A comprehensive study of structure and properties of nanocrystalline zinc peroxide
Abstract Nanocrystalline zinc peroxide (nano-ZnO2) was synthesized through a hydrothermal process and comprehensively studied using several experimental techniques. Its crystal structure was characterized by X-ray diffraction, and the average crystallite size of 22 nm was estimated by Rietveld refinement. The temperature-dependent local environment around zinc atoms was reconstructed using reverse Monte Carlo (RMC) analysis from the Zn K-edge X-ray absorption spectra. The indirect band gap of about 4.6 eV was found using optical absorption spectroscopy. Lattice dynamics of nano-ZnO2 was studied by infrared and Raman spectroscopy. In situ Raman measurements indicate the stability of nano-ZnO…
The role of yttrium and titanium during the development of ODS ferritic steels obtained through the STARS route: TEM and XAS study
Abstract Oxide Dispersion Strengthened Ferritic Steels (ODS FS) are candidate materials for structural components in future fusion reactors. Their high strength and creep resistance at elevated temperatures and their good resistance to neutron radiation damage is obtained through extremely fine microstructures containing a high density of nanometric precipitates, generally yttrium and titanium oxides. This work shows transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS) characterization of Fe-14Cr-2W-0.3Ti-0.24Y ODS FS obtained by the STARS route (Surface Treatment of gas Atomized powder followed by Reactive Synthesis), an alternative method to obtain O…
Investigation of precipitate in an austenitic ODS steel containing a carbon-rich process control agent
This work has been carried out within the framework of the German Helmholtz Association and has received funding from the topic “Materials Research for the Future Energy Supply”. The work of M. Parish and Rainer Ziegler is gratefully acknowledged. Thanks are also due to the team of the chemical laboratory at the KIT for performing the chemical analysis. The help of the beamline staff at ELETTRA (project 20140052 ) synchrotron radiation facility is acknowledged. We acknowledge support by Deutsche Forschungsgemeinschaft and Open Access Publishing Fund of Karlsruhe Institute of Technology.
Hydrogen induced metallization of ZnO (11̅00) surface: Ab initio study
Abstract Results of first principles hybrid calculations are presented for hydrogen atoms adsorbed upon non-polar ZnO (1100) surface. The energy of surface atomic relaxation, H adsorption energy, electronic density redistribution and modification of the electronic structure are discussed. It is shown that hydrogen is adsorbed mainly on the surface oxygen ions and forms a strong bonding with them (2.7 eV). Adsorption of hydrogen on the surface zinc ions is energetically unfavorable (− 4.4 eV). It also shown that surface hydrogen atoms are very shallow donors, thus, contributing to the electronic conductivity, and ZnO metallization.
X-ray absorption study of Ce?Ti oxide films
Abstract X-ray absorption measurements at the Ce L 3 , L 1 and Ti K-edges have been done to study local structure and electronic properties of CeO 2 –TiO 2 thin films produced by reactive d.c. magnetron sputtering. The local environment around titanium and cerium ions can be described as pyramid-like and cube-like polyhedra, respectively, and the films are amorphous (correlation radius about 10 A). The analysis of Ce L 3 -edge XANES data has shown that the position of the Ce 4f 1 5d and 4f 0 5d states progressively shift towards lower energies with decreasing cerium dioxide content in the thin films.
X-Ray studies on optical and structural properties of ZnO nanostructured thin films
Abstract X-ray absorption near-edge fine structure (XANES) studies have been carried out on nanostructured ZnO thin films prepared by atmospheric pressure chemical vapour deposition (APCVD). Films have been characterized by X-ray diffraction (XRD) and optical luminescence spectroscopy exciting with laser light (PL) or X-ray (XEOL). According to XRD measurements, all the APCVD samples reveal a highly (002) oriented crystalline structure. The samples have different thickness (less than 1 μm) and show significant shifts of the PL and XEOL bands in the visible region. Zn K-edge XANES spectra were recorded using synchrotron radiation at BM08 of ESRF (France), by detecting photoluminescence yield…
<title>Iridium L<formula><inf><roman>3</roman></inf></formula>-edge and oxygen K-edge x-ray absorption spectroscopy of nanocrystalline iridium oxide thin films</title>
Structural investigations of the short range order around iridium and oxygen ions in nanocrystalline iridium oxide thin films, prepared by dc magnetron sputtering technique, were performed by x-ray absorption spectroscopy. The Ir L3-edge extended x-ray absorption fine structure and the O K-edge x-ray absorption near edge structure signals were measured at room temperature and analyzed within ab initio multiple-scattering and full-multiple-scattering approaches, respectively. The x-ray absorption spectroscopy results indicate the presence in the films of orderd regions - nanocrystals, having a size of about 10 angstrom and a structure rather close to that in crystalline iridium oxide IrO2. S…
High‐Quality Si‐Doped β‐Ga 2 O 3 Films on Sapphire Fabricated by Pulsed Laser Deposition
The EU Horizon 2020 project CAMART2 is acknowledged for partly supporting the project, and the Ion Technology Centre, ITC, in Sweden is acknowledged for ion beam analysis (ERDA).
Disappearance of correlations in the atom motion upon hydrogen intercalation into ReO3lattice
The influence of hydrogen intercalation on the local structure of rhenium trioxide is studied in-situ by the Re L3-edge EXAFS spectroscopy and analysed using a novel approach, based on the use of evolutionary algorithm and wavelet transform. The proposed method allows us to perform accurate EXAFS analysis within the multiple-scattering approach taking into account contributions from outer coordination shells and to access the information on correlations in atomic thermal motion.
Local structure studies of SrTi16O3and SrTi18O3
In this work we report on the local structure of Ti in SrTi 16 O3 (STO16) and SrTi 18 O3 (STO18) investigated in the low temperature range (6‐300K) by extended x-ray absorption fine structure and x-ray absorption near edge structure (XANES) spectroscopy at Ti K-edge and by optical second harmonic generation (SHG). By comparing XANES of STO16 and STO18 we have identified the isotopic effect which produces at T < 100K a noticeable difference in the measured mean square relative displacements (MSRD) of Ti‐O1 bonds: while STO16 follow the expected Einstein-like behavior, for STO18 we have measured an increase of MSRD values with decreasing temperature. This is an indication of an increasing off…
Local structure and vibrational dynamics in NiWO4
Abstract Systematic studies of nickel tungstate thin film, amorphous and polycrystalline powders were performed by X-ray absorption spectroscopy at the Ni K and W L1,3 edges, X-ray diffraction and Raman spectroscopy. We found that in spite of the similarity of the local environment around nickel and tungsten ions in all three materials, there is strong difference in the Ni-O and W-O interactions for thin film/amorphous powder and polycrystalline powder. The nickel-oxygen bonding becomes stronger by going from thin film or amorphous powder to polycrystalline tungstate at the expense of the tungsten-oxygen bonding strength. Besides, in thin film and amorphous NiWO4, nickel and tungsten ions h…
EPR Study of Gd3+local structure in ScF3crystal with negative thermal expansion coefficient
Zero field splitting (ZFS) of Gd3+ impurity in ScF3 is studied by electron paramagnetic resonance at 77 and 295 K. ZFS parameter b4 values obtained from angular dependence simulations show that regardless of negative thermal expansion in ScF3 temperature dependence of |b4| is similar to other cubic fluoroperovskites. Our analysis of ZFS parameters indicates that the local structure of Gd3+ centres expands positively with temperature.
Short and Medium Range Order in Se1-xTexGlasses
Complementary XAFS measurements (LURE and NSLS) of Se 1 - x Te x glasses have been carried out on both the Se and Te K-edges at low and room temperatures. Using a multi-shell best fit analysis procedure, we have reconstructed the Se and Te local environment: (i) first shell intrachain nearest neighbors (Se-Se 1 , Se-Te 1 , Te-Se 1 ,and Te-Te 1 ); (ii) second shell intrachain (Se-Se 2 and Se-Te 2 ) and interchain next nearest neighbors (Se⇔Se 3 single scattering in the chains Se-Se 1 -Se 3 and Se-Te 1 -Se 3 ). For the first and second coordination shells we suggest that the intrachain chemical order increases with Te content. On the other hand, we propose a model of random distribution of Se…
Ab-Initio Calculations of Oxygen Vacancy in Ga2O3 Crystals
The research has been funded by the Science Committee of the Ministry of Education and Science of the Republic of Kazakhstan (Grant No. AP08856540). J. Purans and A.I.Popov acknowledge the ERAF project 1.1.1.1/20/A/057 “Functional Ultrawide Bandgap Gallium Oxide and Zinc Gallate Thin Films and Novel Deposition Technologies”. The Institute of Solid State Physics, University of Latvia (Latvia) as the Centre of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD01-2016-2017-Teaming Phase2 under grant agreement No. 739508, project CAMART2.
Tendencies in ABO3 Perovskite and SrF2, BaF2 and CaF2 Bulk and Surface F-Center Ab Initio Computations at High Symmetry Cubic Structure
This research was partly funded by the Latvian Council of Science project No. LZP‐ 2020/2‐0009 (for R. Eglitis), as well as the ERAF Project No. 1.1.1.1/18/A/073. We express our gratitude for the financial support from Latvian–Ukraine cooperation Project No. Latvia–Ukraine LV‐ UA/2021/5. The Institute of Solid State Physics, University of Latvia (Latvia), as the Centre of Excellence has received funding from the European Unions Horizon 2020 Framework Pro‐ gramme H2020‐WIDESPREAD01‐2016‐2017‐Teaming Phase2 under Grant Agreement No. 739508, project CAMART2.
<title>Local structure of Ta-Re mixed oxide thin films studied by x-ray absorption spectroscopy</title>
Mixed Ta-Re oxide thin films were synthesized for the first time by dc magnetron co-sputtering. Local environment around tantalum and rhenium atoms was studied by the Ta and Re L3-edges x-ray absorption spectroscopy in pure Ta2O5 and mixed Ta-Re oxide thin films (Ta:Re = 50:50, 38:62, 20:80 as determined from the ratio of the Ta-to-Re absorption edges). It was found that rhenium atoms are four-fold coordinated by oxygen atoms with R(Re-O) = 1.74 ± 0.01 Å and the mean square relative displacement (MSRD) σ2 = 0.0012 ± 0.0005 Å2. In pure Ta2O5 thin film, tantalum ions are coordinated by six oxygen atoms at R(Ta-O) = 2.02 ± 0.01 Å with the MSRD σ2 = 0.010 ± 0.001 Å2. The addition of rhenium ion…
Structural, electrical and optical characteristics of Al-doped zinc oxide thin films deposited by reactive magnetron sputtering
ZnO:Al (AZO) thin films on glass were deposited by DC reactive magnetron sputtering at approximately 300°C substrate temperature. Structural, electrical and optical properties were investigated as a function of oxygen flow. XRD data shows that AZO thin films are polycrystalline with pronounced c-axis orientation and the grain size increasing with the oxygen flow. The lowest achieved resistivity within the deposited set of samples was 7.6·10 -4 Ωcm. The transmittance of AZO films was above 80 % at 550 nm with the optical band gap between 3.4 and 3.8 eV.
XAFS study of interchain and intrachain order inSe1−xTexglasses: Nearest neighbors
XAFS measurements (LURE and NSLS) of ${\mathrm{Se}}_{1\ensuremath{-}x}{\mathrm{Te}}_{x}$ glasses have been carried out on both the Se and Te $K$ edges at low and room temperatures. Using a multishell best-fit analysis procedure, we have reconstructed the Se and Te local environment: first-shell intrachain nearest neighbors $(\mathrm{Se}\ensuremath{-}{\mathrm{Se}}_{1}, \mathrm{Se}\ensuremath{-}{\mathrm{Te}}_{1}, \mathrm{Te}\ensuremath{-}{\mathrm{Se}}_{1},$ and $\mathrm{Te}\ensuremath{-}{\mathrm{Te}}_{1}).$ We conclude that the intrachain chemical order (preferential of Se-Te pairs) increases with Te content in the glasses. On the other hand, we suggest a random distribution of Se and Te atom…
Ab initio calculations of CaZrO3 (011) surfaces: systematic trends in polar (011) surface calculations of ABO3 perovskites
Financial support via Latvian-Ukrainian Joint Research Project No. LV-UA/2018/2 for A. I. Popov, Latvian Council of Science Project No. 2018/2-0083 “Theoretical prediction of hybrid nanostructured photocatalytic materials for efficient water splitting” for R. I. Eglitis and J. Kleperis as well as ERAF project No. 1.1.1.1/18/A/073 for R. I. Eglitis and J. Purans is greatly acknowledged.
Extended X-Ray Absorption Fine Structure Spectroscopy of Perovskite-Type Compounds
Application of the extended x-ray absorption fine structure (EXAFS) spectroscopy to a study of the local atomic structure in perovskitetype materials is discussed on the example of several compounds (m-WO3, NaxWO3, ReO3 and FeF3). The sensitivity of the EXAFS to the out-of-center and rotational distortions is discussed in details.
Molecular dynamics simulations of EXAFS in germanium
AbstractClassical molecular dynamics simulations have been performed for crystalline germanium with the aim to estimate the thermal effects within the first three coordination shells and their influence on the single-scattering and multiple-scattering contributions to the Ge K-edge extended x-ray absorption fine structure (EXAFS).
Interpretation of the U L3-edge EXAFS in uranium dioxide using molecular dynamics and density functional theory simulations
X-ray absorption spectroscopy is employed to study the local structure of pure and Cr-doped UO2 at 300 K. The U L3-edge EXAFS spectrum is interpreted within the multiplescattering (MS) theory using the results of the classical and ab initio molecular dynamics simulations, allowing us to validate the accuracy of theoretical models. The Cr K-edge XANES is simulated within the full-multiple-scattering formalism considering a substitutional model (Cr at U site). It is shown that both unrelaxed and relaxed structures, produced by ab initio density functional theory (DFT) calculations, fail to describe the experiment.
EXAFS study of mixed nickel molybdenum oxide thin films at the Ni and Mo K-edges
Mixed nickel molybdenum oxide thin films were produced by DC magnetron co-sputtering technique with the nickel content about 8, 16 and 25 at%. X-ray absorption spectroscopy at the Ni and Mo K-edges was used to study the local atomic structure in the films. The best-fit analysis of the EXAFS signals suggests that (i) the films are amorphous, except for the highest nickel content (25 at%), at which a segregation of NiO phase was observed; (ii) nickel and molybdenum atoms are octahedrally coordinated by oxygen atoms. Opposite to the NiO6 octahedra, the MoO6 octahedra are strongly distorted, that results in an existence of two groups of oxygen atoms—four nearest at B1.76 ( A and two distant at …
High power impulse magnetron sputtering of Zn/Al target in an Ar and Ar/O2 atmosphere: The study of sputtering process and AZO films
Financial support provided by Scientific Research Project for Students and Young Researchers Nr. SJZ/2017/4 realised at the Institute of Solid State Physics, University of Latvia is greatly acknowledged.
Temperature-dependent EXAFS study of the local structure and lattice dynamics in cubic Y2O3
The local structure and lattice dynamics in cubic Y2O3were studied at the YK-edge by X-ray absorption spectroscopy in the temperature range from 300 to 1273 K. The temperature dependence of the extended X-ray absorption fine structure was successfully interpreted using classical molecular dynamics and a novel reverse Monte Carlo method, coupled with the evolutionary algorithm. The obtained results allowed the temperature dependence of the yttria atomic structure to be followed up to ∼6 Å and to validate two force-field models.
X-ray-absorption spectroscopy ofNd3+-exchanged β-alumina crystal
The results of x-ray-absorption spectroscopy investigations of ${\mathrm{Nd}}^{3+}$ ions in a nearly fully exchanged (93%) sodium \ensuremath{\beta}-alumina crystal are reported. The ${\mathrm{Nd}}^{3+}$ local environment is reconstructed using a multishell best fit procedure and is compared with existing structural models. The experimental extended x-ray-absorption fine-structure (EXAFS) spectra are also compared with model ab initio FEFF6 calculations based on the x-ray-diffraction data for the ${\mathrm{Nd}}^{3+}$ ions located at the BR(2d) and interstitial A(6h) sites of \ensuremath{\beta}-alumina. Neodymium ions are mainly found near the BR(2d) sites of the conduction plane, where they…
Double-Electron Excitations in L-edges X-ray-Absorption Spectra of W, Ir and Cs Oxide Compounds
Very strong double-electron excitations have been observed for the first time in the W, Ir L 3-edge and Cs L 1,2,3-edges X-ray-absorption spectra of tungsten and iridium oxide thin films and cesium oxide containing glasses. They are expressed as peaks with a width of several electron-volts located at the absorption background above the edge. The positions of these features are in good agreement with atomic calculations in the Z+1 approximation. They can be attributed to the transitions 2p4d → 5d5d for the L 2,3-edges and 2s4d → 6p5d for the L 1-edge with the dipole selection rules for the angular and total angular momentum ΔL=±1, ΔJ=0,±1.
Vacancy Defects in Ga2O3: First-Principles Calculations of Electronic Structure
This research was funded by the Science Committee of the Ministry of Education and Science of the Republic of Kazakhstan (Grant No. AP08856540) as well as by the Latvian research council via the Latvian National Research Program under the topic ?High-Energy Physics and Accelerator Technologies?, Agreement No: VPP-IZM-CERN-2020/1-0002 for A.I. Popov. In addition, J. Purans is grateful to the ERAF project 1.1.1.1/20/A/057 while A. Platonenko was supported by Latvian Research Council No. LZP-2018/1-0214. The authors thank A. Lushchik and M. Lushchik for many useful discussions. The research was (partly) performed in the Institute of Solid State Physics, University of Latvia ISSP UL. ISSP UL as…
First principles hybrid Hartree-Fock-DFT calculations of bulk and (001) surface F centers in oxide perovskites and alkaline-earth fluorides
Valuable discussions with E. A. Kotomin are gratefully acknowledged. Research contribution of R. E. and A. I. P. has been performed within the framework of the EUROfusion Enabling Research project: ENR-MFE19.ISSP-UL-02 “Advanced experimental and theoretical analysis of defect evolution and structural disordering in optical and dielectric materials for fusion applications.” The views and opinions expressed herein do not necessarily reflect those of the European Commission.
Amorphous p-Type Conducting Zn-x Ir Oxide (x > 0.13) Thin Films Deposited by Reactive Magnetron Cosputtering
Zinc-iridium oxide (Zn-Ir-O) thin films have been demonstrated as a p-type conducting material. However, the stability of p-type conductivity with respect to chemical composition or temperature is still unclear. In this study we discuss the local atomic structure and the electrical properties of Zn-Ir-O films in the large Ir concentration range. The films are deposited by reactive DC magnetron co-sputtering at two different substrate temperatures-without intentional heating and at 300 {\deg}C. Extended X-ray absorption fine structure (EXAFS) analysis reveals that strongly disordered ZnO4 tetrahedra are the main Zn complexes in Zn-Ir-O films with up to 67.4 at% Ir. As the Ir concentration in…
Changes in the local structure of nanocrystalline electrochromic films of hydrated nickel vanadium oxide upon ozone-induced coloration
Hydrated thin films of nickel vanadium oxide (Ni1−xVxOy), made by reactive DC magnetron sputtering, were studied by x-ray absorption spectroscopy at the Ni and V K-edges using synchrotron radiation. The XANES signals were analysed within the full-multiple-scattering formalism, whereas EXAFS data were modelled within the multi-shell multiple-scattering approach. We found that transparent films exhibit a nanocrystalline NiO-type structure with homogeneous distribution of V ions substituting Ni ions. Exposure of the films to ozone resulted in dark brown coloration associated with an appearance of Ni3+ ions and accompanied by a modification of the local electronic and atomic structures of the V…
Recent Achievement and Perspectives in Synchrotron Radiation X-Ray Absorption Spectroscopy
During the last 20 years, x-ray absorption spectroscopy (XAS) has found extensive application in the materials science [1, 2, 3]. solution chemistry [4], biology [5]. therapeutic chemistry [6] and geochemistry. However. it is relatively recently XAS methods have been utilized for measurements on archaeological materials [7,8].
Near-infrared luminescence of isolated and exchange-coupled Ni2+ ions in NicMg1−cO solid solutions
NicMg1−cO (0.01 ⩽ c ⩽ 1) solid solutions were studied by near-infrared luminescence, optical absorption and X-ray absorption spectroscopies. It was found that Ni2+ ions form at c < 0.2 the exchange-coupled pairs, strongly bound via 90 ° super-exchange interactions, and are displaced at c ⩽ 0.6 to the ‘off-center’ positions. This explains the origin of the zero-phonon line splitting observed in the optical absorption and luminescence spectra. It was also found that the effective energy transfer from the single Ni2+ ions to the exchange-coupled Ni2+-Ni2+ pairs occurs at temperatures below 40 K.
Structural, electrical and optical properties of zinc‐iridium oxide thin films deposited by DC reactive magnetron sputtering
ZnO-IrO2 thin films were deposited on glass by DC reactive magnetron sputtering at room tem-perature. Structural, electrical and optical properties were investigated as a function of iridium atomic concentra-tion in the films. XRD data shows that ZnO-IrO2 thin films are X-ray amorphous and Raman spectrum resembles the spectrum of IrO2, without any distinct features of wurtzite ZnO structure. The lowest film resistivity and the highest transmittance achieved in the present study were 1.4 × 10-3 Ωcm and 33% at 550 nm, respectively. However, resistivity and transmittance are inversely related to the iridium concentration in the films.
Short- and long-range order in La1−xSrxCoO3 and La1−xBaxCoO3
Abstract The short- and long-range order correlations of the crystal structure in the distorted perovskites La 1− x Sr x CoO 3 and La 1− x Ba x CoO 3 (0.0⩽ x ⩽0.5) have been studied by the neutron powder diffraction (NPD) and the Co K-edge X-ray absorption spectroscopy (XAS) measurements. The results of XAS and NPD indicate a local distortion around the Co 3+ ions in LaCoO 3 at room temperature. The substitution of the La 3+ ions by the Sr 2+ (Ba 2+ ) ions leads to a gradual increase of the Co–O–Co angle and is accompanied by an increase of the mean square relative displacement (MSRD) of the Co–O bond. These results correlate with an increase of the oxygen amplitude vibration in the directi…
Li intercalation in transparent Ti–Ce oxide films: Energetics and ion dynamics
Films of Ti dioxide, mixed Ti–Ce oxide, and Ce dioxide were produced by reactive dc magnetron sputtering. Electrochemical lithiation was probed by chronopotentiometry, cyclic voltammetry together with optical transmittance recording, and impedance spectroscopy. Evidence was found for inserted electrons being accommodated in Ce 4f states; this contention was supported by preliminary results from x-ray absorption fine-structure spectroscopy. These electrons do not produce luminous electrochromism. The variation of the chemical diffusion coefficient of Li, with film composition and Li content, was also studied.
Tribovoltaic Device Based on the W/WO3 Schottky Junction Operating through Hot Carrier Extraction
Characterization of rhenium oxide films and their application to liquid crystal cells
Rhenium trioxide exhibits high electronic conductivity, while its open cubic crystal structure allows an appreciable hydrogen intercalation, generating disordered solid phases, with protonic conductivity. Rhenium oxide thin films have been obtained by thermal evaporation of ReO3 powders on different substrates, maintained at different temperatures, and also by reactive magnetron sputtering of a Re metallic target. A comparative investigation has been carried out on these films, by using micro-Raman spectroscopy and x-ray diffraction. Two basic types of solid phases appear to grow in the films: a red metallic HxReO3 compound, with distorted perovskite structures, like in the bulk material, a…
X-ray absorption spectroscopy studies of the off-center Ni2+ions in Ni c Mg 1-c O solid solutions
In this work we present the x-ray absorption spectroscopy study of NicMg1-cO (0.01 <EQ c <EQ 1) solid solutions. The extended x-ray absorption fine structure (EXAFS) above the Ni K-edge was analyzed using the multi-shell fitting procedure. It was found that nickel ions are located in a distorted environment and shift upon dilution to the off- center positions. This fact follows from two main results: (1) in the first shell, the average Ni- O distance increases linearly upon dilution; (2) in the second shell, the average Ni-Ni distance remains unchanged and decreases slightly at low nickel concentration while the dependence of the Ni-Mg distance has a break at c approximately equals 0.6 and …
Local structure of A-atom in ABO3 perovskites studies by RMC-EXAFS
The measurements of Sr K-edge XAFS were performed under the approval of Proposal No. 97G042 of Photon Factory (KEK) and partially supported by the Research Grants of Hirosaki University. This work was supported by Bruce Ravel providing data for BTO. Boby Joseph acknowledges IISc Bangalore and ICTP Trieste for financial support through the award of the IISc-ICTP fellowship.
Reverse Monte Carlo modeling of thermal disorder in crystalline materials from EXAFS spectra
Abstract In this work we present the Reverse Monte Carlo (RMC) modeling scheme, designed to probe the local structural and thermal disorder in crystalline materials by fitting the wavelet transform (WT) of the EXAFS signal. Application of the method to the analysis of the Ge K-edge and Re L3-edge EXAFS signals in crystalline germanium and rhenium trioxide, respectively, is presented with special attention to the problem of thermal disorder and related phenomena.
Sputtering deposition and characterization of Ru-doped WO3 thin films for electrochromic applications
Mixed tungsten-ruthenium oxide thin films were prepared for the first time by dc magnetron co-sputtering technique and were studied by cyclic voltammetry, optical transmission measurements, Raman spectroscopy and the W L3 and Ru K edges X-ray absorption spectroscopy (XAS) in comparison with pure WO3 films. The Ru concentration was varied in the range from 0 to 28 at.%. XAS results suggest that the average local structure around both tungsten and ruthenium ions remains unchanged within experimental accuracy in all samples, moreover, for tungsten ions, it resembles that of pure WO3 films. However, the presence of the ruthenium ions affects the electrochemical and optical properties of the fil…
Hydrogen adsorption on the ZnO $(1\bar{1}00)$ surface: ab initio hybrid density functional linear combination of atomic orbitals calculations
Hydrogen atoms unavoidably presented in ZnO samples or thin films during their synthesis considerably affect electrical conductivity. Results of first principles hybrid functional linear combination of atomic orbitals calculations are discussed for hydrogen atoms incorporated in bulk or adsorbed upon non-polar ZnO (1¯ 100) surfaces. The energy of H incorporation, atomic relaxation, electronic density redistribution and modification of the electronic structure are compared for both surface adsorption and bulk absorption. It is shown that hydrogen forms a strong bonding with the surface O ions (Eads = 2.7eV) whereas its incorporation into bulk is energetically quite unfavorable. Hydrogen adso…
Structure and composition of sputter-deposited nickel-tungsten oxide films
Films of mixed nickel-tungsten oxide, denoted NixW1-x oxide, were prepared by reactive DC magnetron co-sputtering from metallic targets and were characterized by Rutherford backscattering spectrometry. X-ray photoelectron spectroscopy, X-ray diffractometry and Raman spectroscopy. A consistent picture of the structure and composition emerged, and at x<0.50 the films comprised a mixture of amorphous WO3 and nanosized NiWO4, at x = 0.50 the nanosized NiWO4 phase was dominating, and at x>0.50 the films contained nanosized NiO and NiWO4.
Theoretical and Experimental Studies of Charge Ordering in CaFeO 3 and SrFeO 3 Crystals
<title>Scanning probe microscopy of nanocrystalline iridium oxide thin films</title>
Structural investigations of nanocrystalline iridium oxide thin films, prepared by dc magnetron sputtering technique were performed by scanning probe microscopy (SPM). SPM studies, using both atomic force microscopy (AFM) and scanning tunnelling microscopy (STM), indicate that the thin films are composed of grains with a size of about 20-50 nm. Fine crystallinity and small RMS microroughness of the films, being well below 2 nm, make iridium oxide thin films promising candidates for nanolithographic applications. The possibility to perform nanolithograhpic processes at a scale of less than 150 nm was successfully examined in AFM and STM modes.© (2003) COPYRIGHT SPIE--The International Societ…
Raman, electron microscopy and electrical transport studies of x-ray amorphous Zn-Ir-O thin films deposited by reactive DC magnetron sputtering
Zn-Ir-O thin films on glass and Ti substrates were deposited by reactive DC magnetron sputtering at room temperature. Structural and electrical properties were investigated as a function of iridium concentration in the films. Raman spectrum of Zn-Ir-O (61.5 at.% Ir) resembles the spectrum of rutile IrO2, without any distinct features of wurtzite ZnO structure. SEM images indicated that morphology of the films surface improves with the iridium content. EDX spectroscopy and cross-section SEM images revealed that the films growing process is homogeneous. Crystallites with approximately 2-5 nm size were discovered in the TEM images. Thermally activated conductivity related to the variable range…
Understanding the Conversion Process of Magnetron-Deposited Thin Films of Amorphous ReO$_x$ to Crystalline ReO$_3$ upon Thermal Annealing
Crystal growth & design 20(9), 6147 - 6156 (2020). doi:10.1021/acs.cgd.0c00848
Nanoscale x-ray absorption spectroscopy using XEOL-SNOM detection mode
The first results obtained with the prototype system at the synchrotron beamline ID03 at ESRF are presented and illustrate the possibility to detect an element-specific contrast and to perform nanoscale x-ray absorption spectroscopy experiments at the Zn K and W L 3 absorption edges in mixed zinc oxide-zinc tungstate thin films.
Comparative Hybrid Hartree-Fock-DFT Calculations of ReO3, SrTiO3, BaTiO3, PbTiO3 and CaTiO3 (001) Surfaces
Local Structure Studies of Ti for SrTi16O3 and SrTi18O3 by Advanced X-ray Absorption Spectroscopy Data Analysis
Strontium titanate is a model quantum paraelectric in which in the region of dominating quantum statistics the ferroelectric instability is inhibited due to nearly complete compensation of the harmonic contribution into ferroelectric soft mode frequency by the zero-point motion contribution. The enhancement of atomic masses by the substitution of 18O for 16O decreases the zero-point atomic motion and low-T ferroelectricity in SrTi18O3 is realized. In this study we report on the local structure of Ti in SrTi16O3 and SrTi18O3 by Ti K-edge extended x-ray absorption fine structure measurements in temperature range 6 – 300 K.
Unraveling the Structure and Properties of Layered and Mixed ReO3–WO3 Thin Films Deposited by Reactive DC Magnetron Sputtering
Tungsten trioxide (WO3) is a well-known electrochromic material with a wide band gap, while rhenium trioxide (ReO3) is a “covalent metal” with an electrical conductivity comparable to that of pure metals. Since both WO3 and ReO3 oxides have perovskite-type structures, the formation of their solid solutions (ReO3–WO3 or RexW1–xO3) can be expected, which may be of significant academic and industrial interest. In this study, layered WO3/ReO3, ReO3/WO3, and mixed ReO3–WO3 thin films were produced by reactive DC magnetron sputtering and subsequent annealing in air at 450 °C. The structure and properties of the films were characterized by X-ray diffraction, optical spectroscopy, Hall conductivity…
FIRST-PRINCIPLES LCAO CALCULATIONS ON 5D TRANSITION METAL OXIDES: ELECTRONIC AND PHONON PROPERTIES
ABSTRACT First-principles quantum chemistry calculations within the periodic linear combination of atomic orbitals (LCAO) formalism have been used to probe electronic and phonon properties of crystalline 5d transition metal oxides ReO3, ZnWO4 and CaWO4. The obtained equilibrium crystal structure is in good agreement with known crystallographic data. Rhenium trioxide is correctly predicted to be a metal, whereas both tungstates—a wide gap insulating compounds. The phonon frequencies, calculated by the frozen phonon method, agree rather well with those obtained by infrared and Raman spectroscopies.
Comparative Hybrid Hartree-Fock-DFT Calculations of WO2-Terminated Cubic WO3 as Well as SrTiO3, BaTiO3, PbTiO3 and CaTiO3 (001) Surfaces
We greatly acknowledge the financial support via the ERAF Project No. 1.1.1.1/18/A/073. Calculations were performed using Latvian Super Cluster (LASC), located in the Center of Excellence at Institute of Solid State Physics, the University of Latvia, which is supported by European Union Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-Teaming Phase 2 under Grant Agreement No. 739508, project CAMART.
Influence of the focusing effect on XAFS in ReO3, WO3−x and FeF3
Abstract The role of the focusing effect in the formation of X-ray absorption fine structure (XAFS) is considered for ReO3, non-stoichiometric tungsten oxides WO3−x and FeF3 having the perovskite-type structure. Two cases are mainly discussed: (1) an admixture of rhenium and tungsten L2-edge XAFS in ReO3 and WO3−x crystals to the one above rhenium and tungsten L1-edge and (2) high-order superfocusing effect in Fe0F1Fe2F3Fe4 atomic chain in iron K-edge XAFS of FeF3 which is analysed using an ab initio multiple-scattering approach.
Ab initio molecular dynamics simulations of the Sc K-edge EXAFS of scandium trifluoride
Scandium fluoride ScF3 has a simple cubic structure and attracts attention due to its large negative thermal expansion (NTE) over a wide range of temperatures (0-1100 K). In this study we present ab initio molecular dynamics (AIMD) simulations of ScF3 and their validation using the Sc K-edge EXAFS spectra in the temperature range from 300 K to 1000 K measured at the XAFS beamline of ELETTRA. The obtained results allow an assessement of the employed AIMD model and provide insight into the local structure and the lattice dynamics of ScF3 beyond the harmonic approximation. A strong anisotropy of the fluorine atom vibrations in the direction orthogonal to the -Sc-F-Sc- chain is observed. An exp…
Ab Initio Computations of O and AO as well as ReO2, WO2 and BO2-Terminated ReO3, WO3, BaTiO3, SrTiO3 and BaZrO3 (001) Surfaces
This research received funding from the Latvian-Ukraine cooperation Project No. LV/UA-2021/5. The Institute of Solid State Physics, University of Latvia (Latvia), as the Centre of Excellence, has received funding from the European Unions Horizon 2020 Framework Programme H2020-WIDESPREAD01-2016-2017-Teaming Phase2 under Grant Agreement No. 739508, project CAMART2.
Low-temperature luminescence of ScF3 single crystals under excitation by VUV synchrotron radiation
The work was supported by the Latvian Science Council grant LZP-2018/2-0358. The research leading to this result has also been supported by the project CALIPSO plus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. The author is grateful to K. Chernenko (MAX IV Laboratory, Lund University) for his assistance during beamtime experiments and to A. I. Popov for the fruitful discussions. V.P. also acknowledges Valsts pētījumu programma “Augstas enerģijas fizika un paātrinātāju tehnoloģijas” (Projekta Nr. VPP-IZM-CERN-2020/1-0002). REFERENCES
Atomic and electronic structure of hydrogen on ZnO (11̄00) surface: ab initio hybrid calculations
Hydrogen atoms unavoidably incorporated into ZnO during growth of bulk samples and thin films considerably affect their electrical conductivity. The results of first principles hybrid LCAO calculations are discussed for hydrogen atoms in the bulk and on the non-polar ZnO (100) surface. The incorporation energy, the atomic relaxation, the electronic density redistribution and the electronic structure modifications are compared for the surface adsorption and bulk interstitial H positions. It is shown that hydrogen has a strong binding with the surface O ions (2.7 eV) whereas its incorporation into bulk is energetically unfavorable. Surface hydrogen atoms are very shallow donors, thus, contrib…
XAFS study of short range order in the heavily disordered MoxW1−wO3 oxides
We have done comparative XAFS analysis on the MoK and WL 3 edges of polycrystalline Mo x W 1-x O 3 solid solutions. It was found that their structures are closely related to corner-shared WO 3 -type for x<0.9 while α-MoO 3 -type structure is present for x≥0.9. The obtained structural parameters for the first shell around metal ions allow to distinguish several structural phase transitions due to the change of composition. A set of subshells within the first shell was found, and they are in good agreement with Raman data
EXAFS Study of PressureInduced Phase Transition in SrWO4
Pressure-induced scheelite-to-wolframite structural phase transition in SrWO4 was studied using two complementary techniques—x-ray absorption spectroscopy and x-ray diffraction (XRD). In situ XRD and W L3-edge EXAFS measurements were performed using the synchrotron radiation. The experiments were done at room temperature in the pressure range from 0 to 30 GPa using the diamond anvil cell. The XRD results unambiguously show that SrWO4 transforms from the tetragonal scheelite phase to the monoclinic wolframite-type phase at about 11.7 GPa. Locally this transition appears as a change of the tungsten ions coordination from regular tetrahedral to distorted octahedral. The analysis of the EXAFS d…
ODS steel raw material local structure analysis using X-ray absorption spectroscopy
Oxide dispersion strengthened (ODS) steels are promising materials for fusion power reactors, concentrated solar power plants, jet engines, chemical reactors as well as for hydrogen production from thermolysis of water. In this study we used X-ray absorption spectroscopy at the Fe and Cr K-edges as a tool to get insight into the local structure of ferritic and austenitic ODS steels around Fe and Cr atoms and its transformation during mechanical alloying process. Using the analysis of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) we found that for austenitic samples a transformation of ferritic steel to austenitic steel is detectable after …
EXAFS and XANES Studies of CoxMg1−xO Solid Solutions Using a Laboratory EXAFS Spectrometer
Studies of the local electronic structure and the short-range order in solid solutions CoxMg1−xO with x varying from 0.02 to 1.00 are carried out on the CoK-edge X-ray absorption spectra using a laboratory EXAFS spectrometer. A non-monotonous change of the CoO distance in the first coordination shell with a bent at about x = 0.5 is established. The second coordination shell of cobalt is formed by cobalt and magnesium atoms with a distribution close to a statistical one. [Russian Text Ignored.]
XAFS study of gadolinium and samarium bisporphyrinate complexes.
The comparative X-ray absorption spectroscopy study of gadolinium and samarium bisporphyrinate complexes represented by the formulas Gd(III)H(oep)(tpp), Gd(III)(oep)(2), Gd(III)H(tpp)(2) and Sm(III)H(oep)(tpp), Sm(III)(oep)(2), Sm(III)H(tpp)(2) is reported. The XAFS spectra are recorded on the LURE-DCI storage ring (Orsay, France) in transmission mode on the microcrystalline samples at the Gd and Sm L(3) edges. The local environment for Ln(3+) ions has been reconstructed applying one-shell and two-shell XAFS analysis procedures. The protonated and nonprotonated bisporphyrinate complexes present different XAFS features. After our analysis on the title derivatives, the gadolinium ion (at 80 K…
The effect of Zn vacancies and Ga dopants on the electronic structure of ZnO:Ab initiosimulations
Zinc oxide modied by metal dopants can be used as a low-cost material for production of transparent conducting lms. Its optical and electronic properties vary with the type and the concentration of dopants. In this study we have performed rst-principle calculations on ZnO with Zn vacancies and that with Ga dopants in wurtzite type hexagonal morphology using density functional theory approach. Dependence of the electronic properties on the concentration of dopants has been studied using supercells of dierent sizes.
Ab initio molecular dynamics simulations of negative thermal expansion in ScF3: the effect of the supercell size
The authors sincerely thank S. Ali, A. Kalinko, and F. Rocca for providing experimental EXAFS data, as well as M. Isupova, V. Kashcheyevs, and A. I. Popov for stimulating discussions. Financial support provided by project No. 1.1.1.2/VIAA/l/16/147 (1.1.1.2/16/I/001) under the activity “Post-doctoral research aid” realized at the Institute of Solid State Physics, University of Latvia is greatly acknowledged by D.B. A.K and J.P. would like to thank the support of the Latvian Council of Science project No. lzp-2018/2–0353.
Nanosession: Valence Change Memories - A Look Inside
The local atomic structure and thermoelectric properties of Ir-doped ZnO: hybrid DFT calculations and XAS experiments
We greatly acknowledge the financial support via the ERAF Project No. 1.1.1.1/18/A/073. Calculations have been performed under the Project HPC-EUROPA3 (INFRAIA-2016-1-730897), with the support of the EC Research Innovation Action under the H2020 Programme. A. C. gratefully acknowledges the technical support received from KTH-PDC. Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART2
<title>In-situ x-ray absorption fine structure and x-ray diffraction studies of hydrogen intercalation in tungsten oxides</title>
We present in-situ x-ray absorption fine structure (XAFS) (at the W L 3 -edge) and x-ray diffraction (XRD) studies of hydrogen intercalation into stable monoclinic (m-WO 3 ) and metastable hexagonal (h-WO 3 ) and cubic (c-WO 3 ) phases of tungsten oxide. The analysis of XAFS and XRD data allowed us to reconstruct the local environment around tungsten ions in the first coordination shell. The obtained results are compared with the existing structural models.
Systematic trends in YAlO3, SrTiO3, BaTiO3, BaZrO3 (001) and (111) surface ab initio calculations
We greatly acknowledge the financial support via Latvian-Ukrainian Joint Research Project No. LV-UA/2018/2, Latvian Council of Science Grant No. 2018/2-0083 “Theoretical prediction of hybrid nanostructured photocatalytic materials for efficient water splitting”, Latvian Council of Science Grant No. 2018/1-0214 as well as ERAF Project No. 1.1.1.1/18/A/073.
Interpretation of unexpected behavior of infrared absorption spectra ofScF3beyond the quasiharmonic approximation
Scandium fluoride (${\mathrm{ScF}}_{3}$), having cubic ${\mathrm{ReO}}_{3}$-type structure, has attracted much scientific attention due to its rather strong negative thermal expansion (NTE) in the broad temperature range from 10 to 1100 K. Here we use the results of diffraction and extended x-ray absorption fine-structure (EXAFS) spectroscopy to interpret the influence of NTE on the temperature dependence of infrared absorption spectra of ${\mathrm{ScF}}_{3}$. Original infrared absorption and EXAFS experiments in a large temperature range are presented and interpreted using ab initio lattice dynamics simulations within and beyond quasiharmonic approximations. We demonstrate that ab initio e…
Local structure of perovskites ReO3and ScF3with negative thermal expansion: interpretation beyond the quasiharmonic approximation
We propose an approach beyond the quasiharmonic approximation for interpretation of EXAFS and XRD data and for ab initio calculations of electronic and vibration properties of materials with negative thermal expansion. Ab initio electronic structure and lattice dynamics calculations for cubic and distorted ScF3 were performed using the linear combination of atomic orbitals (LCAO) method. The band gap obtained in calculations for ScF3 is equal to 10.54 eV and agree well with the expected value. The calculated infrared spectra of F displaced (FD) cubic ScF3 allow us to predict that its mean Sc-F-Sc angle within NTE deviates from 180 degree.
Changes in structure and conduction type upon addition of Ir to ZnO thin films
Zn-Ir-O (Zn/Ir ≈ 1/1) thin films have been reported to be a potential p-type TCO material. It is, however, unknown whether it is possible to achieve p-type conductivity at low Ir content, and how the type and the magnitude of conductivity are affected by the film structure. To investigate the changes in properties taking place at low and moderate Ir content, this study focuses on the structure, electrical and optical properties of ZnO:Ir films with iridium concentration varying between 0.0 and 16.4 at.%. ZnO:Ir thin films were deposited on glass, Si, and Ti substrates by DC reactive magnetron co-sputtering at room temperature. Low Ir content (up to 5.1 at.%) films contain both a nano-crysta…
<title>X-ray absorption spectroscopy study of the local environment around tungsten and molybdenum ions in tungsten-phosphate and molybdenum-phosphate glasses</title>
X-ray absorption spectroscopy (XAS) was used to study the local environment around tungsten and molybdenum ions in BaO-P2O5-WO3 and CaO-P2O5-MoO3 glasses having different composition of WO3 and MoO3 oxides. The W L1,3 and Mo K edges x-ray absorption spectra were measured in transmission mode at room temperature using the synchrotron radiation emitted by the ADONE and LURE DCI storage rings, respectively. The analysis of x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) in glasses was performed in comparison with the results for a number of crystalline WO3, CaWO4, Na0.66WO3 alpha- MoO3, beta-MoO3 and amorphous a-WO3, a-MoO3 compounds. The resul…
X-ray absorption study of the electronic structure of tungsten and molybdenum oxides on the O K-edge
Magnetron sputtered amorphous thin films a-WO3, a-MoO3 and doped a-WO3:Ir have been studied by X-ray absorption spectroscopy on the oxygen K-edge in comparison with crystalline oxides as monoclinic m-WO3, orthorhombic α-MoO3, cubic Na0.6WO3, layered-type hexagonal h-WO3 and WO3·H2O, having variable electronic and atomic structure. The changes in the XANES ranging 10–15 eV above the absorption edge are interpreted based on the known band-structure calculations. The high-energy features are related to the multiple-scattering processes (EXAFS) at the nearest atoms.
Femtometer accuracy EXAFS measurements: Isotopic effect in the first, second and third coordination shells of germanium
The analysis of the EXAFS signals from 70Ge and 76Ge has evidenced the low-temperature effect of isotopic mass difference on the amplitude of relative atomic vibrations. This effect is reflected in the difference of the Debye-Waller factors of the first three coordination shells, and on the difference of nearest-neighbour average interatomic distances, evaluated with femtometer accuracy. The experimental results are in agreement with theoretical expectations.
Confocal spectromicroscopy of amorphous and nanocrystalline tungsten oxide films
A Raman confocal spectromicroscopic system was used to study in situ phase composition and surface morphology in amorphous and nanocrystalline tungsten oxide and tungstate thin films, prepared on silicon and glass substrates by dc magnetron co-sputtering technique. The possible use of these films for the phase-change optical recording was demonstrated using 442 nm He–Cd laser with a variable power of up to 50 mW. The formation of nanocrystalline tungsten trioxide or tungstate phases was observed under the laser irradiation. These nanocrystalline phases show relatively strong Raman activity, which can be used for information reading purposes. A multilayer structure composed of several tungst…
ODS ferritic steels obtained from gas atomized powders through the STARS processing route: Reactive synthesis as an alternative to mechanical alloying
Authors acknowledge ALBA synchrotron (Spain) for the provision of beamtime on the beam line BL22-CLAESS (Proposal 2016081797). Transmission electron microscopy observations were accomplished at Centro Nacional de Microscopía Electrónica, CNME-UCM. This work has been carried out within the framework of the EUROfusion Consortium and has received funding from the Euratom research and training programme 2014–2018 under grant agreement No 633053. The views and opinions expressed herein do not necessarily reflect those of the European Commission. Financial support from Basque Government through the ELKARTEK ACTIMAT 2016 project is also acknowledged.
Spectroscopic study of the electric field induced valence change of Fe-defect centers in SrTiO(3)
The electrochemical changes induced by an electric field in Fe-doped SrTiO(3) have been investigated by X-ray absorption spectroscopy (XANES and EXAFS), electron paramagnetic resonance (EPR) and Raman spectroscopy. A detailed study of the Fe dopant in the regions around the anode and cathode reveals new insights into the local structure and valence state of Fe in SrTiO(3) single crystals. The ab initio full multiple-scattering XANES calculations give an evidence of the oxygen vacancy presence in the first coordination shell of iron. Differences in the length and disorder of the Fe-O bonds as extracted from EXAFS are correlated to the unequivocal identification of the defect type by compleme…
In situ XAFS study of phase transitions and hydrogen intercalation in WO3-MoO3 system
Abstract The WO 3 -MoO 3 system has several reconstructive and displacive phase transitions which can be induced by temperature and/or by change of stoichiometry or valence state of metal ions under hydrogen intercalation. We have studied in situ the local electronic and structural changes arising in WO 3 -MoO 3 system with hydrogen intercalation and temperature. In situ XAFS measurements at the Mo K and W L 3 edges in H y Mo x W 1− x O 3 compounds, performed at different hydrogen intercalation level and temperatures (from RT to 500°C), allowed us to determine the rearrangement in the first and second coordination shells of Mo and W cations during phase transitions. It was found that hydrog…
Comparative Ab Initio Calculations of ReO3, SrZrO3, BaZrO3, PbZrO3 and CaZrO3 (001) Surfaces
We performed, for first time, ab initio calculations for the ReO2-terminated ReO3 (001) surface and analyzed systematic trends in the ReO3, SrZrO3, BaZrO3, PbZrO3 and CaZrO3 (001) surfaces using first-principles calculations. According to the ab initio calculation results, all ReO3, SrZrO3, BaZrO3, PbZrO3 and CaZrO3 (001) surface upper-layer atoms relax inwards towards the crystal bulk, all second-layer atoms relax upwards and all third-layer atoms, again, relax inwards. The ReO2-terminated ReO3 and ZrO2-terminated SrZrO3, BaZrO3, PbZrO3 and CaZrO3 (001) surface band gaps at the &Gamma
Interpretation of EXAFS in ReO3using molecular dynamics simulations
Temperature dependent Re L3-edge EXAFS signals from perovskite-type cubic ReO3 have been successfully interpreted using a combination of classical NVT molecular dynamics (MD) and ab initio multiple-scattering approach. The force field model, required for MD simulations, has been determined by fitting the Re-O and O-O pairwise interatomic potentials to a set of experimental data (lattice parameter, elastic constants and bulk modulus) and phonon frequencies, theoretically calculated from the first principles at high symmetry points of the Brillouin zone. The MD simulations reproduce well the anisotropy of thermal vibration for oxygen atoms and confirm a deviation of the mean Re-O-Re angle fro…
XAFS analysis of the low symmetry octahedral molybdenum and tungsten oxides
Abstract Comparative XAFS analysis of the main isostructural crystalline phases of W(Mo)O3 oxides and W(Mo)O3·nH2O hydrates has been done at the W L3 and Mo K edges. These compounds have (1) 3D perovskite-type (PT) structure (m-WO3); (2) 2D PT structure (WO3·H2O and MoO3·nH2O (n = 1,2)); (3) 2D hexagonal-type structure (WO3·1/3H2O) and (4) 2D double layered structure (α-MoO3). The detailed analysis of X-ray absorption fine structure (XAFS) in the low-symmetry structures shows that in order to simulate the experimental spectrum, it is sufficient to take into account single-scattering contributions in the range from 1.7 to ∼ 5.0 A and a number of multiple-scattering paths from nearly linear a…
Electronic structure of cubic ScF$_3$ from first-principles calculations
The first-principles calculations have been performed to investigate the ground state properties of cubic scandium trifluoride (ScF$_3$) perovskite. Using modified hybrid exchange-correlation functionals within the density functional theory (DFT) we have comprehensively compared the electronic properties of ScF$_3$ obtained by means of the linear combination of atomic orbitals (LCAO) and projector augmented-waves (PAW) methods. Both methods allowed us to reproduce the lattice constant experimentally observed in cubic ScF$_3$ at low temperatures and predict its electronic structure in good agreement with known experimental valence-band photoelectron and F 1$s$ X-ray absorption spectra.
Analysis of the U L3-edge X-ray absorption spectra in UO2 using molecular dynamics simulations
This work was supported by a grant from the Swiss National Supercomputing Centre (CSCS) under the project ID s444. The resource allocation within the PSI share at CSCS and on the PSI compute cluster Merlin4 is also acknowledged. D. B. is grateful for a fellowship within the Sciex-NMS programme. A. K. was supported by Latvian Science Council Grant no. 187/2012.
Local Environment of Co2+ Ions in β″-Alumina Crystals
Local dynamics and phase transition in quantum paraelectric SrTiO3 studied by Ti K-edge x-ray absorption spectroscopy
Strontium titanate is a model quantum paraelectric in which, in the region of dominating quantum statistics, the ferroelectric instability is inhibited due to nearly complete compensation of the harmonic contribution into ferroelectric soft mode frequency by the zero- point motion contribution. The enhancement of atomic masses by the substitution of 16 O with 18O decreases the zero-point atomic motion, and low-T ferroelectricity in SrTi18O3 is realized. In this study we report on the local structure of Ti in SrTi16O3 and SrTi18O3 investigated by Extended X-ray Absorption Fine Structure measurements in the temperature range 6 - 300 K.
XAFS STUDIES OF OCTAHEDRAL AMORPHOUS OXIDES
The relationships between the structures of octahedral and tetrahedral amorphous oxides, studied by XAFS spectroscopy, are considered. It was found that a-WO3, a-MoO3, a-V2O5 thin films and glasses have strongly distorted, but well defined, oxygen octahedra, which are joined by vertices (a-WO3, a-MoO3) or by vertices and edges (a-V2O5), and form a random network. At the same time, a-IrO2 and a-NiO have less distorted oxygen octahedra, which form the rutile type and rock salt type nanocrystalline structures. The variation of the structure with the change of the metal valence is considered and the possibility of small radius polaron detection by XAFS is discussed.
Local electronic structure rearrangements and strong anharmonicity in YH3 under pressures up to 180 GPa
The authors acknowledge the ESRF program committee (Grenoble, France) for the opportunity to perform XAFS and XRD measurements. We are grateful to Prof. Dr Marek Tkacz from the Institute of Physical Chemistry, PAS Kasprzaka 44/52, 01-224 Warsaw, Poland, for high quality YH3 samples and to Dr. José A. Flores-Livas for a fruitful discussion. A.P.M. and A.A.I. acknowledge the Russian Foundation for the Basic Research (grant No 18-02-40001_mega) for financial support. J.P., A.K., and I.P. would like to thank the support of the Latvian Council of Science project No. lzp-2018/2-0353. ISSP UL acknowledge the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-20l 6-2017-TeamingPh…
X-ray-absorption study of rheniumL3andL1edges inReO3: Multiple-scattering approach
We present ab initio calculations of x-ray-absorption fine structure for the Re L 3 and L 1 edges in crystalline ReO 3 based on an exact curved-wave multiple-scattering approach. Good agreement between theoretical and experimental data has been found for both edges. We show that, as expected, the contribution of multiple-scattering signals from linear chains, like Re-O-Re and O-Re-O, is very large both in the L 3 - and L 1 -edge spectra due to the strong focusing effect caused by the middle atom
A high-temperature x-ray absorption spectroscopy study of
We present for the first time a high-temperature x-ray absorption spectroscopy study of at the edge. The analysis both of the XANES and of the EXAFS regions shows that, in , a progressive localization of the 5d states following the temperature rise is accompanied at T > 350 K by a distortion of the octahedra, which increases up to the decomposition temperature . The distortion leads to the lowering of the rhenium site symmetry from and is due to the electron - phonon coupling of the 5d electrons with the and phonons and to the Jahn - Teller effect caused by the rhenium electron which becomes localized at high temperature.
Studies of CoxMg1-xO Solid Solutions Using Laboratory EXAFS-Spectrometer
Studies of the local electronic structure and the short-range order in solid solutions Co x Mg1-x O with x equal from 0.02 to 1.00 have been carried out on the Co K-edge X-ray absorption spectra measured using the laboratory EXAFS-spectrometer. A non-monotonous change of the Co-O distance in the first coordination shell with the bent at x=0.5 has been established. The second coordination shell of cobalt has been formed by cobalt and magnesium atoms with a distribution close to statistical.
Optical properties of zinc-iridium oxide thin films
We present the results of an investigation of ultraviolet, visible, near-infrared (UV-Vis-NIR) and X-ray absorption spectroscopy absorption spectra for zinc-iridium oxide (Zn-Ir- O) thin films with various iridium concentrations deposited by reactive DC magnetron sputtering. It is found that the absorption spectra of zinc-iridium oxide thin films contain a broad band with maxima at 446 nm and 710 nm in the visible region, bands with maxima at about 1100 nm and 3300 nm, and a low-intensity absorption band at 1570 nm in the near-infrared region. The obtained absorption bands are associated with iridium ions at valences of Ir3+, Ir4+ and Ir5+. Changes in the oxidation state of iridium ions fro…
XAFS studies of local atomic structure of niobium tellurides
Abstract We present XAFS (K-edge) studies of the local atomic structure around the Nb and Te ions in niobium tellurides (NbTe 2 , Nb 3 Te 4 and NbTe 4 ) in comparison with ZrTe 2 . Using a multi-shell best-fit analysis procedure, we have reconstructed local environments of the Nb and Te ions and compared them with the existing structural models. We found that at the Nb K-edge the XAFS data of NbTe 4 are extremely sensitive to metal clustering and to the subsequent departure from the average crystallographic positions. Moreover, at the Te K-edge the XAFS data allowed us to distinguished the different type of TeTe bonds, for instance: the dimer (TeTe: 2.9 A) and the squares (TeTe: 3.3 A) i…
A new tool for nanoscale X-ray absorption spectroscopy and element-specific SNOM microscopy.
Abstract Investigations of complex nanostructured materials used in modern technologies require special experimental techniques able to provide information on the structure and electronic properties of materials with a spatial resolution down to the nanometer scale. We tried to address these needs through the combination of X-ray absorption spectroscopy (XAS) using synchrotron radiation microbeams with scanning near-field optical microscopy (SNOM) detection of the X-ray excited optical luminescence (XEOL) signal. The first results obtained with the prototype instrumentation installed at the European Synchrotron Radiation Facility (Grenoble, France) are presented. They illustrate the possibi…
Enhanced Reflectivity Change and Phase Shift of Polarized Light: Double Parameter Multilayer Sensor
Herein, the concept of point of darkness based on polarized light phase difference and absorption of light is demonstrated by simulations using low refractive index and extinction coefficient semiconductor and dielectric, and high refractive index nonoxidizing metal multilayer thin film structures. Several multilayer sensor configurations show great sensitivity to thickness and refractive index variation of the detectable material by measuring the reflectivity ratio {\Psi} and phase shift {\Delta}. Focus is on such multilayers, which have sensitivity to both parameters ({\Psi}, {\Delta}) in the visible spectral range, thus opening the possibility for further research on a new biomedical sen…
Systematic Trends in Hybrid-DFT Computations of BaTiO3/SrTiO3, PbTiO3/SrTiO3 and PbZrO3/SrZrO3 (001) Hetero Structures
We acknowledge the financial support from the funder—Latvian Council of Science. The funding number is: Grant No. LZP-2020/1-0345. The Institute of Solid State Physics, University of Latvia (Latvia), as the Centre of Excellence, has received funding from the European Unions Horizon 2020 Framework Programme H2020-WIDESPREAD01-2016-2017-Teaming Phase2 under Grant Agreement No. 739508, project CAMART-2.