midinfrared reflectivity spectra of LaNi (1-x) Fe x O 3 solid solutions that span the passage from LaFeO 3 , a room-temperature antiferromagnetic insulator, to LaNiO 3 , a known metal oxide. Light Ni doping creates defects that induce extra bands assigned to electronic transitions within the insulating gap. An incipient Drude term emerges in the reflectivity spectrum of LaNi 0.39 Fe 0.61 O 3 together with subbands that contribute to the electronic background. At these concentrations the dielectric response shows a picture in which the spectral weigh switches over toward far-infrared frequencies while phonon features develop strong antiresonances near longitudinal-optical modes. Further increment of carriers produces phonon screening and the development of a reflectivity tail that extends beyond 1 eV. We assign extra-non-Drude terms in the 700 endash 4000cm -1 frequency region to transitions due to intrinsic defects. While the increment in reflectivity at far-infrared frequencies is evident for Fe concentrations well above the insulator-metal transition (x∼0.30), the spectral features of a metal oxide, with phonons mostly screened, are found for x=0.23. These metallic spectra show an absorption dip at ∼650cm -1 that is traced to the perovskite symmetric stretching longitudinal mode. Electron-phonon interactions are thus present in solid solutions even when the numbers of effective carriers are those of a metal. This characterization is also supported by the observation of weak reflectivity dips in LaNiO 3 that have a direct correspondence to longitudinal-optical mode frequencies of the insulating phases of our series. We infer that strong electron-phonon interactions play a role in the conductivity of those solid solutions and are likely related to polaron formation and carrier phonon-assisted hopping motion. (Abstract Truncated)

  2. Electrical properties of (1 0 0)-predominant BaTiO3 films derived from alkoxide solutions of two concentrations

    International Nuclear Information System (INIS)

    Guo Yiping; Suzuki, Kazuyuki; Nishizawa, Kaori; Miki, Takeshi; Kato, Kazumi


    Lead-free piezoelectric films with thickness larger than 1 μm integrated on silicon substrates have been receiving considerable attention because of environmental concerns and their potential applications in microelectromechanical systems. We demonstrate that, by chemical solution deposition, it is possible to process (1 0 0)-predominant 1 μm BaTiO 3 films on LaNiO 3 /Pt/TiO x /SiO 2 /Si substrates using thinner high-crystallinity columnar BaTiO 3 films as buffer layers. We point out that this kind of buffer layer prepared with a lower concentration solution on the surface of an LaNiO 3 /Pt electrode is effective in enhancing the crystallinity and orientation degree of final BaTiO 3 films prepared with a higher concentration solution. The 1 μm BaTiO 3 films show good dielectric and insulating characteristics against an applied field, and the conduction current shows Schottky emission behavior at modest voltage and space-charge-limited behavior at higher voltage. We also demonstrate that the (1 0 0)-predominant 1 μm BaTiO 3 films have excellent piezoelectric properties: piezoelectric coefficients d 33 higher than 50 pm/V have been determined for the bare films using atomic force microscopy, which are comparable to those of Pb(Zr,Ti)O 3 films. These results indicate that the (1 0 0)-predominant BaTiO 3 films should be promising candidates for microelectromechanical systems applications

  3. Ordering phenomena in transition-metal-oxide heterostructures

    International Nuclear Information System (INIS)

    Frano Pereira, Alex Manuel


    This doctoral work presents a study of ordered ground states of transition metal oxide compounds and multilayers using resonant elastic soft x-ray scattering. The technique has developed over the last decades and become especially useful when sample sizes are limited like the case of nanometer-scale films and superlattices. By scattering with photon energies on resonance with the element's electronic transitions, it is an element-specific, sensitive tool providing a combination of spectroscopic and spatial information. The thesis is divided into two central topics. The first part focuses on the investigation of perovskite-type, rare-earth nickelate heterostructures. X-rays tuned to the Ni L 3 -edge were used to unveil unprecedented diffraction evidence of long range magnetic order in LaNiO 3 -RXO 3 (RXO 3 = LaAlO 3 , DyScO 3 ) superlattices. We report on the appearance of magnetic order in such systems with a propagation vector of Q SDW = ((1)/(4),(1)/(4),l) in pseudocubic notation, similar to bulk rare earth nickelates with R ≠ La. With LaNiO 3 being paramagnetic in its bulk form, the magnetic Bragg peak is only present in superlattices where the thickness of the LaNiO 3 layers approaches the 2-dimensional limit. Besides the thickness dependence, the magnetic order was probed on samples grown on varying strain-inducing substrates. Azimuthal scans around Q SDW were done to determine the orientation of the spin spiral under these different conditions. We will explain how the reorientation of the spins can be understood by the magneto-crystalline anisotropy which is determined by the relative occupation of the Ni d-orbitals via spin-orbit coupling. First steps towards control of the spin spiral's orientation will be outlined, and along with the high remanent conductivity found in the magnetic spiral state, an outlook for metallic antiferromagnetic spintronics will be discussed. The second part of this thesis will address the observation of charge density wave (CDW) order in single crystals of superconducting YBa 2 Cu 3 O 6+δ (YBCO). With accumulating evidence of a Fermi surface reconstruction suggesting an underlying ordered ground state in underdoped YBCO, diffraction evidence of a CDW was found in YBCO 6.6 single crystals during this PhD project. A thorough study of the energy, temperature, external magnetic field, and doping dependence was done to characterize the details of this ordered state. Together with results obtained on samples doped with non-magnetic Zn impurities, which locally slow the magnetic fluctuations, a competition between the CDW, the spin density wave, and superconducting phase is proposed. Finally, the study extended to investigate the emergence of CDW in SLs comprising fully oxygenated YBCO, a doping level where CDW order eludes single crystals, and half-metallic La 2/3 Ca 1/3 MnO 3 (LCMO). Our main finding is that the order originates at the YBCO interface due a charge transfer of electrons from LCMO. The temperature and magnetic field dependencies of the peak suggest a static, saturated phase in stark contrast to the single crystals' fluctuating order. Thus, this result demonstrates how oxide interfaces can act to nucleate metastable electronic phase transitions.

  4. Novel metal oxides prepared by ingenious synthetic routes

    International Nuclear Information System (INIS)

    Rao, C.N.R.; Gopalakrishnan, J.; Vidyasagar, K.; Ganguli, A.K.; Ramanan, A.; Ganapathi, L.


    Several novel oxides have been prepared by the decomposition of carbonate precursors of calcite structure of the general formulas Mn/sub 1-x/M/sub x/CO 3 (M = Mg,Co,Cd), Ca/sub 1-x/M/sup prime//sub x/CO 3 , and Ca/sub 1-x/-yM/sup //sub x/M/sup double-prime//sub y/CO 3 (M',M'' = Mn,Fe,Co). Typical of the oxides synthesized are a variety of monoxides, Mn/sub 1-x/M/sub x/O, of rocksalt structure and perovskite-related oxides such as Ca 2 FeCoO 5 , Ca 2 Co 2 O 5 , and Ca 3 Fe 2 MnO 8 , many of them exhibiting novel anion-vacancy-ordered superstructures. An interesting series of oxides prepared by the topotactic reduction of Ca 2 Fe/sub 2-x/Mn/sub x/O/sub 6-y/ (synthesized by the decomposition of the corresponding carbonate precursors) is Ca 2 Fe/sub 2-x/Mn/sub x/O 5 where three different coordination polyhedra (octahedra, tetrahedra, and square pyramids) of the transition metals coexist. Topotactic reduction of LaCoO 3 and LaNiO 3 yields new oxides, La 2 Co 2 O 5 and La 2 Ni 2 O 5 , possessing anion-vacancy-ordered superstructures. While La 2 Co 2 O 5 adopts the brownmillerite structure, La 2 Ni 2 O 5 exhibits a new type of vacancy ordering with octahedral and square-planar coordination of Ni 2+ . Slightly reduced LaNiO 3 seem to exhibit crystallographic shear (CS) planes similar to WO/sub 3-x/. Topotactic dehydration of isostructural Mo/sub 1-x/W/sub x/O 3 x H 2 O provides a convenient route for the synthesis of Mo/sub 1-x/W/sub x/O 3 (0 3 -related structure

  5. Magnetism, spin-lattice-orbital coupling and exchange-correlation energy in oxide heterostructures: Nickelate, titanate, and ruthenate (United States)

    Han, Myung-Joon

    Many interesting physical phenomena and material characteristics in transition-metal oxides (TMO) come out of the intriguing interplay between charge, spin, orbital, and lattice degrees of freedom. In the thin film and/or heterointerface form of TMO, this feature can be controlled and thus be utilized. Simultaneously, however, its detailed characteristic is more difficult to be identified experimentally. For this reason, the first-principles-based approach has been playing an important role in this field of research. In this talk, I will try to give an overview of current status of first-principles methodologies especially for the magnetism in the correlated oxide heterostructures or thin films. Nickelate, titanate, and ruthenate will be taken as representative examples to demonstrate the powerfulness of and the challenges to the current methodologies On the one hand, first-principles calculation provides the useful information, understanding and prediction which can hardly be obtained from other theoretical and experimental techniques. Nickelate-manganite superlattices (LaNiO3/LaMnO3 and LaNiO3/CaMnO3) are taken as examples. In this interface, the charge transfer can induce the ferromagnetism and it can be controlled by changing the stacking sequence and number of layers. The exchange-correlation (XC) functional dependence seems to give only quantitatively different answers in this case. On the other hand, for the other issues such as orbital polarization/order coupled with spin order, the limitation of current methodology can be critical. This point will be discussed with the case of tatinate superlattice (LaTiO3/LaAlO3) . For ruthenates (SrRuO3\\ and Sr2RuO4) , we found that the probably more fundamental issue could be involved. The unusually strong dependence on the XC functional parametrization is found to give a qualitatively different conclusion for the experimentally relevant parameter regions. This work was supported by National Research Foundation of Korea (2014R1A1A2057202).

  6. Structurally triggered metal-insulator transition in rare-earth nickelates. (United States)

    Mercy, Alain; Bieder, Jordan; Íñiguez, Jorge; Ghosez, Philippe


    Rare-earth nickelates form an intriguing series of correlated perovskite oxides. Apart from LaNiO 3 , they exhibit on cooling a sharp metal-insulator electronic phase transition, a concurrent structural phase transition, and a magnetic phase transition toward an unusual antiferromagnetic spin order. Appealing for various applications, full exploitation of these compounds is still hampered by the lack of global understanding of the interplay between their electronic, structural, and magnetic properties. Here we show from first-principles calculations that the metal-insulator transition of nickelates arises from the softening of an oxygen-breathing distortion, structurally triggered by oxygen-octahedra rotation motions. The origin of such a rare triggered mechanism is traced back in their electronic and magnetic properties, providing a united picture. We further develop a Landau model accounting for the metal-insulator transition evolution in terms of the rare-earth cations and rationalizing how to tune this transition by acting on oxygen rotation motions.

  7. Thickness dependence of electrical properties in (0 0 1) oriented lead zirconate titanate films by laser ablation

    International Nuclear Information System (INIS)

    Zhu, T.J.; Lu, L.; Lai, M.O.; Soh, A.K.


    Highly (0 0 1)-oriented Pb(Zr 0.52 Ti 0.48 )O 3 (PZT) thin films with LaNiO 3 (LNO) bottom electrodes have been fabricated on amorphous TiN buffered Si substrates by pulsed laser deposition. The polarization-electric field (P-E) hysteresis of the deposited PZT films with different thickness ranging from 25 to 850 nm was measured. Results showed that the coercive field increases with the film thickness scaling down. No P-E loops could be obtained for the film of thickness of 25 nm. The deterioration of ferroelectric property in the thinnest film was attributed to extrinsic effect other than intrinsic size effect. Current-voltage (I-V) characteristics measurement showed the increase in leakage current of the PZT films with the decrease in the thickness of the films under the same bias voltage. At a high field regime, the leakage current of the PZT films of 25 nm thickness remained unchanged with increasing applied voltage. A totally depleted back-to-back Shottky barrier model was used to explain the effect of electrode interfaces on leakage current in the PZT films. It is believed that ferroelectric/electrode interfaces play an important role in the electrical properties of ferroelectric thin films with thickness at nanometer level

  8. Interface depolarization field as common denominator of fatigue and size effect in Pb(Zr0.54Ti0.46)O3 ferroelectric thin film capacitors (United States)

    Bouregba, R.; Sama, N.; Soyer, C.; Poullain, G.; Remiens, D.


    Dielectric, hysteresis and fatigue measurements are performed on Pb(Zr0.54Ti0.46)O3 (PZT) thin film capacitors with different thicknesses and different electrode configurations, using platinum and LaNiO3 conducting oxide. The data are compared with those collected in a previous work devoted to study of size effect by R. Bouregba et al., [J. Appl. Phys. 106, 044101 (2009)]. Deterioration of the ferroelectric properties, consecutive to fatigue cycling and thickness downscaling, presents very similar characteristics and allows drawing up a direct correlation between the two phenomena. Namely, interface depolarization field (Edep) resulting from interface chemistry is found to be the common denominator, fatigue phenomena is manifestation of strengthen of Edep in the course of time. Change in dielectric permittivity, in remnant and coercive values as well as in the shape of hysteresis loops are mediated by competition between degradation of dielectric properties of the interfaces and possible accumulation of interface space charge. It is proposed that presence in the band gap of trap energy levels with large time constant due to defects in small nonferroelectric regions at the electrode—PZT film interfaces ultimately governs the aging process. Size effect and aging process may be seen as two facets of the same underlying mechanism, the only difference lies in the observation time of the phenomena.

  9. Electric and magnetic properties of a CoFe2O4/PZT bilayer grown on (100)SrTiO3 by using PLD

    International Nuclear Information System (INIS)

    Zhang, X. D.; Dho, J. H.


    We have investigated the electric and the magnetic properties of a ferrimagnetic and ferroelectric bilayer CoFe 2 O 4 (CFO)/PbZr 0.2 Ti 0.8 O 3 (PZT) grown on a (100)SrTiO 3 (STO) substrate by using pulsed laser deposition. PZT (100 nm) and CFO (70 nm) layers were sequentially deposited on the (100)STO substrate with a bottom electrode LaNiO 3 (50 nm) layer at 600 - 650 .deg. C. X-ray diffraction for the PZT layer exhibited both (200) and (002) peaks, which are due to the c- and the a-domains, and a decrease of tetragonality after CFO deposition. The electric properties of the CFO/PZT bilayer were characterized by using P-V loop, C-f, and C-V measurements. The remnant polarization and coercivity were slightly decreased after the top-layer CFO deposition while fatigue behavior was distinctively improved. The M-H loop measurement confirmed that the CFO layer possessed a typical ferrimagnetic property at room temperature.

  10. Large piezoelectric strain with ultra-low strain hysteresis in highly c-axis oriented Pb(Zr0.52Ti0.48)O3 films with columnar growth on amorphous glass substrates. (United States)

    Nguyen, Minh D; Houwman, Evert P; Rijnders, Guus


    Thin films of PbZr 0 . 52 Ti 0 . 48 O 3 (PZT) with largely detached columnar grains, deposited by pulsed laser deposition (PLD) on amorphous glass substrates covered with Ca 2 Nb 3 O 10 nanosheets as growth template and using LaNiO 3 electrode layers, are shown to exhibit very high unipolar piezoelectric strain and ultra-low strain hysteresis. The observed increase of the piezoelectric coefficient with increasing film thickness is attributed to the reduction of clamping, because of the increasingly less dense columnar microstructure (more separation between the grains) with across the film thickness. A very large piezoelectric coefficient (490 pm/V) and a high piezoelectric strain (~0.9%) are obtained in 4-µm-thick film under an applied electric field of 200 kV/cm, which is several times larger than in usual PZT ceramics. Further very low strain hysteresis (H≈2-4%) is observed in 4 to 5 µm thick films. These belong to the best values demonstrated so far in piezoelectric films. Fatigue testing shows that the piezoelectric properties are stable up to 10 10 cycles. The growth of high quality PZT films with very large strain and piezoelectric coefficients, very low hysteresis and with long-term stability on a technologically important substrate as glass is of great significance for the development of practical piezo driven microelectromechanical actuator systems.

  11. Comparison of structural and electric properties of PbZr0.2Ti0.8O3 and CoFe2O4/PbZr0.2Ti0.8O3 films on (100)LaAlO3 (United States)

    Zhang, X. D.; Dho, Joonghoe; Park, Sungmin; Kwon, Hyosang; Hwang, Jihwan; Park, Gwangseo; Kwon, Daeyoung; Kim, Bongju; Jin, Yeryeong; Kim, Bog. G.; Karpinsky, D.; Kholkin, A. L.


    In this work, we investigated structural, electrical, and magnetic properties of ferroelectric PbZr0.2Ti0.8O3 (PZT) and ferrimagnetic/ferroelectric [CoFe2O4(CFO)/PZT] bilayers grown on (100)LaAlO3 (LAO) substrates supplied with bottom 50 nm thick LaNiO3 electrodes. Interestingly, structural and electrical properties of the PZT layer exhibited remarkable changes after the top-layer CFO deposition. X-ray diffraction data suggested that both the c- and a-domains exist in the PZT layer and the tetragonality of the PZT decreases upon the top-layer deposition. A variation in the electrical properties of the PZT layer upon the CFO deposition was investigated by polarization versus voltage (P-V), capacitance versus voltage (C-V), and capacitance versus frequency (C-f) measurements. The CFO deposition induced a slight decrease of the remnant polarization and more symmetric behavior of P-V loops as well as led to the improvement of fatigue behavior. The tentative origin of enhanced fatigue endurance is discussed based on the measurement results. These results were corroborated by local piezoelectric measurements. Ferrimagnetic property of the CFO/PZT bilayer was confirmed by magnetic measurement at room temperature.

  12. Polarization recovery in lead zirconate titanate thin films deposited on nanosheets-buffered Si (001

    Directory of Open Access Journals (Sweden)

    Anuj Chopra


    Full Text Available Fatigue behavior of Pb(Zr,TiO3 (PZT films is one of the deterrent factors that limits the use of these films in technological applications. Thus, understanding and minimization of the fatigue behavior is highly beneficial for fabricating reliable devices using PZT films. We have investigated the fatigue behavior of preferentially oriented PZT films deposited on nanosheets-buffered Si substrates using LaNiO3 bottom and top electrodes. The films show fatigue of up to 10% at 100 kHz, whereas no fatigue has been observed at 1 MHz. This frequency dependence of the fatigue behavior is found to be in accordance with Dawber–Scott fatigue model that explains the origin of the fatigue as migration of oxygen vacancies. Interestingly, a partial recovery of remnant polarization up to ∼97% of the maximum value is observed after 4×109 cycles which can be further extended to full recovery by increasing the applied electric field. This full recovery is qualitatively explained using kinetic approach as a manifestation of depinning of domains walls. The understanding of the fatigue behavior and polarization recovery that is explained in this paper can be highly useful in developing more reliable PZT devices.

  13. Polarization recovery in lead zirconate titanate thin films deposited on nanosheets-buffered Si (001) (United States)

    Chopra, Anuj; Bayraktar, Muharrem; Nijland, Maarten; ten Elshof, Johan E.; Bijkerk, Fred; Rijnders, Guus


    Fatigue behavior of Pb(Zr,Ti)O3 (PZT) films is one of the deterrent factors that limits the use of these films in technological applications. Thus, understanding and minimization of the fatigue behavior is highly beneficial for fabricating reliable devices using PZT films. We have investigated the fatigue behavior of preferentially oriented PZT films deposited on nanosheets-buffered Si substrates using LaNiO3 bottom and top electrodes. The films show fatigue of up to 10% at 100 kHz, whereas no fatigue has been observed at 1 MHz. This frequency dependence of the fatigue behavior is found to be in accordance with Dawber-Scott fatigue model that explains the origin of the fatigue as migration of oxygen vacancies. Interestingly, a partial recovery of remnant polarization up to ˜97% of the maximum value is observed after 4×109 cycles which can be further extended to full recovery by increasing the applied electric field. This full recovery is qualitatively explained using kinetic approach as a manifestation of depinning of domains walls. The understanding of the fatigue behavior and polarization recovery that is explained in this paper can be highly useful in developing more reliable PZT devices.

  14. Fabrication and orientation control of highly cation-ordered epitaxial PbSc{sub 0.5}Ta{sub 0.5}O{sub 3} thin films on Si (100)

    Energy Technology Data Exchange (ETDEWEB)

    Chopra, Anuj, E-mail: [Max Planck Institute of Microstructure Physics, Weinberg 2, D-06120 Halle (Saale) (Germany); Faculty of Science and Technology, MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Alexe, Marin [Max Planck Institute of Microstructure Physics, Weinberg 2, D-06120 Halle (Saale) (Germany); Department of Physics, University of Warwick, Coventry CV4 7AL (United Kingdom); Hesse, Dietrich [Max Planck Institute of Microstructure Physics, Weinberg 2, D-06120 Halle (Saale) (Germany)


    Highly cation-ordered (100) and (110)-oriented PbSc{sub 0.5}Ta{sub 0.5}O{sub 3} (PST) films were deposited on buffered Si (100) substrates using pulsed laser deposition. Switching of crystal orientation from (100) to (110) was achieved by replacing the Si (100)/ZrO2:Y2O3 (100)/CeO2 (100)/LaNiO3 (100)/PST (100) heterostructure with Si (100)/ZrO2:Y2O3 (YSZ) (100)/SrRuO3 (110)/PST (110). The out-of-plane and in-plane crystal orientation and internal microstructure of (001) and (110) PST films were analyzed in detail by X-ray diffraction, pole figure measurements, and transmission electron microscopy. XRD superstructure reflections indicate that both (100) and (110) PST films are highly cation-ordered and transmission electron microscopy measurements show nano-domains of 15 nm size. The electrical measurements show that the PST films are ferroelectric and that the ferroelectric properties are linked to the microstructure. We have demonstrated the successful integration of PST films on Si substrates with control on growth orientation; this approach can be extended to other oxides to be integrated on silicon substrates for future device applications.

  15. Development and Characterization of an Electrically Rechargeable Zinc-Air Battery Stack

    Directory of Open Access Journals (Sweden)

    Hongyun Ma


    Full Text Available An electrically rechargeable zinc-air battery stack consisting of three single cells in series was designed using a novel structured bipolar plate with air-breathing holes. Alpha-MnO2 and LaNiO3 severed as the catalysts for the oxygen reduction reaction (ORR and oxygen evolution reaction (OER. The anodic and cathodic polarization and individual cell voltages were measured at constant charge-discharge (C-D current densities indicating a uniform voltage profile for each single cell. One hundred C-D cycles were carried out for the stack. The results showed that, over the initial 10 cycles, the average C-D voltage gap was about 0.94 V and the average energy efficiency reached 89.28% with current density charging at 15 mA·cm−2 and discharging at 25 mA·cm−2. The total increase in charging voltage over the 100 C-D cycles was ~1.56% demonstrating excellent stability performance. The stack performance degradation was analyzed by galvanostatic electrochemical impedance spectroscopy. The charge transfer resistance of ORR increased from 1.57 to 2.21 Ω and that of Zn/Zn2+ reaction increased from 0.21 to 0.34 Ω after 100 C-D cycles. The quantitative analysis guided the potential for the optimization of both positive and negative electrodes to improve the cycle life of the cell stack.

  16. Tunable Noncollinear Antiferromagnetic Resistive Memory through Oxide Superlattice Design (United States)

    Hoffman, Jason D.; Wu, Stephen M.; Kirby, Brian J.; Bhattacharya, Anand


    Antiferromagnets (AFMs) have recently gathered a large amount of attention as a potential replacement for ferromagnets (FMs) in spintronic devices due to their lack of stray magnetic fields, invisibility to external magnetic probes, and faster magnetization dynamics. Their development into a practical technology, however, has been hampered by the small number of materials where the antiferromagnetic state can be both controlled and read out. We show that by relaxing the strict criterion on pure antiferromagnetism, we can engineer an alternative class of magnetic materials that overcome these limitations. This is accomplished by stabilizing a noncollinear magnetic phase in LaNiO3 /La2 /3Sr1 /3MnO3 superlattices. This state can be continuously tuned between AFM and FM coupling through varying the superlattice spacing, strain, applied magnetic field, or temperature. By using this alternative "knob" to tune magnetic ordering, we take a nanoscale materials-by-design approach to engineering ferromagneticlike controllability into antiferromagnetic synthetic magnetic structures. This approach can be used to trade-off between the favorable and unfavorable properties of FMs and AFMs when designing realistic resistive antiferromagnetic memories. We demonstrate a memory device in one such superlattice, where the magnetic state of the noncollinear antiferromagnet is reversibly switched between different orientations using a small magnetic field and read out in real time with anisotropic magnetoresistance measurements.

  17. Energy-storage properties and electrocaloric effect of Pb(1-3x/2)LaxZr0.85Ti0.15O3 antiferroelectric thick films. (United States)

    Zhao, Ye; Hao, Xihong; Zhang, Qi


    Antiferroelectric (AFE) thick (1 μm) films of Pb(1-3x/2)LaxZr0.85Ti0.15O3 (PLZT) with x = 0.08, 0.10, 0.12, and 0.14 were deposited on LaNiO3/Si (100) substrates by a sol-gel method. The dielectric properties, energy-storage performance, electrocaloric effect, and leakage current behavior were investigated in detail. With increasing La content, dielectric constant and saturated polarizations of the thick films were gradually decreased. A maximum recoverable energy-storage density of 38 J/cm(3) and efficiency of 71% were achieved in the thick films with x = 0.12 at room temperature. A large reversible adiabatic temperature change of ΔT = 25.0 °C was presented in the thick films with x = 0.08 at 127 °C at 990 kV/cm. Moreover, all the samples had a lower leakage current density below 10(-6) A/cm(2) at room temperature. These results indicated that the PLZT AFE thick films could be a potential candidate for applications in high energy-storage density capacitors and cooling devices.

  18. Polarization and charge-transfer effect on the transport properties in two-dimensional electron gases/LaNiO3 heterostructure (United States)

    Chen, M. J.; Ning, X. K.; Wang, Z. J.; Liu, P.; Wang, S. F.; Wang, J. L.; Fu, G. S.; Ma, S.; Liu, W.; Zhang, Z. D.


    The film thickness dependent transport properties of the LaNiO3 (LNO) layer epitaxially grown on LaAlO3/SrTiO3 (LAO) 2-dimensional electronic gas (2DEG) have been investigated. The ultrathin LNO films grown on the 2DEG have a sheet resistance below the values of h/e2 in all temperature ranges. The electron density is enhanced by more than one order of magnitude by capping LNO films. X-ray photoelectron spectroscopy shows that the interface undergoes unambiguous charge transfer and electronic reconstruction, leading to modulation doping of such atomically engineered complex oxide heterointerfaces. The polar-catastrophe of the 2DEG is directly linked to the electronic structure and transport properties of the LNO. The transport properties can be well modulated by the thickness of the LAO in the 2DEG, and the data can be well fitted with the polar-catastrophe scenario. These results suggest a general approach to tunable functional films in oxide heterostructures with the 2DEG.

  19. Pulsed laser deposition of piezoelectric lead zirconate titanate thin films maintaining a post-CMOS compatible thermal budget (United States)

    Schatz, A.; Pantel, D.; Hanemann, T.


    Integration of lead zirconate titanate (Pb[Zrx,Ti1-x]O3 - PZT) thin films on complementary metal-oxide semiconductor substrates (CMOS) is difficult due to the usually high crystallization temperature of the piezoelectric perovskite PZT phase, which harms the CMOS circuits. In this work, a wafer-scale pulsed laser deposition tool was used to grow 1 μm thick PZT thin films on 150 mm diameter silicon wafers. Three different routes towards a post-CMOS compatible deposition process were investigated, maintaining a post-CMOS compatible thermal budget limit of 445 °C for 1 h (or 420 °C for 6 h). By crystallizing the perovskite LaNiO3 seed layer at 445 °C, the PZT deposition temperature can be lowered to below 400 °C, yielding a transverse piezoelectric coefficient e31,f of -9.3 C/m2. With the same procedure, applying a slightly higher PZT deposition temperature of 420 °C, an e31,f of -10.3 C/m2 can be reached. The low leakage current density of below 3 × 10-6 A/cm2 at 200 kV/cm allows for application of the post-CMOS compatible PZT thin films in low power micro-electro-mechanical-systems actuators.

  20. Four-state non-volatile memory in a multiferroic spin filter tunnel junction (United States)

    Ruan, Jieji; Li, Chen; Yuan, Zhoushen; Wang, Peng; Li, Aidong; Wu, Di


    We report a spin filter type multiferroic tunnel junction with a ferromagnetic/ferroelectric bilayer barrier. Memory functions of a spin filter magnetic tunnel junction and a ferroelectric tunnel junction are combined in this single device, producing four non-volatile resistive states that can be read out in a non-destructive manner. This concept is demonstrated in a LaNiO3/Pr0.8Ca0.2MnO3/BaTiO3/La0.7Sr0.3MnO3 all-oxide tunnel junction. The ferromagnetic insulator Pr0.8Ca0.2MnO3 serves as the spin filter and the ferromagnetic metal La0.7Sr0.3MnO3 is the spin analyzer. The ferroelectric polarization reversal in the BaTiO3 barrier switches the tunneling barrier height to produce a tunneling electroresistance. The ferroelectric switching also modulates the spin polarization and the spin filtering efficiency in Pr0.8Ca0.2MnO3.

  1. Flexible Pb(Zr0.52Ti0.48)O3 Films for a Hybrid Piezoelectric-Pyroelectric Nanogenerator under Harsh Environments. (United States)

    Ko, Young Joon; Kim, Dong Yeong; Won, Sung Sik; Ahn, Chang Won; Kim, Ill Won; Kingon, Angus I; Kim, Seung-Hyun; Ko, Jae-Hyeon; Jung, Jong Hoon


    In spite of extremely high piezoelectric and pyroelectric coefficients, there are few reports on flexible ferroelectric perovskite film based nanogenerators (NGs). Here, we report the successful growth of a flexible Pb(Zr0.52Ti0.48)O3 (PZT) film and its application to hybrid piezoelectric-pyroelectric NG. A highly flexible Ni-Cr metal foil substrate with a conductive LaNiO3 bottom electrode enables the growth of flexible PZT film having high piezoelectric (140 pC/N) and pyroelectric (50 nC/cm(2)K) coefficients at room temperature. The flexible PZT-based NG effectively scavenges mechanical vibration and thermal fluctuation from sources ranging from the human body to the surroundings such as wind. Furthermore, it stably generates electric current even at elevated temperatures of 100 °C, relative humidity of 70%, and pH of 13 by virtue of its high Curie temperature and strong resistance for water and base. As proof of power generation under harsh environments, we demonstrate the generation of extremely high current at the exhaust pipe of a car, where hot CO and CO2 gases are rapidly expelled to air. This work expands the application of flexible PZT film-based NG for the scavenging mechanical vibration and thermal fluctuation energies even at extreme conditions.

  2. Enhanced dielectric nonlinearity in epitaxial Pb0.92La0.08Zr0.52Ti0.48O3 thin films

    International Nuclear Information System (INIS)

    Ma, Chunrui; Wu, Judy; Ma, Beihai; Mi, Shao-Bo; Liu, Ming


    High quality c-axis oriented epitaxial Pb 0.92 La 0.08 Zr 0.52 Ti 0.48 O 3 films were fabricated using pulsed laser deposition on (001) LaAlO 3 substrates with conductive LaNiO 3 buffers. Besides confirmation of the in-plane and out-of-plane orientations using X-ray diffraction, transmission electron microscopy study has revealed columnar structure across the film thickness with column width around 100 nm. Characterization of ferroelectric properties was carried out in comparison with polycrystalline Pb 0.92 La 0.08 Zr 0.52 Ti 0.48 O 3 films to extract the effect of epitaxial growth. It is found that the ratio between the irreversible Rayleigh parameter and reversible parameter increased up to 0.028 cm/kV at 1 kHz on epitaxial samples, which is more than twice of that on their polycrystalline counterparts. While this ratio decreased to 0.022 cm/kV with increasing frequency to100 kHz, a much less frequency dependence was observed as compared to the polycrystalline case. The epitaxial Pb 0.92 La 0.08 Zr 0.52 Ti 0.48 O 3 films exhibited a higher mobility of domain wall and the higher extrinsic contribution to the dielectric properties, as well as reduced density of defects, indicating that it is promising for tunable and low power consumption devices

  3. PLZT Film Capacitors for Power Electronics and Energy Storage Applications

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Beihai; Hu, Zhongqiang; Koritala, Rachel E.; Lee, Tae H.; Dorris, Stephen E.; Balachandran, Uthamalingam


    Ceramic film capacitors with high dielectric constant and high breakdown strength hold special promise for applications demanding high power density. By means of chemical solution deposition, we deposited ≈2-μm-thick films of lanthanum-doped lead zirconate titanate (PLZT) on LaNiO3-buffered Ni (LNO/Ni) foils and platinized silicon (PtSi) substrates. The dielectric properties and energy storage performance of the resulting samples were determined under a high level of applied electric field. X-ray diffraction stress analysis revealed that PLZT on LNO/Ni bears a compressive stress of ≈370 MPa while PLZT on PtSi endures a tensile stress of ≈250 MPa. Compressive stress was found to lead to heightened polarization, improved tunability, increased irreversible domain wall motion, and enhanced breakdown strength for PLZT deposited on the LNO/Ni as compared with the PtSi substrate. We observed a tunability of ≈55 and ≈40 % at room temperature under 100 kV/cm applied field, remanent polarization of ≈23.5 and ≈7.4 µC/cm^2, coercive electric field of ≈25.6 and ≈21.1 kV/cm, and dielectric breakdown strength of ≈2.6 and ≈1.5 MV/cm for PLZT deposited on LNO/Ni foils and PtSi substrates, respectively. A high recoverable energy density of ≈85 J/cm^3 and energy conversion efficiency of ≈65 % were measured on the PLZT film grown on LNO/Ni.

  4. Room Temperature Tunable Multiferroic Properties in Sol-Gel-Derived Nanocrystalline Sr(Ti1−xFexO3−δ Thin Films

    Directory of Open Access Journals (Sweden)

    Yi-Guang Wang


    Full Text Available Sr(Ti1−xFexO3−δ (0 ≤ x ≤ 0.2 thin films were grown on Si(100 substrates with LaNiO3 buffer-layer by a sol-gel process. Influence of Fe substitution concentration on the structural, ferroelectric, and magnetic properties, as well as the leakage current behaviors of the Sr(Ti1−xFexO3−δ thin films, were investigated by using the X-ray diffractometer (XRD, atomic force microscopy (AFM, the ferroelectric test system, and the vibrating sample magnetometer (VSM. After substituting a small amount of Ti ion with Fe, highly enhanced ferroelectric properties were obtained successfully in SrTi0.9Ti0.1O3−δ thin films, with a double remanent polarization (2Pr of 1.56, 1.95, and 9.14 μC·cm−2, respectively, for the samples were annealed in air, oxygen, and nitrogen atmospheres. The leakage current densities of the Fe-doped SrTiO3 thin films are about 10−6–10−5 A·cm−2 at an applied electric field of 100 kV·cm−1, and the conduction mechanism of the thin film capacitors with various Fe concentrations has been analyzed. The ferromagnetic properties of the Sr(Ti1−xFexO3−δ thin films have been investigated, which can be correlated to the mixed valence ions and the effects of the grain boundary. The present results revealed the multiferroic nature of the Sr(Ti1−xFexO3−δ thin films. The effect of the annealing environment on the room temperature magnetic and ferroelectric properties of Sr(Ti0.9Fe0.1O3−δ thin films were also discussed in detail.

  5. Investigation of the electroforming and resistive switching mechanisms in Fe-doped SrTiO3 thin films

    International Nuclear Information System (INIS)

    Menke, Tobias


    To overcome the physical limits of todays memory technologies new concepts are needed. The resistive random access memory (RRAM), which bases on a nonvolatile and repeatable change of the resistance by external electrical stimuli, seems to be one promising candidate. Within the scope of this work, the model system Strontium titanate (SrTiO 3 ) has been investigated to get a deeper understanding of the underlying physical mechanism related to the resistance change. The electrical properties of SrTiO 3 (STO) can be modulated from a band insulator to metallic conduction by a self-doping with oxygen vacancies which act as shallow donors. A local accumulation or depletion of oxygen vacancies at the vicinity of the surface will lead to a local redox process which is responsible for the resistance change. To study the influence of the interfaces on the switching properties of SrTiO 3 thin films, epitaxial films of Fe-doped SrTiO 3 were grown on different bottom electrodes (SrRuO 3 , LaNiO 3 und Nb:STO) by a ''Pulsed Laser Deposition'' technique. An atomic force microscope equipped with a conductive tip (LC-AFM) allowed studying the conductivity of the deposited films on the nanometer scale. Resistive switching of lateral structures smaller than ∝5 nm could be realized which represents the potential of this material for a further downscaling of RRAM devices. The deposition of top electrodes, made of Platinum or Titanium, allowed the electrical characterization of metal-insulator-metal (MIM) structures. An extensive investigation of pristine MIM-devices by impedance spectroscopy showed the big impact of the metal-insulator interface on the overall device resistance. Furthermore, a chemical polarization was studied by dynamical current sweeps and identified as a volatile resistance variation. Usually a forming procedure is needed to ''enable'' the resistive switching properties in MIM devices. The electroforming of these devices was extensively studied and could be assigned, for samples exhibiting a Schottky contact, to a local bypassing of the Schottky depletion layer. Additional, annealing experiments under defined atmospheric conditions led to the result that the electroforming process can be identified as a loss of oxygen from the device. The investigations allowed drawing a detailed model of the electroformation of the prepared devices. Furthermore, two different switching mechanisms (interface related, bulk related) were identified and characterized. By variation of the voltage amplitude applied, a repeatable switching between both mechanisms could be demonstrated. Both mechanisms have been separately and extensively characterized (e.g. by impedance spectroscopy), which allowed drawing models for both types of switching effects. The interface related switching mechanism was attributed to the oxygen related opening and closing of conducting channels at the upper or lower interface and follows therewith the conventional explanations. In case of the bulk related switching effect, the resistance change is explained by the electrically induced internal redistribution of mobile donors leading to a p-n doping profile. The main features of this switching mechanism are its improved switching stability and large resistance ratios achieved. In case of the bulk related switching mechanism, switching times of 30 ns, retention times longer than 9 hours and the storage of two bits per cell (multibit capability) could be realized. These results demonstrate the great potential of SrTiO 3 as possible material for a future RRAM cell. (orig.)

  6. Manganites in Perovskite Superlattices: Structural and Electronic Properties

    KAUST Repository

    Jilili, Jiwuer


    Perovskite oxides have the general chemical formula ABO3, where A is a rare-earth or alkali-metal cation and B is a transition metal cation. Perovskite oxides can be formed with a variety of constituent elements and exhibit a wide range of properties ranging from insulators, metals to even superconductors. With the development of growth and characterization techniques, more information on their physical and chemical properties has been revealed, which diversified their technological applications. Perovskite manganites are widely investigated compounds due to the discovery of the colossal magnetoresistance effect in 1994. They have a broad range of structural, electronic, magnetic properties and potential device applications in sensors and spintronics. There is not only the technological importance but also the need to understand the fundamental mechanisms of the unusual magnetic and transport properties that drive enormous attention. Manganites combined with other perovskite oxides are gaining interest due to novel properties especially at the interface, such as interfacial ferromagnetism, exchange bias, interfacial conductivity. Doped manganites exhibit diverse electrical properties as compared to the parent compounds. For instance, hole doped La0.7Sr0.3MnO3 is a ferromagnetic metal, whereas LaMnO3 is an antiferromagnetic insulator. Since manganites are strongly correlated systems, heterojunctions composed of manganites and other perovskite oxides are sunject to complex coupling of the spin, orbit, charge, and lattice degrees of freedom and exhibit unique electronic, magnetic, and transport properties. Electronic reconstructions, O defects, doping, intersite disorder, magnetic proximity, magnetic exchange, and polar catastrophe are some effects to explain these interfacial phenomena. In our work we use first-principles calculations to study the structural, electronic, and magnetic properties of manganite based superlattices. Firstly, we investigate the electronic structure of bulk CaMnO3 and LaNiO3. An onsite Coulomn interaction term U is tested for both the Mn and Ni atoms. G-type antiferromagnetism and insulating properties of CaMnO3 are reproduced with U = 3 eV and ferromagnetic ordering is favorable when CaMnO3 is strained to the substrate lattice constant. This implies that the CaMnO3 magnetism is sensitive to both strain and the U parameter. Antiparallel orientation of the Mn and Ti moments has been found experimentally in the BiMnO3/SrTiO3 superlattice. By introducing O defects at different layers, we find similar patterns when the defect is located in the BiO layer. The structural, electronic and magnetic properties are analysed. Strong hybridization between the d3z2−r2 orbitals of the Mn and Ti atoms near the O defect is found. The effect of uniaxial strain for the formation of a two-dimensional electron gas and the interfacial Ti magnetic moments of the (LaMnO3)2/(SrTiO3)2 superlattice are investigated. By tuning the strain state from compressive to tensile, we predict under which conditions the spin-polarization of the electron gas is enhanced. Since the thickness ratio of the superlattice correlates with the strain state, we also study the structural, electronic and magnetism trends of (LaMnO3)n/(SrTiO3)m superlattices with varying layer thicknesses. The main finding is that half-metallicity will vanish for n, m > 8. Reduction of the minority band gaps with increasing n and m originates mainly from an energetic downshift of the Ti dxy states. Along with these, the interrelation between the interface geometry and the electronic properties of the antiferromagnetic/ferromagnetic superlattice BiFeO3/ La0.7Sr0.3MnO3 is investigated. The magnetic and optical properties are also analysed by first principles calculations. The half-metallic character of bulk La0.7Sr0.3MnO3 is maintained in the superlattice, which implies potential applications on spintronics and memory devices.