Effect of oxygen off-stoichiometry on the structural and magnetic properties of La0.15Sr0.85MnO3-d (d = 0.02,0.14) has been studied employing low-temperature x-ray diffraction, calorimetry, electrical-transport and magnetization. The nearly stoichiometric composition under goesfirst order phase-transition from cubic to tetragonal P4/mmm at 238 K accompanied by magnetic and electrical phase-transitions. On the contrary the off-stoichiometric composition does not show any transition and remains cubic Pm-3m down to 80 K. Offstoichiometry induced oxygen-vacancy seems to suppress the cooperative JT distortion and possibly stabilize a G-type antiferromagnetic phase with localized cantedspins. Thus we demonstrate that controlling oxygen stoichiometry is a way of structure/property engineering in electron-doped-like manganites.
We report on the magnetic and structural properties of ferromagnetic-insulating La$_2$CoMnO$_6$ thin films grown on top of (001) STO substrates by means of RF sputtering technique. Careful structural analysis, by using synchrotron X-ray diffraction, allows identifying two different crystallographic orientations that are closely related to oxygen stoichiometry and to the features (coercive fields and remanence) of the hysteresis loops. Both Curie temperature and magnetic hysteresis turn out to be dependent on the oxygen stoichiometry. In situ annealing conditions allow tailoring the oxygen cont…
In many transition metal oxides (TMOs), oxygen stoichiometry is one of the most critical parameters that plays a key role in determining the structural, physical, optical, and electrochemical properties of the material. However, controlling the growth to obtain high quality single crystal films having the right oxygen stoichiometry, especially in a high vacuum environment, has been viewed as a challenge. In this work, we show that through proper control of the plume kinetic energy, stoichiometric crystalline films can be synthesized without generating oxygen defects, even in high vacuum. We us…
Vanadium oxides are strongly correlated materials which display metal-insulator transitions as well as various structural and magnetic properties that depend heavily on oxygen stoichiometry. Therefore, it is crucial to precisely control oxygen stoichiometry in these materials, especially in thin films. This work demonstrates a high-vacuum gas evolution technique which allows for the modification of oxygen concentration in VOX thin films by carefully tuning thermodynamic conditions. We were able to control the evolution between VO2, V3O5, and V2O3 phases on sapphire substrates, overcoming the n…
We present X-ray photoelectron spectroscopy data which show that the chemisorbed oxygen previously observed to be on the surface of thin AlOx layers formed by room temperature thermal oxidation is bound by oxygen vacancies in the oxide. Increasing the electric field across the oxide, either by over-coating with a metallic electrode, or by electron bombardment, drives this surface chemisorbed oxygen into the vacancy sites. Due to the low bonding energies of these oxygen sites, subsequent oxygen exposures draw these ions back to the surface, reforming chemisorbed O$_2^-$. Al/AlOx/Al tunnel junct…
The effect of oxygen content on the magnetic and transport properties of the ferromagnetic Eu0.9Ca0.1BaCo2O5.5+δ has been carried out. Unlike the increase in TC with calcium content, paradoxally the TC value decreases with the increase in oxygen (Co4+) content as observed in the undoped phase. This result unveils the hidden generic magnetic feature of the LnBaCo2O5.5 system in the calcium doped phase. This behaviour supports strongly the appearance of Co3+ disproportion action into Co4+ and Co2+ and the magnetic phase separation scenario of ferromagnetic domains embedded in an antiferromagneti…
The possible redox (oxidation reduction) chemical methods for precisely determining the oxygen content in the perovskite manganites including hole-doped La1-xCaxMnOy and electron-doped La1-xTexMnOy compounds are described. For manganites annealed at different temperatures, the oxygen content of the samples was determined by a redox back titration in which the powder samples taken in a quartz crucible were dissolved in (1+1) sulfuric acid containing an excess of sodium oxalate, and the excess sodium oxalate was titrated with permanganate standard solution. The results indicate that the method i…
Oxygen nonstoichiometry, electrical conductivity and thermal expansion of La2 xSrxNiO4-δphases with high levels of strontium substitution (1 =< x =< 1.4) have been investigated in air and oxygen atmosphere in the temperature range 20-1050 degrees C. These phases retain the K2NiF4-type structure of La2NiO4 (tetragonal, space group I4/mmm). The oxygen vacancy fraction was determined independently from thermogravimetric and neutron diffraction experiments, and is found to increase considerably on heating. The electrical resistivity, thermal expansion and cell parameters with temperature show pecu…
Inelastic neutron scattering was employed to study the crystal-field interaction in the strontium-doped rare-earth compounds R(x)Sr(1-x)CoO(3-z) (R=Pr, Nd, Ho, and Er). Particular emphasis is laid on the effect of oxygen deficiencies which naturally occur in the synthesis of these compounds. The observed energy spectra are found to be the result of a superposition of crystal fields with different nearest-neighbor oxygen coordination at the R sites. The experimental data are interpreted in terms of crystal-field parameters which behave in a consistent manner through the rare-earth series, there…
We have prepared a series of polycrystalline samples La$_{0.5}$Sr$_{0.5}$CoO$_{3-δ}$} with $0 < δ\le 0.21$ and characterized their oxygen content, crystal structure, and magnetic properties. While the fully oxygenated samples are good ferromagnets, samples with larger $δ$ values display increasingly broad magnetic transitions. The saturation magnetization at 5 K falls rapidly as $δ$ increases. First principles electronic structure calculations provide insights into the magnetic behavior of the fully oxygenated compound, and the manner in which ferromagnetic ordering is affected by increasing o…
The impact of oxygen deficiency on physical properties of Na2/3CoO2-x has been investigated. From the combined thermogravimetric, magnetic susceptibility and synchrotron X-ray Laue diffraction studies, it is demonstrated that Na2/3CoO2 shows no superlattice ordering due to Na ions; however Na2/3CoO1.98, which has the same Co valence as that of Na0.71CoO2, shows nearly identical magnetic and transport properties and the same simple hexagonal superlattice ordering of sqrt(12)a. It is proposed that the Na ion ordering found in Na2/3CoO1.98 is identical to the ideal Na0.71CoO2 of large sqrt(12)a x…
In view of the strong anisotropy of oxygen diffusion in high-Tc ceramic YBa2Cu3Ox, it is supposed that a polycrystalline sample of this material can be presented as consisting of crystal grains where each grain was formed by a certain sequence of layers with tetragonal or orthorhombic phase structure. The theory of scattering by mixed-layer crystals was taken as a basis for calculating theoretical X-ray patterns for different sequences of the layers. Some modifications were made in the theory due to crystal structure features of the YBa2Cu3Ox phases. The results obtained agreed quantitatively …
Crystal structure, cobalt and iron speciation and oxygen non-stoichiometry of La0.6Sr0.4Co1-yFeyO3-d nanorods for IT-SOFC cathodes
Pontificia Universidad Javeriana（波哥大耶稣会天主教大学）；Centro Atómico Constituyentes, Comisión Nacional de Energía Atómica（康塞普西翁原子中心，国家原子能委员会）；Instituto de Nanociencia y Nanotecnología (INN), CNEA-CONICET（纳米科学与技术研究所，国家原子能委员会-国家科学研究和技术研究委员会）；CONICET / Laboratorio de Cristalografía Aplicada, Escuela de Ciencia y Tecnología, Universidad Nacional de Gral. San Martín（国家科学研究和技术研究委员会/应用晶体学实验室，科学与科技学院，圣马丁国立大学）；CNPEM, Laboratório Nacional de Luz Síncrotron（巴西纳米技术国家研究中心，同步光国家实验室）；Instituto de Física, Universidade de São Paulo（物理研究所，圣保罗大学）
We present a specially designed evolutionary algorithm for the prediction of surface reconstructions. This new technique allows one to automatically explore all the low-energy configurations with variable surface atoms and variable surface unit cells through the whole chemical potential range. The power of evolutionary search is demonstrated by the efficient identification of diamond 2*1 (100) and 2*1 (111) surfaces with a fixed number of surface atom and a fixed cell size. With further variation of surface unit cells, we study the reconstructions of the polar surface MgO (111). Experiment has…
The impact of oxygen deficiency on physical properties of Na2/3CoO2-x has been investigated. From the combined thermogravimetric, magnetic susceptibility and synchrotron X-ray Laue diffraction studies, it is demonstrated that Na2/3CoO2 shows no superlattice ordering due to Na ions; however Na2/3CoO1.98, which has the same Co valence as that of Na0.71CoO2, shows nearly identical magnetic and transport properties and the same simple hexagonal superlattice ordering of sqrt(12)a. It is proposed that the Na ion ordering found in Na2/3CoO1.98 is identical to the ideal Na0.71CoO2 of large sqrt(12)a x…
Metal-insulator transitions (MIT),an intriguing correlated phenomenon induced by the subtle competition of the electrons' repulsive Coulomb interaction and kinetic energy, is of great potential use for electronic applications due to the dramatic change in resistivity. Here, we demonstrate a reversible control of MIT in VO2 films via oxygen stoichiometry engineering. By facilely depositing and dissolving a water-soluble yet oxygen-active Sr3Al2O6 capping layer atop the VO2 at room temperature, oxygen ions can reversibly migrate between VO2 and Sr3Al2O6, resulting in a gradual suppression and a …
Designing heterostructures to control oxygen stoichiometry in helimagnetic perovskite strontium ferrite
Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory（斯坦福材料能源科学研究所，SLAC国家加速器实验室）；Department of Applied Physics, Stanford University（斯坦福大学应用物理系）；Department of Materials Science and Engineering, Northwestern University（西北大学材料科学与工程系）；Catalan Institute of Nanoscience and Nanotechnology (ICN2)（加泰罗尼亚纳米科学与纳米技术研究所（ICN2））；School of Applied and Engineering Physics, Cornell University（康奈尔大学应用与工程物理学院）；Center for Nanophase Materials Sciences, Oak Ridge National Laboratory（橡树岭国家实验室纳米材料科学中心）；Department of Material Science Engineering, Pusan National University（釜山大学材料科学与工程系）；Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory（SLAC国家加速器实验室斯坦福同步辐射光源）
We performed neutron powder diffraction measurements on (Bi$_{0.5}$Na$_{0.5+x}$)TiO$_3$ and (Bi$_{0.5+y}$Na$_{0.5}$)TiO$_3$ to study structural evolution induced by the non-stoichiometry. Despite the non-stoichiometry, the local structure ($r$$\leq$ 3.5 Å) from the pair distribution function analysis is barely affected by the sodium deficit of up to -5 mol%. With increasing pair distance, however, the atomic pair correlations weaken due to the disorder caused by the sodium deficiency. Although the sodium and the bismuth share the same crystallographic site, their non-stoichiometry have rather …
The effect of the variation of oxygen content on structural, magnetic and transport properties in the electron-doped manganites La0.9Te0.1MnOy has been investigated. All samples show a rhombohedral structure with the space group . The Curie temperature decreases and the paramagnetic-ferromagnetic (PM-FM) transition becomes broader with the reduction of oxygen content. The resistivity of the annealed samples increases slightly with a small reduction of oxygen content. Further reduction in the oxygen content, the resistivity maximum increases by six orders of magnitude compared with that of the …
The oxygen stoichiometry has a large influence on the physical and chemical properties of complex oxides. Most of the functionality in e.g. catalysis and electrochemistry depends in particular on control of the oxygen stoichiometry. In order to understand the fundamental properties of intrinsic surfaces of oxygen-deficient complex oxides, we report on in situ temperature dependent scanning tunnelling spectroscopy experiments on pristine oxygen deficient, epitaxial manganite films. Although these films are insulating in subsequent ex situ in-plane electronic transport experiments at all tempera…
We have carried out a systematic experimental investigation to address the question why thin films of Fe$_3$O$_4$ (magnetite) generally have a very broad Verwey transition with lower transition temperatures as compared to the bulk. We observed using x-ray photoelectron spectroscopy, x-ray diffraction and resistivity measurements that the Verwey transition in thin films is drastically influenced not only by the oxygen stoichiometry but especially also by the substrate-induced microstructure. In particular, we found (1) that the transition temperature, the resistivity jump, and the conductivity …
La1-xCaxMnO3+delta and La1-xNaxMnO3+delta samples with well defined cation molecularity and oxygen contents are analyzed with XRPD, electrical conductivity, electron paramagnetic resonance and static magnetization measurements. Point defects are introduced in the structure by: i) aliovalent cation doping (substitutional defects), ii) oxygen over-stoichiometry (cation vacancies) and iii) oxygen under-stoichiometry (oxygen vacancies). The cation doping mainly influences the material by affecting the tolerance factor and the oxidation of the Mn ions; the cation vacancies affect the magnetic prope…
CaxCu3Ti4O12 polycrystalline powders with variation in calcium content were prepared via the oxalate precursor route. The structural, morphological and dielectric properties of the ceramics fabricated using these powders were studied using x ray diffraction, Scanning Electron Microscope along with Energy Dispersive X ray Analysis, Transmission Electron Microscopy, Electron Spin Resonance (ESR) spectroscopy and Impedance analyzer. The X ray diffraction patterns obtained for the x = 0.97, 1.0 and 1.1 powdered ceramics could be indexed to a body centered cubic perovskite related structure associa…
We report measurements on MgB2 up to ~40GPa. Increasing pressure yields a monotonous decrease of the lattice parameters and of the c/a ratio, but no structural transition down to parameters smaller than those of AlB2. The transition superconducting temperature also decreases with temperature in a sample dependent way. The results are explained by an increase of the filling of the 2D pxy bands with pressure, the Mg stoichiometry determining the starting position of the Fermi level. Our measurements indicate that these hole bands are the relevant ones for superconductivity.
A correlation between lattice parameters, oxygen composition, and the thermoelectric and Hall coefficients is presented for single-crystal Li(0.9)Mo(6)O(17), a quasi-one-dimensional (Q1D) metallic compound. The possibility that this compound is a compensated metal is discussed in light of a substantial variability observed in the literature for these transport coefficients.
The presence in the graphyne sheets of a variable amount of sp2/sp1 atoms, which can be transformed into sp3-like atoms by covalent binding with one or two fluorine atoms, respectively, allows one to assume the formation of fulorinated graphynes (fluorographynes) with variable F/C stoichiometry. Here, employing DFT band structure calculations, we examine a series of fluorographynes, and the trends in their stability, structural and electronic properties have been discussed as depending on their stoichiometry: from C2F3 (F/C= 1.5) to C4F7 (F/C= 1.75).
Local Structure of Epitaxial Single Crystal UO$_{2+x}$ Thin Films
School of Physics, University of Bristol（布里斯托大学物理学院）；Department of Materials, University of Oxford（牛津大学材料系）；Department of Complex Matter, Josef Stefan Institute（约瑟夫·斯特凡研究所复杂物质系）；School of Chemistry, University of Bristol（布里斯托大学化学学院）；Department of Chemistry, Washington State University（华盛顿州立大学化学系）
The results of the synthesis and characterization of the optimally doped (La)1.4(Sr1-yCay)1.6Mn2O7 solid solution with y=0, 0.25 and 0.5 are reported. By progressively replacing the Sr with the smaller Ca, while keeping fixed the hole-concentration due to the divalent dopant, the 'size effect' of the cation itself on the structural, transport and magnetic properties of the bilayered manganite has been analysed. Two different annealing treatments of the solid solution, in pure oxygen and in pure argon, allowed also to study the effect of the oxygen content variation. Structure and electronic pr…
Stoichiometry-Controlled Structural Order and Tunable Antiferromagnetism in $\mathrm{Fe}_{x}\mathrm{NbSe_2}$ ($0.05 \le x \le 0.38$)
Tsung-Dao Lee Institute, School of Physics and Astronomy, Shanghai Jiao Tong University（上海交通大学物理与天文学院李政道研究所）；Shenzhen Institute for Quantum Science and Engineering, Southern University of Science and Technology（南方科技大学量子科学与工程研究院）；International Quantum Academy（国际量子科学院）；Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University（上海交通大学张江高等研究院）；State Key Laboratory of Micro-nano Engineering Science, Shanghai Jiao Tong University（上海交通大学微纳制造技术国家重点实验室）
The study of high pressure (2 GPa) synthesized MgB2-based materials allows us to conclude that higher borides (with near MgB12 stoichiometry) and oxygen-enriched Mg-B-O inclusions can be pinning centers in nanostructural magnesium diboride matrix (with average grain sizes of 15-37 nm). It has been established that additions of Ti or SiC as well as manufacturing temperature can affect the size, amount and distribution of these inclusions in the material structure and thus, influence critical current density. The superconducting behavior of materials with near MgB12 stoichiometry of matrix is di…
We have succeeded in preparing high-quality Gd-doped single-crystalline EuO films. Using Eu-distillation-assisted molecular beam epitaxy and a systematic variation in the Gd and oxygen deposition rates, we have been able to observe sustained layer-by-layer epitaxial growth on yttria-stabilized cubic zirconia (001). The presence of Gd helps to stabilize the layer-by-layer growth mode. We used soft x-ray absorption spectroscopy at the Eu and Gd M4,5 edges to confirm the absence of Eu3+ contaminants and to determine the actual Gd concentration. The distillation process ensures the absence of oxyg…
We have investigated the effect of synthesis and growth conditions on the magnetic, structural, and compositional properties of pyrochlore oxide holmium titanate and demonstrate a method for growing high quality stoichiometric single crystals. A series of polycrystalline samples with various contents of Ti (-0.08 \leqslant x \leqslant 0.08, and nominal compositions of Ho2Ti2+xO7) were synthesized at different temperatures, and characterized using powder X-ray diffraction. The results show that synthesizing powders at a higher temperature of 1500 °C yield single phase compounds. Ti deficient po…
We have grown and studied high quality SrRuO3 films grown by MBE as well as PLD. By changing the oxygen activity during deposition we were able to make SrRuO3 samples that were stoichiometric (low oxygen activity) or with ruthenium vacancies (high oxygen activity). Samples with strontium vacancies were found impossible to produce since the ruthenium would precipitate out as RuO2. The volume of the unit cell of SrRuO3 becomes larger as more ruthenium vacancies are introduced. The residual resistivity ratio (RRR) and room temperature resistivity were found to systematically depend on the volume …
Control of materials through custom design of ionic distributions represents a powerful new approach to develop future technologies ranging from spintronic logic and memory devices to energy storage. Perovskites have shown particular promise for ionic devices due to their high ion mobility and sensitivity to chemical stoichiometry. In this work, we demonstrate a solid-state approach to control of ionic distributions in (La,Sr)CoO$_{3}$ thin films. Depositing a Gd capping layer on the perovskite film, oxygen is controllably extracted from the structure, up-to 0.5 O/u.c. throughout the entire 36…
A structural study is presented of ab-initio molecular dynamics simulations of Ge-As-Se calcogenide glasses performed at the same mean coordination number but differing stoichiometry ranging between Se rich and Se poor glasses. Starting configurations are generated via Reverse Monte Carlo (RMC) simulations of Extended X-ray Absorption Fine Structure (EXAFS) measurements of experimental samples. Structural analysis is presented illustrating the bonding trends found with changing stoichiometry.
Oxygen stoichiometry is one of the most important elements in determining the physical properties of transition metal oxides (TMOs). A small fractional change in the oxygen content, resulting in the variation of valence state of the transition metal, can drastically modify the materials functionalities. In particular, TMOs with mixed valences have attracted attention for many energy applications. Previous studies also showed that the ability to control the number of d-band electron populations and detailed spin configurations is critical for improved catalytic performance of TMOs. In this cont…
Defects in semiconductors can exhibit multiple charge states, which can be used for charge storage applications. Here we consider such charge storage in a series of oxygen deficient phases of TiO$_2$, known as Magnéli phases. These Ti$_n$O$_{2n-1}$ Magnéli phases present well-defined crystalline structures, i. e., their deviation from stoichiometry is accommodated by changes in space group as opposed to point defects. We show that these phases exhibit intermediate bands with the same electronic quadruple donor transitions akin to interstitial Ti defect levels in TiO$_2$-rutile. Thus, the Magné…
Stoichiometric Epitaxial Strontium Titanate Thin Films on Silicon by High-Temperature Sr Segregation
Imec；Department of Materials Engineering (MTM), KU Leuven（荷语鲁汶大学材料工程系）；Physics Department, Jean Monnet University（圣艾蒂安让·穆内大学物理系）；Department of Information Technology (INTEC), Photonics Research Group, Ghent University（根特大学信息与科技学院光子学研究组）
Precise control of lattice mismatch accommodation and cation interdiffusion across the interface is critical to modulate correlated functionalities in epitaxial heterostructures, particularly when the interface composition is positioned near a compositional phase transition boundary. Here we select La1-xSrxMnO3 (LSMO) as a prototypical phase transition material and establish vertical epitaxial interfaces with NiO to explore the strong interplay between strain accommodation, stoichiometry modification, and localized electron transport across the interface. It is found that localized stoichiomet…
We investigated a method for obtaining a sintered bulk sample of single-phase Sr2MoO4, which has recently increased in importance due to its similarities to superconducting Sr2RuO4. We discovered that with the aid of Ti2O3 as a p(O2) buffer, high-purity Sr2MoO4 is successfully synthesized in a sealed tube. We confirmed the space group and determined the exact elemental composition of the compound in order to establish its stoichiometry. The guideline for the rational choice of a p(O2)-buffer material is discussed.
Near-Atomic-Scale Compositional Complexity in a 2D Transition Metal Oxide
Max Planck Institute for Sustainable Materials（马克斯·普朗克可持续材料研究所）；Tel Aviv University（特拉维夫大学）；West Pomeranian University of Technology in Szczecin（什切青西波美拉尼亚理工大学）；Univ Rouen Normandie, CNRS, INSA Rouen Normandie, Groupe de Physique des Matériaux, UMR 6634（鲁昂诺曼底大学，法国国家科学研究中心，鲁昂国立应用科学学院，物质物理研究组）
The zero-field $^{139}$La and $^{55}$Mn nuclear magnetic resonances were studied in $\rm La_{0.8}Ca_{0.2}MnO_{3+δ}$ with different oxygen stoichiometry $δ$. The signal intensity, peak frequency and line broadening of the $^{139}$La NMR spectrum show that excess oxygens have a tendency to concentrate and establish local ferromagnetic ordering around themselves. These connect the previously existed ferromagnetic clusters embedded in the antiferromagnetic host, resulting in percolative conduction paths. This phase separation is not a charge segregation type, but a electroneutral type. The magneto…
We report on the fabrication of conducting interfaces between LaAlO$_3$ and SrTiO$_3$ by 90$^o$ off-axis sputtering in an Ar atmosphere. At a growth pressure of 0.04 mbar the interface is metallic, with a carrier density of the order of $10^{13}$ cm$^{-2}$ at 3 K. By increasing the growth pressure, we observe an increase of the out-of-plane lattice constants of the LaAlO$_3$ films while the in-plane lattice constants do not change. Also, the low-temperature sheet resistance increases with increasing growth pressure, leading to an insulating interface when the growth pressure reaches 0.10 mbar.…
We reveal a correlation between the M-X bond energy descriptor EMX for the optimal catalyst in a family of stoichiometry MiXj, and an intensive quantity defined as the standard enthalpy of the catalyzed reaction normalized to one mole of element X transferred by this reaction from reactants to products. M is a transition element, and the stoichiometry MiXj is fixed at the solid/fluid interface by the reaction conditions. We illustrate this for a relevant set of reactions involved in solar energy and industrial applications such as oxygen evolution, oxygen reduction and hydrogen evolution in el…
Epitaxial LaRh1/2Mn1/2O3 thin films have been grown on (001)-oriented LaAlO3 and SrTiO3 substrates using pulsed laser deposition. The optimized thin film samples are semiconducting and ferromagnetic with a Curie temperature close to 100 K, a coercive field of 1200 Oe, and a saturation magnetization of 1.7muB per formula unit. The surface texture, structural, electrical, and magnetic properties of the LaRh1/2Mn1/2O3 films was examined as a function of the oxygen concentration during deposition. While an elevated oxygen concentration yields thin films with optimal magnetic properties, slightly l…
We report on Raman and photoluminescence spectroscopic studies on oxygen vacancy induced structural disorder in Gd2Ti2O7-d single crystals grown by optical floating zone technique under argon atmosphere. The oxygen vacancies in Gd2Ti2O7-d wafers decrease with thermal annealing in an air atmosphere. The full width at half maximum of X-ray diffraction rocking curve decreases from 245 to 157 arc-second and the optical transmittance increases from 23 to 87 % (at 1000 nm) upon post growth thermal annealing. Raman spectroscopic studies reveal a monotonic increase in intensity of O-Gd-O (Eg) and Ti-O…
The crystal structure and oxygen stoichiometry in two-layer Na0.74CoO2 and Na0.38CoO2 at room temperature are analyzed by powder neutron diffraction. Two sets of diffraction data for each sample, taken at different incident neutron wavelengths, lambda=1.1968 Angstroms and lambda=1.5403 Angstroms, are analyzed simultaneously by the Rietveld method, allowing for the independent refinement of all structural parameters. The fractional oxygen site occupancies are found to be 1.01(1) for Na0.74CoO2 and 0.99(2) for Na0.38CoO2 respectively. These results indicate that the oxygen content of these phase…
Disorder, primarily in the form of oxygen vacancies, cation stoichiometry and atomic inter-diffusion, appear to play vital roles in the electronic and transport properties of the metallic electron liquid at the oxide hetero-interfaces. Antisite disorder is also understood to be a key player in this context. In order to delineate the roles of two of these key factors, oxygen vacancy and antisite disorder, we have investigated the effect of oxygen vacancy on the antisite disorder at a number of interfaces separating two La-based transition metal oxides using density functional theory. Oxygen vac…
We present a Density Functional Theory (DFT) study of the structural and electronic properties of bare rutile VO$_{2}$(110) surfaces and its oxygen-rich terminations. We discuss the performance of various DFT functionals, including PBE, PBE+U (U = 2 eV), SCAN and SCAN+rVV functionals with non-magnetic and ferromagnetic spin ordering. We predict the presence of a ring-like termination that is electronically and structurally related to a V$_{2}$O$_{5}$(001) monolayer and shows a higher stability than pure oxygen adsorption phases. Despite the fact that the calculated phase stabilities depend on …
Nanoscale Spatial Tuning of Superconductivity in Cuprate Thin Films via Direct Laser Writing
Politecnico di Milano（米兰理工大学）；Institut de Ciència de Materials de Barcelona, ICMAB-CSIC（巴塞罗那材料科学研究所）；Universitat Autònoma de Barcelona（巴塞罗那自治大学）；Université de Liège（列日大学）
The thermally-induced structural evolution of silicon- and oxygen-containing hydrogenated amorphous carbon (a-C:H:Si:O) was investigated by X-ray photoelectron and absorption spectroscopy, as well as molecular dynamics (MD) simulations. The spectroscopic results indicate that the introduction of Si and O in hydrogenated amorphous carbon (a-C:H) increases the activation energy for the conversion of sp3- to sp2-bonded C. MD simulations indicate that the higher thermal stability of a-C:H:Si:O compared to a-C:H derives from the lower fraction of strained C-C sp3 bonds in a-C:H:Si:O.
We investigated SrFeO$_{3-x}$ thin films on a SrTiO$_3$ (001) substrate prepared via pulsed laser epitaxy using an optical spectroscopy technique. The oxygen vacancy level ($x$) was controlled by post-annealing processes at different oxygen partial pressures. We achieved a brownmillerite(BM) structure at $x =$ 0.5 and observed the evolution of the crystal structure from BM into perovskite(PV) as the oxygen concentration increased. We observed the evolution of infrared-active phonons with respect to the oxygen concentration, which was closely related to the structural evolution observed via X-r…
Effect of FABr Over-Stoichiometry on the Morphology and Optoelectronic Properties of Wide-Bandgap FAPbBr_3 Films
Istituto di Struttura della Materia - CNR (ISM-CNR)（物质结构研究所-意大利国家研究委员会）；Centre for Hybrid and Organic Solar Energy (CHOSE), Department of Electronic Engineering, Tor Vergata University of Rome（罗马托尔维加塔大学电子工程系混合与有机太阳能中心）；Department of Chemical Sciences and Technologies, Tor Vergata University of Rome（罗马托尔维加塔大学化学科学与技术系）
Silicon suboxide is currently considered as a unique candidate for lithium ion batteries anode materials due to its considerable capacity. However, no adequate information exist about the role of oxygen content on its performance. To this aim, we used density functional theory to create silicon suboxide matrices of various Si:O ratios and investigated the role of oxygen content on the structural, dynamic, electronic properties and lithiation behavior of the matrices. Our study demonstrates that the O atoms interact strongly with the inserted Li atoms resulting in a disintegration of the host m…
