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…

Low temperature X-ray absorption spectroscopy study of $CuMoO_{4}$ and $CuMo_{0.90}W_{0.10}O_4$ using reverse Monte-Carlo method

Radiation physics and chemistry 175, 108411 (2020). doi:10.1016/j.radphyschem.2019.108411

Disorder-induced Raman scattering in rhenium trioxide (ReO3)

Raman scattering in cubic metallic perovskite (ReO3) was studied at room temperature for well-crystallized monolith, polycrystalline powder and thin film samples. Defect-induced first-order Raman scattering was detected from the sub-surface region, given by the penetration depth of a 633 nm laser, and its origin was explained on the basis of a rigid-ion vibrational model for bulk ReO3. A quenching of the Raman intensity was observed in crystalline monolithic ReO3 upon increasing the temperature up to 250 °C and was related to crystal surface reconstruction/annealing.

Atomistic simulations of the FeK-edge EXAFS in FeF3using molecular dynamics and reverse Monte Carlo methods

Atomistic simulations of the experimental Fe K-edge extended x-ray absorption fine structure (EXAFS) of rhombohedral (space group ) FeF3 at T = 300 K were performed using classical molecular dynamics and reverse Monte Carlo (RMC) methods. The use of two complementary theoretical approaches allowed us to account accurately for thermal disorder effects in EXAFS and to validate the developed force-field model, which was constructed as a sum of two-body Buckingham-type (Fe–F and F–F), three-body harmonic (Fe–F–Fe) and Coulomb potentials. We found that the shape of the Fe K-edge EXAFS spectrum of FeF3 is a more sensitive probe for the determination of potential parameters than the values of stru…

Adsorption of Rare Earth Elements onto DNA-Functionalized Mesoporous Carbon.

The recovery and separation of rare earth elements (REEs) are of national importance owing to the specific usages, high demand, and low supply of these elements. In this research, we have investigated the adsorption of rare earth elements onto DNA-functionalized mesoporous carbons with a BET surface area of 605 m2/g and a median mesopore width of 48 A. Three types of single-stranded DNA, one with 100 base units of thymine, another with 20 units of thymine, and the third, a 2000 unit long DNA from salmon milt were grafted on the carboxylated mesoporous carbon surface. All of the DNA-functionalized mesoporous carbons demonstrated higher adsorption of REEs compared to pristine mesoporous carbo…

<title>Quantum chemistry studies of the O K-edge x-ray absorption in WO<formula><inf><roman>3</roman></inf></formula> and AWO<formula><inf><roman>3</roman></inf></formula></title>

In this work we present an interpretation of experimental O K-edge x-ray absorption near edge structure (XANES) in perovskite-type WO3 and AWO3 compounds (A = H and Na) using three different first principles approaches: (i) fullmultiple- scattering (FMS) formalism (the real-space FEFF code), (ii) hybrid density functional theory (DFT) method with partial incorporation of exact Hartree-Fock exchange using formalism of the linear combination of atomic orbitals (LCAO) as implemented in the CRYSTAL code; (iii) plane-wave DFT method using formalism of the projectoraugmented waves (PAW) as implemented in the VASP code.

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.

Revealing the local structure of CuMo1−xWxO4 solid solutions by multi-edge X-ray absorption spectroscopy

I.P. and A.K. would like to thank the support of the Latvian Council of Science project No. lzp-2019/1-0071. I.P. acknowledges the L’OREAL Baltic “For Women In Science Program” with the support of the Latvian National Commission for UNESCO and the Latvian Academy of Sciences. The experiment at the Elettra synchrotron was performed within project No. 20150303. 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.

Extended x-ray absorption fine structure spectroscopy and first-principles study of SnWO4

The local atomic structure in α- and β-SnWO 4 was studied bysynchrotron radiation W L 3 -edge X-ray absorption spectroscopy at 10 and 300 K.Strongly distorted WO 6 octahedra were found in α-SnWO 4 , whereas nearly regularWO 4 tetrahedra were observed in β-SnWO 4 , confirming previous results. Thestructural results obtained were supported by the first-principles calculations,suggesting that the second-order Jahn-Teller effect is responsible for octahedraldistortion.

Study of High-Temperature Behaviour of ZnO by Ab Initio Molecular Dynamics Simulations and X-ray Absorption Spectroscopy

Wurtzite-type zinc oxide (w-ZnO) is a widely used material with a pronounced structural anisotropy along the c axis, which affects its lattice dynamics and represents a difficulty for its accurate description using classical models of interatomic interactions. In this study, ab initio molecular dynamics (AIMD) was employed to simulate a bulk w-ZnO phase in the NpT ensemble in the high-temperature range from 300 K to 1200 K. The results of the simulations were validated by comparison with the experimental Zn K-edge extended X-ray absorption fine structure (EXAFS) spectra and known diffraction data. AIMD NpT simulations reproduced well the thermal expansion of the lattice, and the pronounced …

Study of the thermochromic phase transition in CuMo1−xWxO4 solid solutions at the W L3-edge by resonant X-ray emission spectroscopy

Abstract Polycrystalline CuMo 1 − x W x O 4 solid solutions were studied by resonant X-ray emission spectroscopy (RXES) at the W L 3 -edge to follow a variation of the tungsten local atomic and electronic structures across thermochromic phase transition as a function of sample composition and temperature. The experimental results were interpreted using ab initio calculations. The crystal-field splitting parameter Δ for the 5d(W)-states was obtained from the analysis of the RXES plane and was used to evaluate the coordination of tungsten atoms. Temperature-dependent RXES measurements were successfully employed to determine the hysteretic behaviour of the structural phase transition between t…

Raman study of the phase transitions sequence in pure WO3 at high temperature and in HxWO3 with variable hydrogen content

Abstract An extensive investigation of the temperature dependence of Raman spectra has been carried out on WO 3 powders from room temperature to 800°C. In particular the orthorhombic-to-tetragonal phase transition occurring at about 740°C has been studied for the first time. The Raman active mode at 710 cm −1 of the orthorhombic phase disappears from the spectrum at temperature below the phase transition point and the Raman activity in the tetragonal phase results very low. A comparative study of hydrogenated tungsten bronzes H x WO 3 ( x ≤0.23), where the same transition sequence is driven by an increase of the proton concentration from x =0 to 0.23, reveals similar behaviour of the high f…

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…

Probing NiO nanocrystals by EXAFS spectroscopy

Abstract The structure relaxation in nanocrystalline NiO (nano-NiO, 13 nm crystallite size) has been studied by X-ray absorption spectroscopy at the Ni K-edge at 300 K. Conventional single-scattering analysis of the EXAFS signals from the first two coordination shells showed a lattice volume expansion by about 1% and a contraction of the Ni–O bonds by about 0.5% in nano-NiO compared to microcrystalline NiO. A more sophisticated approach, based on a combination of classical molecular dynamics and ab initio multiple-scattering EXAFS theory, allowed us to interpret both static relaxation and lattice dynamics in nano-NiO.

The Grain Boundary Wetting Phenomena in the Ti‐Containing  High‐Entropy Alloys: A Review

This review is written during the preparation of M‐era.Net full proposal  ʺGrain boundaries in multicomponent alloys without principal componentʺ (A.K., A.K., G.A.L.  and E.R., application No. 9345). The Institute of Solid State Physics, University of Latvia, as a cen‐ ter of excellence, has received funding from the European Union’s Horizon 2020 Framework Pro‐ gramme H2020‐WIDESPREAD‐01‐2016‐2017‐TeamingPhase2 under grant agreement no. 739508,  project CAMART2. 

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 of Multiferroic $\mathrm{MnWO_4}$ and $\mathrm{Mn_{ 0.7} Co_{0.3}WO_4}$ Revealed by the Evolutionary Algorithm

A novel reverse Monte Carlo/evolutionary algorithm scheme was applied to the analysis of the W L3-edge and Mn(Co) K-edges EXAFS spectra from multiferroic MnWO4 and Mn0.7Co0.3WO4. A 3D structural model, consistent with the experimental data, was obtained, and the influence of composition and temperature on the local structure of tungstates is discussed.

Zn K-edge XANES in nanocrystalline ZnO

Zn K-edge XANES in ZnO has been calculated within the full-multiple-scattering (FMS) and finite difference method (FDM) formalism using the ab initio FDMNES code. The influence of non-muffin-tin potential, bulk defects, surface termination and polarization effects on XANES has been analysed. The obtained theoretical results are compared with available experimental data for polycrystalline and nanocrystalline zinc oxide systems.

Al driven peculiarities of local coordination and magnetic properties in single phase Alx CrFeCoNi high entropy alloys

The authors thank the Helmholtz-Zentrum Berlin for the provision of access to synchrotron radiation facilities and allocation of synchrotron radiation at the PM2-VEKMAG, BAMline, and UE46_PGM-1 beamlines of BESSY II at HZB as well as measurement time for magnetometry at HZB CoreLab for Quantum Materials. A. S. acknowledges personal funding from CALIPSOplus project (the Grant Agreement no. 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020). The financial support for the VEKMAG project and the PM2-VEKMAG beamline by the German Federal Ministry for Education and Research (Nos. BMBF 05K10PC2, 05K10WR1, 05K10KE1) and by HZB is cordially acknowledged by all co-author…

Study of the thermochromic phase transition in CuMo1−xWxO4 solid solutions at the W L3-edge by resonant X-ray emission spectroscopy

This is the peer reviewed version of the following article: I. Pudza, A. Kalinko, A. Cintins, A. Kuzmin, Acta Mater. 205 (2021) 116581, which has been published in final form at https://www.sciencedirect.com/science/article/abs/pii/S1359645420310181 This article may be used for non-commercial purposes in accordance with Elsevier Terrms and Conditions for Self-Archiving.

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…

Formation of dislocations in LiF irradiated with 3He and 4He ions

Influence of the irradiation with 13.5 MeV 3He and 5 MeV 4He ions on the micro-structure and mechanical properties of LiF single crystals was studied. The depth profiles of nanoindentation, dislocation mobility, selective chemical etching and photoluminescence served for the characterization of damage. Strong ion-induced increase of hardness and decrease in dislocation mobility at the stage of track overlapping due to accumulation of dislocations and other extended defects was observed. At high fluences (1015 ions/cm2) the hardness saturates at about 3.5 GPa (twofold increase in comparison to a virgin crystal) thus confirming high efficiency of light projectiles in modifications of structur…

Oxidation State and Local Structure of Chromium Ions in LaOCl

This research is funded by the Latvian Council of Science, project “Novel transparent nanocomposite oxyfluoride materials for optical applications”, project No. LZP-2018/1-0335. 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.

Nanoscale X-ray detectors based on individual CdS, SnO2 and ZnO nanowires

Abstract The development of nanoscale X-ray sensors is of crucial importance to achieve higher spatial resolution in many X-ray-based techniques playing a key role in materials science, healthcare, and security. Here, we demonstrate X-ray detection using individual CdS, SnO 2 , and ZnO nanowires (NWs). The NWs were produced via vapor–liquid–solid technique and characterized using X-ray diffraction, scanning, and transmission electron microscopy . Electrical measurements were performed under ambient conditions while exposing two-terminal NW-based devices to X-rays generated by a conventional tungsten anode X-ray tube. Fast and stable nanoampere-range X-ray beam induced current (XBIC) in resp…

Origin of Pressure-Induced Metallization in Cu 3 N: An X-ray Absorption Spectroscopy Study

The authors are grateful to Professor Alain Polian for providing the NDAC cell.

Synthesis and Vibration Spectroscopy of Nano-Sized Manganese Oxides

The present study has been supported by the Latvian National Research Program IMIS2. One of us, IS, was supported by MES RF RFMEFI61615X0064.

Synthesis and characterization of GaN/ReS2, ZnS/ReS2 and ZnO/ReS2 core/shell nanowire heterostructures

This research was funded by the ERDF project “Smart Metal Oxide Nanocoatings and HIPIMS Technology”, project number: 1.1.1.1/18/A/073. 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.

Neural Network Approach for Characterizing Structural Transformations by X-Ray Absorption Fine Structure Spectroscopy

AIF acknowledge support by the US Department of Energy, Office of Basic Energy Sciences under Grant No. DE-FG02 03ER15476. AIF acknowledges support by the Laboratory Directed Research and Development Program through LDRD 18-047 of Brookhaven National Laboratory under U.S. Department of Energy Contract No. DE-SC0012704 for initiating his research in machine learning methods. The help of the beamline staff at ELETTRA (project 20160412) synchrotron radiation facility is acknowledged. RMC-EXAFS and MD-EXAFS simulations were performed on the LASC cluster-type computer at Institute of Solid State Physics of the University of Latvia.

Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment

Financial support provided by Scientific Research Project for Students and Young Researchers, Latvia Nr. SJZ/2018/7 realized at the Institute of Solid State Physics, University of Latvia is greatly acknowledged. 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>Influence of radiation defects on exciton-magnon interactions in nickel oxide</title>

Influence of radiation defects on the optical absorption spectrum of nickel oxide (NiO) was studied at 6 K in the near-IR energy range of 7750-8300 cm-1 corresponding to the magnetic-dipole transition 3A 2g(F )->3T 2g(F ) at nickel sites. NiO single crystals grown by the method of chemical transport reactions on the MgO(100) substrates were irradiated by the neutron fluences up to 5x1018 cm-2. Two sharp lines were observed at the low-energy side of the band: the peak at 7805 cm-1 is assigned to the pure exciton transition, whereas the peak at 7845 cm-1, to the exciton-magnon excitation that occurs at the Brillouin zone-center (BZC). An increase of the defect concentration at higher fluences…

The Use of X-ray Absorption Spectra for Validation of Classical Force-Field Models

Abstract Extended X-ray absorption fine structure (EXAFS) spectroscopy and molecular dynamics (MD) simulations are two complementary techniques widely used to study the atomic structure of materials. Their combined use, known as the MD-EXAFS approach, allows one to access the structural information, encoded in EXAFS, far beyond the nearest coordination shells and to validate the accuracy of the interaction potential models. In this study we demonstrate the use of the MD-EXAFS method for a validation of several force-field models on an example of the cubic-perovskite SrTiO3 and hexagonal wurtzite-type ZnO crystals.

Thermal disorder and correlation effects in anti-perovskite-type copper nitride

This work has been supported by the Latvian National Research Program IMIS2. The EXAFS experiment has been financed from the European Community's Seventh Framework Programme under grant agreement No. 226716 (Project I-20100098 EC). J.T. also gratefully acknowledges support from the National Science Foundation under the DMREF program Grant No. CHE-1534184.

High Entropy Alloys for Energy Conversion and Storage: A Review of Grain Boundary Wetting Phenomena

This research was funded by the Russian Ministry of Science and Higher Education (contract no. 075-15-2021-945 grant no. 13.2251.21.0013). Support from the University of the Basque Country (project GIU19/019) and from the Basque Government (project IT1714-22) is also acknowledged.

Tuning the Photoresponse of Nano‐Heterojunction: Pressure‐Induced Inverse Photoconductance in Functionalized WO 3 Nanocuboids

S.R. and S.S. contributed equally to this work. This work was mainly supported by the Natural Science Foundation of China (Grant No. 11874076), National Science Associated Funding (NSAF, Grant No. U1530402), and Science Challenging Program (Grant No. TZ2016001). D.E. thanks the financial support from Spanish MINECO under Grant No. MAT2016-75586-C4-1-P and from Generalitat Valenciana under Grant Prometeo/2018/123, EFIMAT. The X-ray diffraction measurements were performed at the BL15U1 station, Shanghai Synchrotron Radiation Facility (SSRF) in China. The HP XAS measurements were performed at 20 ID-C, APS, ANL. APS is supported by DOE-BES, under contract no. DE-AC02-06CH11357. The authors grat…

Jahn-Teller distortion aroundFe4+inSr(FexTi1−x)O3−δfrom x-ray absorption spectroscopy, x-ray diffraction, and vibrational spectroscopy

$\mathrm{Sr}({\mathrm{Fe}}_{x}{\mathrm{Ti}}_{1\ensuremath{-}x}){\mathrm{O}}_{3\ensuremath{-}\ensuremath{\delta}}$ perovskites (strontium titanate ferrite solid solution) with well-defined oxygen stoichiometry have been studied as a function of iron concentration by x-ray diffraction, Fe and Ti $K$-edge x-ray absorption spectroscopy (XAS), and vibrational (Raman and infrared) spectroscopy. In reduced $\mathrm{Sr}({\mathrm{Fe}}_{x}{\mathrm{Ti}}_{1\ensuremath{-}x}){\mathrm{O}}_{3\ensuremath{-}x∕2}$ samples, the analysis of the Fe $K$-edge extended x-ray absorption fine structure indicates the expected presence of oxygen vacancies ${\mathrm{V}}_{\mathrm{O}}^{∙∙}$ in the first coordination shell…

Evidence of nickel ions dimerization in NiWO4 and NiWO4-ZnWO4 solid solutions probed by EXAFS spectroscopy and reverse Monte Carlo simulations

Abstract The existence of exchange-coupled Ni 2 + ions – the so-called magnetic dimers – in wolframite-type NiWO 4 and Zn c Ni 1 − c WO 4 solid solutions with high nickel content was discovered by X-ray absorption spectroscopy combined with reverse Monte Carlo (RMC) simulations. Temperature- (10–300 K) and composition-dependent X-ray absorption spectra were measured at the Ni K-edge, Zn K-edge, and W L 3 -edge of microcrystalline NiWO 4 , Zn c Ni 1 − c WO 4 and ZnWO 4 . Structural models were obtained from simultaneous analysis of the extended X-ray absorption fine structure (EXAFS) spectra at three metal absorption edges using RMC simulations. The obtained radial distribution functions for…

X-ray diffraction and Raman spectroscopy studies in Na1/2Bi1/2TiO3-SrTiO3-PbTiO3 solid solutions

The long and short range orders in 0.4Na1/2Bi1/2TiO3-(0.6-x)SrTiO3-xPbTiO3 solid solutions were studied by x-ray diffraction and Raman spectroscopy. X-ray diffraction patterns for these composition...

Structural disorder and electronic hybridization in NicMg1−cO solid solutions probed by XANES at the oxygen K edge

A series of NicMg1−cO solid solutions has been studied for the first time looking at the structural disorder by means of x-ray absorption near-edge-structure (XANES) spectroscopy at the oxygen K edge. The experimental XANES signals were analysed within the full multiple scattering formalism and were interpreted taking into account clusters of up to 15 coordination shells around an absorbing oxygen atom. The substitution of nickel atoms by magnesium atoms results in a dramatic decrease of the empty density of states in the conduction band close to the Fermi level due to an exchange of the 3d(Ni)–2p(O) interaction with 3p(Mg)–2p(O). Besides, a simultaneous small decrease of the 3d(Ni)–2p(O) h…

Ab initio LCAO study of the atomic, electronic and magnetic structures and the lattice dynamics of triclinic CuWO4

Abstract The electronic, structural and phonon properties of antiferromagnetic triclinic CuWO 4 have been studied using the first-principles spin-polarized linear combination of atomic orbital (LCAO) calculations based on the hybrid exchange–correlation density functional (DFT)/Hartree–Fock (HF) scheme. In addition, the local atomic structure around both Cu and W atoms has been probed using extended X-ray absorption fine structure (EXAFS) spectroscopy. We show that, by using the hybrid DFT–HF functional, one can accurately and simultaneously describe the atomic structure (the unit cell parameters and the atomic fractional coordinates), the band gap and the phonon frequencies. In agreement w…

X-ray Absorption Study of Gallium Arsenide at the Ga and As K-edges

We present X-ray absorption study of gallium arsenide at the Ga and As K-edges. The analysis of the X-ray absorption fine structure was done in the framework of the multiple-scattering theory. Both XANES and EXAFS regions are considered. The calculated signals are in very good agreement with experimental data. It is shown that for both edges multiple-scattering contributions are negligible for wavevector values greater than 3 Å-1, and single-scattering analysis can be used without significant loss of accuracy in that region.

<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 and Magnetic Properties of Nickel Oxide Nanopowders

Structure and magnetic properties of nickel oxide (NiO) nanopowders have been studied by X-ray/neutron diffraction, SQUID magnetometer, and micro-Raman spectroscopy. Our diffraction data indicate that at room temperature all NiO powders are antiferromagnetically ordered and have a rhombohedral (R-3m) phase. The SQUID magnetometry and Raman spectroscopy measurements support the presence of the antiferromagnetic ordering.

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).

Structural characterization of mixed Ta–Re oxide films

Thin films of mixed Ta and Re oxides have been produced by reactive dc magnetron co-sputtering of pure Ta and Re metal targets in Ar–O2 atmosphere. The structural evolution of these films has been studied as a function of the composition, starting from a pure tantalum oxide film up to about 82% rhenium content. The composition and the structure of the films have been investigated by using X-ray diffraction and micro-Raman spectroscopy. For low Re content (20%), islands of a well crystallized phase, based on ReO4 groups, appear in the films still composed by pure amorphous tantalum oxide, while a mixed disordered solid phase is found for the highest Re concentration (82%). © 2006 Elsevier B.…

Local structure relaxation in nanocrystalline Ni1−xO thin films

Abstract Non-stoichiometric nickel oxide (Ni 1 − x O) thin films were prepared by DC magnetron sputtering technique in mixed Ar/O 2 atmosphere and studied by synchrotron radiation Ni K-edge x-ray absorption spectroscopy, x-ray diffraction and scanning electron microscopy. The use of advanced modelling technique, combining classical molecular dynamics with ab initio multiple-scattering extended x-ray absorption fine structure calculations, allowed us to describe the structure relaxation and dynamics in nanocrystallites and to estimate their size and the concentration of nickel vacancies.

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 …

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.

Interpretation of the Cu K-edge EXAFS spectra of Cu3N using ab initio molecular dynamics

Financial support provided by ERDF 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. This work was supported by a grant from the Swiss National Supercomputing Centre (CSCS) under the project ID s681 .

Unexpected Epitaxial Growth of a Few WS2 Layers on {11̅00} Facets of ZnO Nanowires

Core–shell nanowires are an interesting and perspective class of radially heterostructured nanomaterials where epitaxial growth of the shell can be realized even at noticeable core–shell lattice mismatch. In this study epitaxial hexagonally shaped shell consisting of WS2 nanolayers was grown on {1100} facets of prismatic wurtzite-structured [0001]-oriented ZnO nanowires for the first time. A synthesis was performed by annealing in a sulfur atmosphere of ZnO/WO3 core–shell structures, produced by reactive dc magnetron sputtering of an amorphous a-WO3 layer on top of ZnO nanowire array. The morphology and phase composition of synthesized ZnO/WS2 core–shell nanowires were confirmed by scanning…

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…

Recent progress in high pressure X-ray absorption spectroscopy studies at the ODE beamline

I.J. and A.K. are grateful to the Latvian Council of Science project no. lzp-2018/2-0353 for financial support. The research leading to these results has been partially supported by the project CALIPSOplus under the Grant Agreement No. 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020.

Some aspects of pulsed laser deposition of Si nanocrystalline films

International audience; Nanocrystalline silicon films were deposited by a picosecond laser ablation on different substrates in vacuum at room temperature. A nanocrystalline structure of the films was evidenced by atomic force microscopy (AFM), optical and Raman spectroscopies. A blue shift of the absorption edge was observed in optical absorption spectra, and a decrease of the optical phonon energy at the Brillouin zone centre was detected by Raman scattering. Early stages of nanocrystalline film formation on mica and HOPG substrates were studied by AFM. Mechanism of nanocrystal growth on substrate is discussed.

Proton presence and motion in rhenium-oxide films and their application to liquid-crystalline cells

Disordered solid phases, containing appreciable amounts of hydrogen ions, are grown at the surface of rhenium oxide crystals, because of the high reactivity of this compound with ambient moisture. To investigate such phenomena, a comparative study is performed on ground powder and thermally evaporated or sputtered films using x-ray diffraction and micro-Raman spectroscopy. Two types of solid phases were found in the films: HxReO3 distorted perovskite structures, based on corner-sharing ReO6 octahedra as in the bulk crystals, and ordered HReO4 crystalline structures, based on tetrahedral perrhenate ions. The complex impedance measurements on ReO3 films support the hypothesis of mobile hydrog…

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.

Effect of cobalt doping on the local structure and dynamics of multiferroic MnWO4and Mn0.7Co0.3WO4

The local atomic structure and dynamics in multiferroic MnWO4 and Mn0.7Co0.3WO4 have been studied by X-ray absorption spectroscopy at the Co(Mn) K-edge and W L3-edge. The analysis of the first coordination shell of metal ions using single-shell Gaussian approximation and regularization-like method allowed us to determine a distortion of Mn(Co)O6 and WO6 octahedra. It was found that the local environment of Co2+ ions in Mn0.7Co0.3WO4 is close to that in CoWO4, whereas the presence of cobalt ions reduces the distortion of MnO6 octahedra in comparison with pure MnWO4.

EDA: EXAFS data-analysis software package

The EXAFS data-analysis software package EDA consists of a suite of programs running under a Windows operating system environment that is designed to perform all steps of conventional EXAFS data analysis such as extraction of the XANES/EXAFS parts of the X-ray absorption coefficient, Fourier filtering and EXAFS fitting using the Gaussian and cumulant models. The package also includes two advanced approaches which allow the reconstruction of the radial distribution function (RDF) from EXAFS based on the regularization-like method and the calculation of configuration-averaged EXAFS using a set of atomic configurations obtained from molecular-dynamics or Monte Carlo simulations.---- / / / ----…

Local structure of copper nitride revealed by EXAFS spectroscopy and a reverse Monte Carlo/evolutionary algorithm approach

Physica scripta 91(5), 054003 (2016). doi:10.1088/0031-8949/91/5/054003

Low-temperature polymorphism in tungsten trioxide powders and its dependence on mechanical treatments

The polymorphism of WO3 powder samples, resulting from mild mechanical treatments and from temperature changes between 30 K and room temperature, has been investigated by using Raman spectroscopy and X-ray di⁄raction. A transition from the monoclinic (I) c-phase to the triclinic d-phase after moderate mechanical treatments has been observed for untreated powder, just what happens when the same samples are rapidly cooled to low-temperature. Evidences of the low temperature monoclinic (II) polar e-phase have been found at room temperature in samples after a stronger milling treatment. The sequence of the low-temperature phase transitions appears to be strongly dependent on the mechanical hist…

A comparative study of heterostructured CuO/CuWO4 nanowires and thin films

Authors are grateful to Reinis Ignatans for XRD measurements.

Oxygen K-edge XANES investigation of NicMg1−cO solid solutions

A series of Ni(c)Mg(1-c)O solid solutions are characterized by means of synchrotron radiation X-ray diffraction and X-ray absorption near-edge-structure spectroscopy at oxygen K-edge (532 eV). A dramatic drop of the pre-edge peak intensity is observed in the Ni(c)Mg(1-c)O system upon dilution. It can be attributed to a decrease of 3d(8)(Ni(2+))-2p(O(2-)) mixing upon dilution with magnesium ions due to a decrease of the number of 3d vacancies as nickel ion is replaced by magnesium ion. Similarly, the decrease of the number of 4s and 4p vacancies also leads to a decrease of 4s4p(Ni(2+))-2p(O(2-)) hybridization, and hence a drop of intensities of features B and C. The features E and F are more…

Influence of hydrogen intercalation on the local structure around Re ions in perovskite‐type ReO 3

octahedra with the Re-O-Re angle equal to 169° and the Re-O distance of about 1.90 A [9]. More accurate information on the local atomic and electronic structure of the bronzes can be ob-tained using XAS, which is a structural method complimentary to diffraction. To our knowledge, no such works have been performed until now. In this work, we present the first results of the in-situ XAS study of hydrogen intercalation into ReO

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…

<title>Raman scattering by phonons and magnons in Ni<formula><inf><roman>c</roman></inf></formula>Mg<formula><inf><roman>1-c</roman></inf></formula>O solid solutions</title>

ABSTRACT The Raman scattering by phonons and magnons was studied at room temperature in polycrystalline solid solutions NiMg1O and pure NiO. The experimental Raman spectrum of NiO consists of six well resolved bands, whose originis due to the disorder-induced one-phonon scattering (bands at 400 and 500 cm'), two-phonon scattering (bands at 750,900 and 1 100 cm) and two-magnon scattering (band at 1500 cm). In NiMg1O solid solutions, a relative increase ofone-phonon scattering is observed upon a dilution of nickel oxide by magnesium ions: at room temperature, the two-magnon band becomes invisible for c<O.7, whereas the two-phonon contribution disappears at c<O.5. Such behaviour isexplained by…

Local structure aroundEr3+inSiO2−HfO2glassy waveguides using EXAFS

${\mathrm{Er}}^{3+}$-doped $\mathrm{Si}{\mathrm{O}}_{2}\text{\ensuremath{-}}\mathrm{Hf}{\mathrm{O}}_{2}$ glassy waveguides with $\mathrm{Hf}{\mathrm{O}}_{2}$ concentrations ranging from $10\phantom{\rule{0.3em}{0ex}}\text{to}\phantom{\rule{0.3em}{0ex}}50\phantom{\rule{0.3em}{0ex}}\mathrm{mol}\phantom{\rule{0.2em}{0ex}}%$ were prepared using the sol-gel route and deposited on $v\text{\ensuremath{-}}\mathrm{Si}{\mathrm{O}}_{2}$ substrates using the dip-coating technique. The local environment around ${\mathrm{Er}}^{3+}$ ions was determined from Er ${L}_{3}$-edge extended x-ray-absorption fine-structure (EXAFS) measurements. The first coordination shell around ${\mathrm{Er}}^{3+}$ ions is comp…

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.

Topological analysis of chemical bonding in the layered FePSe3 upon pressure-induced phase transitions

The authors acknowledge the assistance of the University Computer Center of Saint-Petersburg State University in the accomplishment of high-performance computations. A.K. is grateful to the Latvian Council of Science project no. lzp-2018/2-0353 for financial support. 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.

Neutron diffraction studies of structural and magnetic properties of niobium doped cobaltites.

Neutron powder diffraction studies of the structural and magnetic properties of the La(1-x)Sr(x)Nb(y)Co(1-y)O(3) solid solutions (x = 0.2, 0.5; y = 0, 0.075, 0.1) have been performed. Substitution of Co(2+) by Nb(5+) prevents the formation of Co(4+) and leads to stabilization of the Co(3+) ions in the high- or intermediate-spin state. This is accompanied by the significant change of the Co-O bond length as well as Co-O-Co bond angle in the CoO(6) octahedron. The obtained data are in agreement with the negative sign of the magnetic exchange interactions Co(3+)-O-Co(3+) in a relatively wide range of the Co-O-Co bond angles. Diamagnetic dilution by the niobium ions prevents long-range magnetic…

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…

Wavelet data analysis of EXAFS spectra

Abstract The application of wavelet transform to the analysis of the extended X-ray absorption fine structure (EXAFS) from perovskite-type compounds is presented on the example of the Re L 3 -edge in ReO 3 and Co K-edge in LaCoO 3 . We propose a modified wavelet transform procedure, which allows better discrimination of the overlapped contributions into the EXAFS signal.

Plasmonic photoluminescence enhancement by silver nanowires

Strong enhancement of photoluminescence is demonstrated for CdS nanocrystals and ruthenium-based dye (N719) due to localized surface plasmon resonance of silver nanowires placed on silver film. Alternative reasons for photoluminescence modulation such as mirror effect and uneven coating by dye or nanocrystals due to geometrical factors are discussed. An artifact such as carbon contamination at the surface of silver nanowires at high laser power is demonstrated and taken into consideration. Silver nanowire on silver film is proved to be an effective system for photoluminescence enhancement by localized surface plasmon resonance.

Template-based synthesis of nickel oxide

Nanocrystalline NiO has been produced using a facile template-based synthesis from nickel nitrate solutions using cellulose as a template. Thus obtained oxides were studied by scanning electron microscopy, x-ray diffraction, Raman scattering spectroscopy, photoluminescence spectroscopy and confocal spectromicroscopy. The filamentary/coral morphology of the samples has been evidenced and is built up of agglomerated nanocrystallites with a size in the range of about 26-36 nm. The presence of two-magnon contribution in Raman scattering spectra suggests the existence of antiferromagnetic ordering at room temperature. Finally, the observed near-infrared photoluminescence band at 850 nm has been …

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.

Local Structure of Multiferroic MnWO4 and Mn0.7Co0.3WO4 Revealed by the Evolutionary Algorithm

A novel reverse Monte Carlo/evolutionary algorithm scheme was applied to the analysis of the W L3-edge and Mn(Co) K-edges EXAFS spectra from multiferroic MnWO4 and Mn0.7Co0.3WO4. A 3D structural model, consistent with the experimental data, was obtained, and the influence of composition and temperature on the local structure of tungstates is discussed.

Pressure-induced insulator-to-metal transition in α-SnWO4

In-situ high-pressure W L1 and L3 edges x-ray absorption and mid-infrared spectroscopies complemented by first-principles calculations suggest the existence of pressure- induced insulator-to-metal transition in α-SnWO4 in the range of 5-7 GPa. Its origin is explained by a symmetrization of metal-oxygen octahedra due to a strong interaction of Sn 5s, W 5d and O 2p states along the b-axis direction, leading to a collapse of the band gap.

Chemical-state analyses of Ni, Zn, and W ions in NiWO$_4$-ZnWO$_4$ solid solutions by X-ray photoelectron spectroscopy

The chemical states of Ni, Zn, and W in microcrystalline NiWO$_4$-ZnWO$_4$ solid solutions were studied by X-ray photoelectron spectroscopy. The recorded spectra of the Ni 2p, Zn 2p, and W 4f photoelectron lines and Ni L$_2$M$_{23}$M$_{45}$, Zn L$_3$M$_{45}$M$_{45}$, and W N$_4$N$_{67}$N$_{7}$ Auger-transition lines show pronounced changes with increasing Zn concentration. The positions of the resolved photoelectron and Auger-transition lines were combined to construct so-called chemical-state plots (Wagner or Auger-parameter plots) for metal ions in solid solutions. With increasing Zn concentration, the Auger parameter increases for Ni and decreases for W, thus evidencing a lowering and an…

In Situ Study of Zinc Peroxide Decomposition to Zinc Oxide by X‐Ray Absorption Spectroscopy and Reverse Monte Carlo Simulations

The authors wish to thank Dr. R. Kalendarev for the synthesis of ZnO2 sample. A.K. would like to thank the financial support of the ERDF Project No. 1.1.1.1/20/A/060. The experiment at the MAX IV synchrotron was performed within the project 20190823. 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.

Magnon and Phonon Excitations in Nanosized NiO

Single-crystal, microcrystalline and nanocrystalline nickel oxides (NiO) have been studied by Raman spectroscopy. A new band at ~200 cm-1 and TO-LO splitting of the band at 350–650 cm-1 have been found in the spectra of single-crystals NiO(100), NiO(110) and NiO(111). The Raman spectra of microcrystalline (1500 nm) and nanocrystalline (13–100 nm) NiO resemble those of the single crystals. They all contain the two-magnon band at 1500 cm-1, indicating that the oxides remain at room temperature in the antiferromagnetic phase. Besides, a new sharp Raman band has been observed at 500 cm-1 in nanocrystalline NiO. Its temperature dependence suggests the magnetic origin of the band, possibly associ…

Ab initio study of the electronic and atomic structure of the wolframite-type ZnWO4

Abstract Ab initio quantum chemistry calculations of the structural and electronic properties of monoclinic wolframite-type ZnWO 4 crystal have been performed within the periodic linear combination of atomic orbitals (LCAO) method using six different Hamiltonians, based on density functional theory (DFT) and hybrid Hartree-Fock-DFT theory. The obtained results for optimized structural parameters, band gap and partial density of states are compared with available experimental data, and the best agreement is observed for hybrid Hamiltonians. The calculations show that zinc tungstate is a wide band gap material, with the direct gap about 4.6 eV, whose valence band has largely O 2p character, w…

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.

Origin of pressure-induced insulator-to-metal transition in the van der Waals compound FePS3 from first-principles calculations

The authors acknowledge the assistance of the University Computer Center of Saint‐Petersburg State University in the accomplishment of high‐performance computations. A.K. is grateful to the Latvian Council of Science project no. lzp‐2018/2‐0353 for financial support.

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…

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&lt;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&gt;0.50 the films contained nanosized NiO and NiWO4.

Theoretical and Experimental Studies of Charge Ordering in CaFeO 3 and SrFeO 3 Crystals

EXAFS study of hydrogen intercalation into ReO 3 using the evolutionary algorithm.

In this study we have investigated the influence of hydrogen intercalation on the local atomic structure of rhenium trioxide using a new approach to EXAFS data analysis, based on the evolutionary algorithm (EA). The proposed EA-EXAFS method is an extension of the conventional reverse Monte Carlo approach but is computationally more efficient. It allows one to perform accurate analysis of EXAFS data from distant coordination shells, taking into account both multiple-scattering and disorder (thermal and static) effects. The power of the EA-EXAFS method is first demonstrated on an example of the model system, pure ReO3, and then it is applied to an in situ study of hydrogen bronze HxReO3 upon …

Influence of diamagnetic impurity on mid‐IR absorption in antiferromagnetic insulator NiO

-1 was studied in polycrystalline Ni c Mg 1-c O solid solutions with c=0.99, 0.98, 0.97, 0.95, 0.90, 0.80, 0.70 and 0.60. The composition and temperature dependences of the absorption suggest that the band has magnetic origin re- lated to simultaneous excitation of two-magnons at the Brillouin-zone boundary and one phonon. -1 in polycrystalline NicMg1-cO solid solutions. Polycrystalline solid solutions NicMg1-cO (c=0.99, 0.98, 0.97, 0.95, 0.90, 0.80, 0.70 and 0.60) were prepared using ceramic technology from the appropriate amounts of aqueous solutions of Mg(NO3)2·6H2O and Ni(NO3)2·6H2O salts, which were mixed and slowly evaporated. The remaining dry 'flakes' were heated up to 500-600 oC to…

Influence of Nb-doping on the local structure and thermoelectric properties of transparent TiO2:Nb thin films

The experiment at HASYLAB/DESY was performed within the project I-20180036 EC. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. Filipe Correia is grateful to the Fundação para a Ciência e Tecnologia (FCT, Portugal) for the Ph.D. Grant SFRH/BD/111720/2015 . Joana Ribeiro is grateful to the Project WinPSC - POCI-01-0247-FEDER-017796, for the research grant, co-funded by the European Regional Development Fund (ERDF) , through the Operational Programme for Competitiveness and Internationalisation (COMPETE 2020), under the PORTUGAL 2020 Partnership Agreement…

Magnetic Ion Exchange Interactions in NiO—MgO Solid Solutions

In this work, a review of recent experimental data and their interpretation for NicMg1−c O solid solutions is given. In particular, the influence of exchange interactions between Ni2+ ions on the structural, optical, magnetic, and vibrational properties is discussed.

&lt;title&gt;Scanning probe microscopy of nanocrystalline iridium oxide thin films&lt;/title&gt;

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…

Neutron diffraction study of microstructural and magnetic effects in fine particle NiO powders

Nickel oxide powders with grain sizes ranging from 100 to 1500 nm have been studied by high-resolution neutron diffraction. We have found that the atomic structure, the antiferromagnetic ordering, and the value of the nickel magnetic moments inherent in the bulk material of NiO are still preserved and are nearly independent of the average size of the grains. The sizes of the coherently scattering atomic and magnetic domains were estimated independently owing to a complete separation of the nuclear and magnetic peaks in the neutron diffraction patterns. It is shown that the finite-size and surface disorder effects in particles at the submicron scale have a more pronounced influence on the ma…

Molecular dynamics and reverse Monte Carlo modeling of scheelite-type AWO4(A = Ca, Sr, Ba) WL3-edge EXAFS spectra

Classical molecular dynamics (MD) and reverse Monte Carlo methods coupled with ab initio multiple-scattering extended x-ray absorption fine structure (EXAFS) calculations were used for modeling of scheelite-type AWO4 (A = Ca, Sr, Ba) W L 3-edge EXAFS spectra. The two theoretical approaches are complementary and allowed us to perform analysis of full EXAFS spectra. Both methods reproduce well the structure and dynamics of tungstates in the outer coordination shells, however the classical MD simulations underestimate the W–O bond MSRD due to a neglect of quantum zero-point-motion. The thermal vibration amplitudes, correlation effects and anisotropy of the tungstate structure were also estimat…

High-pressure x-ray absorption spectroscopy study of tin tungstates

Room-temperature pressure-dependent (0-25 GPa) x-ray absorption spectroscopy at the W -edges of α-SnWO4 and β-SnWO4 was performed using a dispersive setup and a high-pressure nanodiamond anvil cell. The detailed analysis of experimental x-ray absorption near-edge structure and extended x-ray absorption fine structure data suggests that upon increasing pressure, a displacement of tungsten atoms by about 0.2 A toward the center of the WO6 octahedra occurs in α-SnWO4, whereas the coordination of tungsten atoms changes from tetrahedral to distorted octahedral in β-SnWO4.

Local structure and magnetization of ferromagnetic Cu-doped ZnO films: No magnetism at the dopant?

Abstract Relationship between magnetism and structure of Cu-doped ZnO was investigated at macroscopic and microscopic levels. Thin Zn1−xCuxO films (x = 0.02, 0.04, 0.07 and 0.10) were prepared by a pulsed laser deposition and characterized via superconducting quantum interference device (SQUID) magnetometry, high-resolution x-ray diffraction, and Cu K-edge and Zn K-edge x-ray absorption, x-ray linear dichroism and x-ray circular magnetic dichroism spectroscopy. Even though the samples exhibit room-temperature ferromagnetism with magnetization that increases with Cu concentration, we did not detect signatures of local magnetic moments associated with Cu atoms, as evidenced by the lack of any…

Raman and infrared spectromicroscopy of manganese oxides

Abstract Confocal micro-Raman and micro-FT-IR spectroscopies have been used to probe the phase composition of nominally pure single-crystal MnO and mixed MnO–Mn 3 O 4 samples, grown by the method of chemical transport reactions on MgO(1 0 0) substrate. The presence of spinel Mn 3 O 4 phase has been clearly detected in both samples by Raman and FT-IR spectroscopies. The size of the spinel Mn 3 O 4 phase regions has been estimated to be below 20 μm.

Electronic excitations in ZnWO4 and ZnxNi1−x WO4 (x = 0.1 − 0.9) using VUV synchrotron radiation

The photoluminescence spectra and luminescence excitation spectra of pure microcrystalline and nano-sized ZnWO4 as well as the Zn x Ni1−x WO4 solid solutions were studied using vacuum ultraviolet (VUV) synchrotron radiation. The samples were also characterized by x-ray powder diffraction. We found that: (i) the shape of the photoluminescence band at 2.5 eV, being due to radiative electron transitions within the [WO6]6− anions, becomes modulated by the optical absorption of Ni2+ ions in the Zn x Ni1−x WO4 solid solutions; and (ii) no significant change in the excitation spectra of Zn0.9Ni0.1WO4 is observed compared to pure ZnWO4. At the same time, a shift of the excitonic bands to smaller en…

Local structure of nanosized tungstates revealed by evolutionary algorithm

Nanostructured tungstates, such as CoWO4 and CuWO4, are very promising catalytic materials, particularly for photocatalytic oxidation of water. The high catalytic activity of tungstate nanoparticles partially is a result of their extremely small sizes, and, consequently, high surface-to-volume ratio. Therefore their properties depend strongly on the atomic structure, which differ significantly from that of the bulk material. X-ray absorption spectroscopy is a powerful technique to address the challenging problem of the local structure determination in nanomaterials. In order to fully exploit the structural information contained in X-ray absorption spectra, in this study we employ a novel ev…

Short-range order around Er3+ in silica waveguides containing aluminium, titanium and hafnium

Er3+-doped silica waveguides, co-doped with aluminium, titanium, and hafnium oxides, were prepared using the sol-gel method and dip-coating processing. Here, we present a characterisation of the local environment around Er3+ ions, as determined from the Er L3-edge extended X-ray absorption fine structure (EXAFS) measurements performed at ESRF (France). The first coordination shell is composed of 5-6 oxygen atoms at distances ~2.32-2.35 A , slightly varying as a function of the modifier oxide. Er3+ nearest neighbors distance does not show a significant compositional dependence. On the contrary, outer shells analysis shows significant differences: Al2O3 doping (less than 2% mol) induces an or…

Evaluation of multiple-scattering contribution in extended X-ray absorption fine structure for MO4 and MO6 clusters

Abstract We present a theoretical ab initio evaluation of the multiple-scattering contribution in the extended X-ray absorption fine structure for MO4 and MO6 clusters with M = Mg, Ca, Mn, Zn, Se, Sr, Mo, Ag, Te, Ba, Nd, Tb, W, Au or Bi. The dependence of the multiple-scattering signal on the absorber type, the photoelectron angular momentum and the local distortion is discussed. It is shown that the multiple-scattering contribution is significant in the photoelectron wave-vector range up to 6–7 A−1 and strongly depends on both the path geometry and the atomic species involved in the scattering process.

Temperature dependence of the local structure and lattice dynamics of wurtzite-type ZnO

Temperature-dependent (10–300 K) Zn K-edge extended X-ray absorption fine structure (EXAFS) spectra of polycrystalline wurtzitetype ZnO were analyzed using ab initio multiple-scattering theory and taking into account anisotropy of the crystallographic structure and thermal disorder. We employed two different simulation approaches: classical molecular dynamics (MD) and reverse Monte Carlo coupled with an evolutionary algorithm (RMC/EA method). The accuracy of several force-field models, which are commonly used in the MD simulations of bulk and nanostructured ZnO, was tested based on a comparison between the experimental and simulated Zn K-edge EXAFS spectra. It was found that available force…

Object size effect on the contact potential difference measured by scanning Kelvin probe method

International audience; Contact potential difference (CPD) was measured by macroscopic Kelvin probe instrument and scanning Kelvin probe microscope on Al, Ni and Pt on ITO substrates at ambient conditions. CPD values measured by scanning Kelvin probe microscope and macroscopic Kelvin probe are close within the error of about 10-30% for large studied objects, whereas scanning Kelvin probe microscope signal decreases, when the object size becomes smaller than 1.4 m. CPD and electric field signals measured using many-pass technique allowed us to estimate the influence of electrostatic field disturbance, especially, in the case of small objects.

Study of Copper Nitride Thin Film Structure

Abstract X-ray diffraction and x-ray absorption spectroscopy at the Cu K-edge were used to study the atomic structure in copper nitride (Cu3N) thin films. Textured nanocrystalline films are obtained upon dc magnetron sputtering on substrates heated at about 190 °C, whereas amorphous films having strongly disordered structure already in the second coordination shell of copper are deposited in the absence of heating.

X-ray absorption spectroscopy of strongly disordered glasses: Local structure around Ag ions ing−Ag2O∙nB2O3

The local structure around Ag ions in silver borate glasses $g\text{\ensuremath{-}}{\mathrm{Ag}}_{2}\mathrm{O}∙n{\mathrm{B}}_{2}{\mathrm{O}}_{3}$ $(n=2,4)$ was studied by x-ray absorption spectroscopy at the Ag $K$ edge for temperatures from $77\phantom{\rule{0.3em}{0ex}}\text{to}\phantom{\rule{0.3em}{0ex}}450\phantom{\rule{0.3em}{0ex}}\mathrm{K}$. Extended x-ray absorption fine structure (EXAFS) analysis based on cumulant expansion or multishell Gaussian model fails for these systems. Therefore, the radial distribution functions (RDFs) around Ag ions were reconstructed using a method based on the direct inversion of the EXAFS expression. The RDFs consist of about eight atoms (oxygens and b…

Understanding the Conversion Process of Magnetron-Deposited Thin Films of Amorphous ReO$_x$ to Crystalline ReO$_3$ upon Thermal Annealing

Crystal growth &amp; 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.

Influence of Pressure and Temperature on X-Ray Induced Photoreduction of Nanocrystalline CuO

The authors are grateful to Prof. Alain Polian for providing NDAC cell. Parts of the present research have been carried out at the ODE beamline at SOLEIL.

One‐magnon Raman scattering in Ni c Mg 1–c O solid solutions

The one-magnon Raman scattering was studied for the first time in antiferromagnetic NicMg1–cO solid solutions as a function of temperature and composition. We found that (i) the one-magnon frequency extrapolated to T = 0 K experiences an abrupt change between c = 0.99 and c = 0.9 and (ii) the one-magnon energy for highly diluted nickel oxide vanishes significantly below the Neel temperature. The obtained dependences are compared to the theoretical predictions within the mean field approximation. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Static and dynamic structure of $ZnWO_4$ nanoparticles

Abstract Static and dynamic structure of ZnWO 4 nanoparticles, synthesized by co-precipitation technique, has been studied by temperature dependent x-ray absorption spectroscopy at the Zn K-edge and W L 3 -edge. Complementary experimental techniques, such as x-ray powder diffraction, Raman and photoluminescence spectroscopies, have been used to understand the variation of vibrational, optical, and structural properties of nanoparticles, compared to microcrystalline ZnWO 4 . Our results indicate that the structure of nanoparticles experiences strong relaxation leading to the significant distortions of the WO 6 and ZnO 6 octahedra, being responsible for the changes in optical and vibrational …

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…

EXAFS study of the local structure of crystalline and nanocrystalline Y2O3using evolutionary algorithm method

Temperature-dependent local structure and lattice dynamics of yttria (Y2O3) were studied by X-ray absorption spectroscopy. Novel method, which combines the reverse Monte Carlo and evolutionary algorithm techniques, was applied for the analysis of extended X-ray absorption fine structure at the Y K-edge. This approach allowed us to reconstruct 3D atomic structure models of crystalline and nanocrystalline Y2O3.

Growth and optical properties of transition metal oxides single crystal solid solutions

Abstract NiO, CoO, MnO single crystals and single crystal solid solutions of Ni c Mg 1− c O, Co c Mg 1− c O and Mn c Mg 1− c O were grown by the method of chemical transport reaction (the “sandwich” technique). The nature of the observed absorption and luminescence bands is explained in terms of the electronic transition of bivalent nickel, cobalt and manganese. The fine structure of the observed bands in NiO and MnO are connected to the pure exciton transition and to the exciton-magnon excitation.

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.

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 Fe0F1Fe2F3Fe4 atomic chain in iron K-edge XAFS of FeF3 which is analysed using an ab initio multiple-scattering approach.

Local structure and lattice dynamics of cubic Y2O3: an x-ray absorption spectroscopy study

Classical molecular dynamics was used to interpret the temperature dependent (300-1273 K) Y K-edge x-ray absorption spectra of cubic c-Y2O3 and to validate two force-field models. It was shown that both models reproduce well thermal disorder effect, however are less accurate in description of static octahedra distortion around yttrium atoms. The temperature dependencies of mean-square displacements and mean-square relative displacements were obtained from molecular dynamics simulations for the first two shells of yttrium. The importance of anharmonic effects was demonstrated by comparison of molecular dynamics and lattice dynamics results.

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…

Local atomic and electronic structure of tungsten ions in AWO4 crystals of scheelite and wolframite types

Abstract X-ray absorption spectroscopy was used to study the local atomic and electronic structure of tungsten ions in polycrystalline scheelite CaWO4 and wolframite-type ZnWO4 and NiWO4. The W L1- and L3-edges X-ray absorption near edge structure (XANES) signals suggest tetrahedral coordination of tungsten ions in CaWO4 and strongly distorted octahedral coordination in ZnWO4 and NiWO4. Accurate analysis of the W L3-edge extended X-ray absorption fine structure (EXAFS) signals by the regularization procedure was performed to reconstruct the radial distribution functions within the first coordination shell around tungsten atoms in AWO4 crystals and polycrystalline WO3, which was utilized for…

Including atomic vibrations in XANES calculations: polarization-dependent damping of the fine structure at the Cu K edge of (creat)$_{2}$CuCl$_{4}$

Atomic vibrations are usually not taken into account when analyzing x-ray absorption near edge structure (XANES) spectra. One of the reasons is that including the vibrations in a formally exact way is quite complicated while the effect of vibrations is supposed to be small in the XANES region. By analyzing polarized Cu K edge x-ray absorption spectra of creatinium tetrachlorocuprate [(creat)$_{2}$CuCl$_{4}$], we demonstrate that a technically simple method, consisting in calculating the XANES via the same formula as for static systems but with a modified free-electron propagator which accounts for fluctuations of interatomic distances, may substantially help in understanding XANES of some l…

Grain Boundary Wetting Phenomena in High Entropy Alloys Containing Nitrides, Carbides, Borides, Silicides, and Hydrogen: A Review

This review was written during the preparation of M-era.Net full proposal “Grain boundaries in multicomponent alloys without principal component” (A.Ko., A.Ku., G.L., and E.R., application No 9345). We also acknowledge the support of the KIT-Publication Fund of the Karlsruhe Institute of Technology. The Institute of Solid State Physics, University of Latvia, as a 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.

Quantum mechanics-molecular dynamics approach to the interpretation of x-ray absorption spectra.

The quantum mechanics-molecular dynamics approach to the simulation of configuration-averaged EXAFS spectra is proposed, and its application is discussed for the example of the Ti K-edge EXAFS spectrum in cubic perovskite SrTiO(3). Proper use of ab initio quantum mechanics allows a number of empirical parameters, used in the molecular dynamics simulation, to be reduced, whereas the molecular dynamics allows us to account for temperature effects. All together, the approach provides a way of accounting for static and dynamic disorder in EXAFS signals from the coordination shells above the first one, where many-atom (multiple-scattering) effects are often important.

X-ray absorption and Raman spectroscopy studies of tungstates solid solutions ZncNi1-cWO4 (c=0.0-1.0)

G.B. acknowledges the financial support provided by the State Education Development Agency for project No. 1.1.1.2/VIAA/3/19/444 (agreement No. 1.1.1.2/16/I/001) realized at the Institute of Solid State Physics, University of Latvia. A.K. and A.K. would like to thank the support of the Latvian Council of Science project No. lzp-2019/1-0071. 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.

Pressure-induced structural changes in α-MoO3 probed by X-ray absorption spectroscopy

The authors are grateful to Prof. Alain Polian for providing NDAC cell. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. The work was supported by philanthropist MikroTik and administrated by the University of Latvia Foundation.

Fast-Response Single-Nanowire Photodetector Based on ZnO/WS 2 Core/Shell Heterostructures

This work was supported by the Latvian National Research Program IMIS2 and ISSP project for Students and Young Researchers Nr. SJZ/2016/6. S.P. is grateful to the ERA.Net RUS Plus WATERSPLIT project no. 237 for the financial support. S.V. is grateful for partial support by the Estonian Science Foundation grant PUT1689.

Interpretation of EXAFS in scheelite-type AWO4(A = Ca, Sr, Ba) compounds using molecular dynamics simulations

In this work we successfully interpret the W L3-edge EXAFS spectra in scheelite-type AWO4 (A = Ca, Sr, Ba) compounds using a combination of classical NVT molecular dynamics (MD) and ab initio multiple-scattering (MS) theory. The configuration-averaged EXAFS spectra show good agreement with our room temperature experimental data supporting the reliability of the developed force-field models. The contributions from all coordination shells up to 6 A are elucidated. The contribution of the MS effects into the total EXAFS signal in AWO4 compounds is small, being around 10%.

Raman and photoluminescence spectroscopy of zinc tungstate powders

ZnWO4 powders, synthesized using co-precipitation technique and annealed in air at different temperatures in the range of 80-800 � C, were studied by Raman and photoluminescence spectroscopy. ZnWO4 single crystal was used for comparison. The interpretation of the observed variations of the Raman spectra and intrinsic photoluminescence band upon annealing is suggested.

Quantum mechanics-classical molecular dynamics approach to EXAFS

Recently developed approach to the simulation of configuration-averaged EXAFS spectra using the combination of quantum mechanics and classical Molecular Dynamics (MD) methods is presented on the example of the Ti K-edge in SrTiO3 at T = 300 K. The method allows one to significantly reduce the number of fitting parameters required in the EXAFS signal calculation and to account entirely for disorder contributions. We show also that the sensitivity of configuration-averaged EXAFS spectra to the force field model employed in the MD simulations allows one to use them as additional information for the force field parameters fitting.

Octahedral Tilting in Homologous Perovskite Series CaMoO3-SrMoO3-BaMoO3 Probed by Temperature-Dependent EXAFS Spectroscopy

This research was funded by the State Education Development Agency project No. 1.1.1.2/VIAA/3/19/444 (agreement No. 1.1.1.2/16/I/001) realized at the Institute of Solid State Physics, University of Latvia; the Institute of Solid State Physics, University of Latvia, as the Center of Excellence received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART2.

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

Nanocrystalline CaWO$_4$ and ZnWO$_4$ Tungstates for Hybrid Organic-Inorganic X-ray Detectors

The experiment at the DESY PETRA-III synchrotron was performed within project No. I-20211105 EC at the Institute of Solid State Physics, University of Latvia, as the Cen ter of Excellence has received funding from the European Union’s Horizon 2020 Framework Pro gramme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART2.

Effect of Pressure and Temperature on the Local Structure and Lattice Dynamics of Copper(II) Oxide

Abstract Microcrystalline and nanocrystalline (6 nm) CuO were studied in situ by the Cu K-edge X-ray absorption spectroscopy as a function of pressure (0-20 GPa) and temperature (10-300 K). Pressure dependence of X-ray absorption near edge structure (XANES) was interpreted within the full-multiple-scattering formalism based on the relaxed atomic structure determined by ab initio linear combination of atomic orbital (LCAO) calculations. Temperature dependence of the mean-square relative displacement (MSRD) for the four shortest Cu–O distances was obtained from the analysis of extended X-ray absorption fine structure (EXAFS) and described by the correlated Einstein model with the characterist…

Full multiple scattering analysis of X-ray absorption near edge structure at the Eu L3-edge in EuO

Abstract X-ray absorption near edge structure (XANES) at the Eu L 3 -edge in crystalline EuO is interpreted within full multiple scattering (FMS) formalism. Our theoretical results, based on the ab initio self-consistent (SC) potential calculations, are in good agreement with experimental data. The main features in the experimental signal are reproduced taking into account a cluster of about five coordination shells, centred at the europium atom and having EuO structure. An addition of more distant coordination shells makes features only better resolved. The relatively high intensity of the peak, located just above the Eu L 3 -edge, indicates that 5d states are well localised. Comparative a…

Peculiarities of the local structure in new medium- and high-entropy, low-symmetry tungstates

G. Bakradze acknowledges financial support provided by the Latvian Council of Science for project no. 1.1.1.2/VIAA/3/19/444 (agreement no. 1.1.1.2/16/I/001) realized at the Institute of Solid State Physics, University of Latvia. The Institute of Solid State Physics, University of Latvia, as a centre 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.

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.]

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.

Structure and dielectric properties of Na0.5Bi0.5TiO3-CaTiO3 solid solutions

Despite wide studies of Na0.5Bi0.5TiO3, structure of this material and its connection with the observed physical properties still raise numerous questions due to mutually contradicting results obtained. Here, structure and dielectric properties of poled and unpoled Na0.5Bi0.5TiO3-CaTiO3 solid solutions are studied, projecting the obtained concentration dependence of structure and dielectric properties on pure Na0.5Bi0.5TiO3 as the end member of this material group. X-ray diffraction patterns for Na0.5Bi0.5TiO3-CaTiO3 solid solutions reveal dominating of an orthorhombic Pnma phase, even for the compositions approaching the end composition (Na0.5Bi0.5TiO3), whereas structure of pure Na0.5Bi0.…

Treatment of disorder effects in X-ray absorption spectra beyond the conventional approach

The contribution of static and thermal disorder is one of the largest challenges for the accurate determination of the atomic structure from the extended X-ray absorption fine structure (EXAFS). Although there are a number of generally accepted approaches to solve this problem, which are widely used in the EXAFS data analysis, they often provide less accurate results when applied to outer coordination shells around the absorbing atom. In this case, the advanced techniques based on the molecular dynamics and reverse Monte Carlo simulations are known to be more appropriate: their strengths and weaknesses are reviewed here.

Nanosession: Valence Change Memories - A Look Inside

Oxygen K-edge x-ray absorption near-edge structure in crystalline and amorphous molybdenum trioxides

X-ray absorption near-edge structure (XANES) signals at the oxygen K edge in polycrystalline α-MoO3 and amorphous a-MoO3 thin film were analysed within the full-multiple-scattering (FMS) formalism. Significantly different XANES signals were found for non-equivalent oxygen atoms in low-symmetry layered-type α-MoO3 structure. The obtained results are in agreement with the experimental data and allow us to interpret all XANES peaks for α-MoO3. Besides, the FMS XANES simulations, performed for several fragments of α-MoO3 structure, allowed us to explain the O K-edge XANES in amorphous a-MoO3 thin film. We found that although the crystallographic structures of α-MoO3 and a-MoO3 are strongly diff…

Probing the Thermochromic Phase Transition in CuMoO 4 by EXAFS Spectroscopy

The work was supported by philanthropist MikroTik and administrated by the University of Latvia Foundation. The experiment at HASYLAB/DESY was performed within the project I-20160149 EC.

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

&lt;title&gt;In-situ x-ray absorption fine structure and x-ray diffraction studies of hydrogen intercalation in tungsten oxides&lt;/title&gt;

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.

X-ray absorption spectroscopy study of local dynamics and thermal expansion in ReO3

The thermal expansion of polycrystalline ${\mathrm{ReO}}_{3}$ is studied in vacuum by x-ray diffraction from 300 to 600 K and by extended x-ray absorption fine structure (EXAFS) at the Re ${L}_{3}$ edge from 30 to 600 K. A detailed EXAFS analysis is presented up to the sixth coordination shell around Re. The crystal thermal expansion is weak throughout the explored range, negative below 100 K, positive from 150 to 500 K, and negative again above 500 K. The analysis of mean square relative displacements obtained by EXAFS and of mean square displacements available from x-ray and neutron diffraction measurements confirms the presence of significant static disorder in the investigated samples. …

Ab initio calculations of the Ni K ‐edge XANES in Ni c Mg 1‐c O solid solutions

An interpretation of the Ni K-edge X-ray absorption near edge structure (XANES) in pure NiO and NicMg1-cO solid solutions is given based on three types of ab initio theoretical calculations: the full-multiple-scattering (FMS) approach, the finite difference method (FDM) and the full potential linear muffin-tin orbital (FP-LMTO) method within the LSDA+U approach. The first two methods differ in the cluster potential approximation: the spherically symmetric muffin-tin potential is used in the FMS approach, whereas a non-muffin-tin numerical potential makes the core of the FDM. We found that the FMS and FDM techniques allow rather accurate description of the experimental XANES signal especiall…

Behavior of one-magnon frequency in antiferromagneticNicMg1−cOsolid solutions

The one-magnon scattering was studied in antiferromagnetic ${\mathrm{Ni}}_{c}{\mathrm{Mg}}_{1\ensuremath{-}c}\mathrm{O}$ solid solutions. We observed unpredicted behavior of both temperature and composition dependences of one-magnon excitation energies. First, the abrupt change of the one-magnon frequency by $7--8\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$ occurs between $c=0.98$ and $c=0.9$ in the limit of $T\ensuremath{\rightarrow}0\phantom{\rule{0.3em}{0ex}}\mathrm{K}$. Second, upon increasing temperature, the one-magnon energy for highly diluted nickel oxide vanishes significantly below the N\'eel temperature.

Advanced approach to the local structure reconstruction and theory validation on the example of the W L 3 -edge extended x-ray absorption fine structure of tungsten

The authors gratefully acknowledge the assistance of the ELETTRA XAFS beamline staff members during the EXAFS experiment No 20150303. 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.

Interpretation of the Co K-edge EXAFS in LaCoO3 using molecular dynamics simulations

Abstract Temperature dependent (180–400 K) Co K-edge EXAFS spectra from perovskite-type rhombohedral ( R 3 ¯ c ) LaCoO 3 have been successfully interpreted using a combination of classical NVT molecular dynamics (MD) and ab initio multiple-scattering (MS) theory. The method allowed us to account entirely for thermal disorder and to interpret reliably the contribution from the coordination shells beyond the first one into the total EXAFS spectrum taking into account many-body effects. The best agreement between experimental and configuration-averaged EXAFS spectra was obtained for pure ionic La 3+ and partially ionic Co 1.35+ and O 1.45− charges indicating the mixed ionic-covalent character …

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.

X-ray absorption near edge spectroscopy of thermochromic phase transition in CuMoO4

Thermochromic phase transition was studied in CuMoO4 using the Cu and Mo K-edge x-ray absorption spec-troscopy in the temperature range of 10-300 K. The hysteretic behavior has been evidenced from the tempera-ture dependence of the pre-edge shoulder intensity at the Mo K-edge, indicating that the transition from brown-ish-red γ-CuMoO4 to green α-CuMoO4 occurs in the temperature range of 230-280 K upon heating, whereas the α-to-γ transition occurs between 200 and 120 K upon cooling. Such behavior of the pre-edge shoulder at the Mo K-edge correlates with the change of molybdenum coordination between distorted tetrahedral in α-CuMoO4 and distorted octahedral in γ-CuMoO4. This result has been s…

&lt;title&gt;X-ray absorption spectroscopy study of the local environment around tungsten and molybdenum ions in tungsten-phosphate and molybdenum-phosphate glasses&lt;/title&gt;

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.

Preparation and Characterization of Tin Tungstate Thin Films

Tin tungstate thin films were prepared by dc magnetron sputtering method and studied by x-ray diffraction, confocal microscopy and Raman spectroscopy. It is shown that the films are composed mainly of nanocrystalline α-SnWO4 phase. The possibility to use these films as write-once optical recording media is demonstrated.

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…

First-principles LCAO study of the low and room temperature phases of CdPS$_3$

A.K. is grateful to the Latvian Council of Science project no. lzp-2018/2-0353 for financial support. 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.

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.

The role of nano-perovskite in the negligible thorium release in seawater from Greek bauxite residue (red mud)

AbstractWe present new data about the chemical and structural characteristics of bauxite residue (BR) from Greek Al industry, using a combination of microscopic, analytical, and spectroscopic techniques. SEM-EDS indicated a homogeneous dominant “Al-Fe-Ca-Ti-Si-Na-Cr matrix”, appearing at the microscale. The bulk chemical analyses showed considerable levels of Th (111 μg g−1), along with minor U (15 μg g−1), which are responsible for radioactivity (355 and 133 Bq kg−1 for 232Th and 238U, respectively) with a total dose rate of 295 nGy h−1. Leaching experiments, in conjunction with SF-ICP-MS, using Mediterranean seawater from Greece, indicated significant release of V, depending on S/L ratio,…

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…

Neutron scattering study of structural and magnetic size effects in NiO

Nickel oxide powders with the grain size of 13–1500 nm have been studied by neutron scattering, scanning electron microscopy and vibrating sample magnetometry. We have found that the atomic structure and the antiferromagnetic ordering are nearly independent of the average size of grains. The existence of the uncompensated spins in nanoparticles with the grain size below 100 nm has been detected.

Analysis of extended x-ray absorption fine structure data from copper tungstate by the reverse Monte Carlo method

The static disorder and lattice dynamics of crystalline materials can be efficiently studied using reverse Monte Carlo simulations of extended x-ray absorption fine structure spectra (EXAFS). In this work we demonstrate the potentiality of this method on an example of copper tungstate CuWO4. The simultaneous analysis of the Cu K and W L3 edges EXAFS spectra allowed us to follow local structure distortion as a function of temperature.

Polarisation dependent Raman study of single-crystal nickel oxide

Abstract The magnetic domain structure and Raman scattering have been studied in NiO single-crystals with three different (100), (110) and (111) orientations. Twin-domain structure was observed in NiO(100) and NiO(110) single-crystals using cross-polarized optical microscopy. We found that the ratio of the two-magnon (at 1500 cm−1) to the two-phonon (2LO, at 1100 cm−1) Raman bands intensity is sensitive in a particular way to the type of the twin-domain pattern.

First-principles LCAO study of phonons in NiWO4

Abstract The electronic, structural and phonon properties of antiferromagnetic wolframite-type NiWO4 have been studied using first-principles spin-polarized LCAO calculations based on the hybrid Hartree-Fock (HF)/density functional (DFT) scheme. The influence of different percentages of HF contribution, i.e. different correlation strength, on the structure and phonon frequencies has been investigated and compared with the available experimental data.

Unprecedented pressure-driven metallization and topological charge transport in an anion radical salt

Abstract The hybrid inorganic/organic closed π -stacking and soft lattice of a copper anion radial (Copper-7,7,8,8-tetracyanoquinodimethane) renders its electrical conductivity and structural modifications, which are susceptible to temperature and pressure. The geometry of its metal-ligand construction contemplates the concept of topology with a charge-transfer instability. A pressure-induced ionic-neutral phase transition occurs and accompanies an anomalously large electrical conductivity, carries topological charges, and possesses a low energy gap smaller than the Coulomb gap. X-ray absorption spectroscopy of the metal establishes the high electrical conduction by the topological charges.…

Effect of atomic vibrations in XANES: polarization-dependent damping of the fine structure at the Cu K-edge of (creat)2CuCl4

Polarization-dependent damping of the fine structure in the CuK-edge spectrum of creatinium tetrachlorocuprate [(creat)2CuCl4] in the X-ray absorption near-edge structure (XANES) region is shown to be due to atomic vibrations. These vibrations can be separated into two groups, depending on whether the respective atoms belong to the same molecular block; individual molecular blocks can be treated as semi-rigid entities while the mutual positions of these blocks are subject to large mean relative displacements. The effect of vibrations can be efficiently included in XANES calculations by using the same formula as for static systems but with a modified free-electron propagator which accounts f…

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…

External pressure and composition effects on the atomic and electronic structure of SnWO4

The atomic and electronic structure of tin tungstates, α-SnWO4, α-Sn1.03W0.99O4 and β-SnWO4 ,w as studied by the W L3-edge X-ray absorption spectroscopy and first-principles linear combination of atomic orbital (LCAO) calculations based on the hybrid exchange-correlation density functional (DFT)/ Hartree–Fock (HF) scheme. It was found that the crystal structure of both α-phases is built up of strongly distorted WO6 octahedra, whereas that of β-SnWO4 is composed of nearly regular WO4 tetrahedra. In addition, there are distorted SnO6 octahedra in both α- and β-phases. The metal–oxygen octahedra distortion is explained by the second-order Jahn–Teller effect. The influence of pressure on the st…

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…

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.

Negative thermal expansion of ScF 3 : first principles vs empirical molecular dynamics

The calculations were performed on the Paul Scherrer Institute cluster Merlin4, HPC resources of the Swiss National Supercomputing Centre in Lugano (project ID s626) as well as at the Latvian SuperCluster (LASC). Authors are greatly indebted to S. Ali, D. Gryaznov, R.A. Evarestov, M. Isupova, A. Kalinko, V. Kashcheyevs, V. Pankratov, S. Piskunov, A. I. Popov, J. Purans, F. Rocca, L. Shirmane, P. Zˇguns, and Yu. F. Zhukovskii for many 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.

Local Environment of Co2+ Ions in β″-Alumina Crystals

X-ray absorption spectroscopy of Cu-doped $WO_{3}$ films for use inelectrochemical metallization cell memory

Abstract We have performed the first synchrotron radiation X-ray absorption spectroscopy (EXAFS/XANES) study of the local atomic and electronic structure around Cu and W ions in WO 3 /Cu/WO 3 /Si and WO 3 /Cu/Si multilayered structures, aimed for the application in the electrochemical metallization cell memory. The influence of low-temperature annealing at 135 °C has been investigated in details, and a structural model of Cu-doped WO 3 films is proposed.

Isotopic Effect In Extended X-Ray-Absorption Fine Structure of Germanium

Extended x-ray absorption fine structure has been measured on two powdered samples of 70Ge and 76Ge as a function of temperature from 20 to 300 K. The effect of isotopic mass difference on the amplitude of relative atomic vibrations is neatly evidenced by the temperature dependence of the difference of Debye-Waller factors. The isotopic effect is also detected on the difference of nearest-neighbor average ineratomic distances, thanks to a resolution better than 10 fm. (DOI: 10.1103/PhysRevLett.100.055901)

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.

High-temperature X-ray absorption spectroscopy study of thermochromic copper molybdate

Financial support provided by Scientific Research Project for Students and Young Researchers Nr. SJZ/2017/5 and SJZ/2018/1 realized at the Institute of Solid State Physics, University of Latvia is greatly acknowledged. The work was also supported by philanthropist MikroTik and administrated by the University of Latvia Foundation . The experiment at the Elettra synchrotron was performed within the project No. 20150303 .

The influence of Sb doping on the local structure and disorder in thermoelectric ZnO:Sb thin films

The experiment at HASYLAB/DESY was performed within the project I-20200161 EC. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. 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. This work was carried out in part through the use of the INL Advanced Electron Microscopy, Imaging and Spectroscopy Facility. This work (proposal ID 2018–020-022469) was car…

Thorium partitioning in Greek industrial bauxite investigated by synchrotron radiation and laser-ablation techniques

Abstract Typical red–brown (Fe-rich) and high-quality white–grey (Fe-depleted) bauxite samples from active mines of the Parnassos-Ghiona area, central Greece, were investigated. According to XRF and ICP-MS analyses their actinide content, and particularly of Th, is relatively increased. Fe-depleted samples contain up to 62.75 ppm Th corresponding to 220 Bq/kg due to 228Ac (232Th-series), whereas Fe-rich samples are less Th-radioactive (up to 58.25 ppm Th, 180 Bq/kg due to 228Ac). Powder-XRD patterns showed that Th-enriched (Fe-depleted) bauxite consists mostly of diaspore (AlOOH polymorph), anatase and rutile (TiO2 polymorphs). SEM-EDS indicated the presence of Ti–Fe–containing phases (e.g.…

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

EXAFS and XANES analysis of oxides at the nanoscale

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence.

The Grain Boundary Wetting Phenomena in the Ti-Containing High-Entropy Alloys: A Review

In this review, the phenomenon of grain boundary (GB) wetting by melt is analyzed for multicomponent alloys without principal components (also called high-entropy alloys or HEAs) containing titanium. GB wetting can be complete or partial. In the former case, the liquid phase forms the continuous layers between solid grains and completely separates them. In the latter case of partial GB wetting, the melt forms the chain of droplets in GBs, with certain non-zero contact angles. The GB wetting phenomenon can be observed in HEAs produced by all solidification-based technologies. GB leads to the appearance of novel GB tie lines Twmin and Twmax in the multicomponent HEA phase diagrams. The so-cal…

The role of Ga and Bi doping on the local structure of transparent zinc oxide thin films

The experiment at HASYLAB/DESY was performed within the project I-20180036 EC. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. Filipe Correia is grateful to the Fundação para a Ciência e Tecnologia (FCT, Portugal) for the Ph.D. Grant SFRH/BD/111720/2015. Joana Ribeiro is grateful to the Project WinPSC - POCI-01-0247-FEDER-017796, for the research grant from the Agência Nacional de Inovação, co-funded by the European Regional Development Fund (ERDF), through the Operational Programme for Competitiveness and Internationalisation (COMPETE 2020), under the…

XAS, XRD, AFM and Raman studies of nickel tungstate electrochromic thin films

Abstract Systematic studies of nanocrystalline nickel tungstate, NiWO 4 , thin films were performed by several experimental techniques such as Ni K- and W L 1,3 -edges X-ray absorption spectroscopy, X-ray diffraction, Raman spectroscopy, atomic force microscopy and cyclic voltammetry measurements. We found that the NiWO 4 thin films exhibit electrochromic properties similar to that of amorphous tungsten trioxide films, but show better structural stability upon multiple colouring/bleaching cycling. It was observed that a nanocrystallinity of the thin films results in strong modifications of the NiO and WO interactions, which affect both local atomic and vibrational structures.

XANES and EXAFS modelling of configurational disorder in silver borate glasses

The sensitivity of X-ray absorption spectroscopy (XAS) to the local structure around a selected atomic species (symmetry, distances and angles) is commonly exploited to quantitatively describe systems where all the configurations around the absorbing atoms may be approximated by the mean one. However, in many cases of disordered systems a simple description of the local structure with singleconfiguration models cannot be reconciled with experimental spectra. In this paper the necessity to analyse the XAS spectra by considering a multiplicity of atomic structural configurations is demonstrated in the case of silver borate glasses. The local coordination around Ag cations in (Ag2O.nB2O3) glas…

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.

Structural Studies of Titanium Oxide Multilayers

Multilayers of titanium oxide on conductive glasses (silica, covered with indium/tin and tin oxides) were obtained by different methods (from suspension, by sol–gel, by vacuum sputtering). X-ray diffraction and positron annihilation depth-resolved characterization of these samples are presented. The data allow us to determine optimal deposition parameters, in order to obtain the anatase phase, important in practical applications in photoelectrochemical cells.

Synthesis and characterization of ZnO/ZnS/MoS2 core-shell nanowires

The present research was supported by the Latvian National Research Program IMIS2 . Authors are grateful for Dr. Robert Kalendarev and Martins Zubkins for assistance in magnetron sputtering, Dr. Krisjanis Smits for TEM measurements, Dr. Roberts Zabels for AFM measurements and Reinis Ignatans for XRD measurements.

Depth profiles of damage creation and hardening in MgO irradiated with GeV heavy ions

This work 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.

Luminescence of polymorphous SiO2

Abstract The luminescence of self-trapped exciton (STE) was found and systematically studied in tetrahedron structured silica crystals (α-quartz, coesite, cristobalite) and glass. In octahedron structured stishovite only host material defect luminescence was observed. It strongly resembles luminescence of oxygen deficient silica glass and γ or neutron irradiated α-quartz. The energetic yield of STE luminescence for α-quartz and coesite is about 20% of absorbed energy and about 5(7)% for cristobalite. Two types of STE were found in α-quartz. Two overlapping bands of STEs are located at 2.5–2.7 eV. The model of STE is proposed as Si–O bond rupture, relaxation of created non-bridging oxygen (N…

Local structure relaxation in nanosized tungstates

Abstract The atomic structure of nanosized and microcrystalline tungstates MeWO 4 (Me=Co, Ni, Cu, Zn), synthesized by co-precipitation technique, has been studied by x-ray absorption spectroscopy at the W L 3 -edge and Co/Ni/Cu/Zn K-edges, x-ray diffraction, Raman and Fourier transform infrared spectroscopies. The distortion of metal–oxygen octahedra is caused by the electron–lattice coupling and is further enhanced in nanosized tungstates due to formation of the double tungsten–oxygen bonds at the nanoparticle surface.

Raman scattering in nanosized nickel oxide NiO

Magnetic ordering in nanosized (100 and 1500 nm) nickel oxide NiO powders, prepared by the plasma synthesis method, was studied using Raman scattering spectroscopy in a wide range of temperatures from 10 to 300 K. It was observed that the intensity of two- magnon band decreases rapidly for smaller crystallites size. This effect is attributed to a decrease of antiferromagnetic spin correlations and leads to the antiferromagnetic-to- paramagnetic phase transition .

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…

Interpretation of the Ni K-edge EXAFS in nanocrystalline nickel oxide using molecular dynamics simulations

Abstract Analysis of atomic structure at the nanoscale is a challenging task, complicated by relaxation phenomena and thermal disorder. In this work, the x-ray absorption spectroscopy at the Ni K-edge was used to address this problem in nanocrystalline NiO (nano-NiO) at 300 K. The analysis of the first two coordination shells using conventional two-shell single-scattering approximation allowed us to determine the expansion of the average lattice but contraction of the Ni―O bonds in the first coordination shell in nano-NiO in comparison with the bulk nickel oxide. The EXAFS signal generated within the first six coordination shells (up to ~ 6.5 A) was successfully interpreted using classical …

Local structure and dynamics of wurtzite‐type ZnO from simulation‐based EXAFS analysis

Conventional methods of EXAFS data analysis are often limited to the nearest coordination shells of the absorbing atom due to the difficulties in accurate accounting for the so-called multiple-scattering effects. Besides, it is often difficult to resolve the non-equivalent groups of atoms in a single coordination shell due to strong correlation between structural parameters. In this study we overcome these problems by applying two different simulation-based methods, i.e., classical molecular dynamics (MD) and reverse Monte with evolutionary algorithm (EA), to the analysis of the Zn K-edge EXAFS data for wurtzite-type bulk ZnO. The RMC/EA-EXAFS method allowed us to separate the contributions…

Low Temperature Optical Absorption by Magnons in KNiF3 and NiO Single-Crystals

Optical absorption spectra of KNiF3 and NiO stoichiometric single-crystals were measured at 5 K in the range from 4000 to 50000 cm-1. The observed bands are interpreted based on the energy levels diagram for Ni2+ (3d 8 ) ion in a cubic crystal field. The crystal-field parameter Dq is equal to 766 cm-1 in KNiF3 and 890 cm-1 in NiO. Particular attention is paid to the band due to the magnetic-dipole 3A2g(F)→3T2g(F) transition, located at 7700 cm-1 in KNiF3 and at 8900 cm-1 in NiO. We show that the energy difference between the two peaks, located at the low energy side of the band, is related to the zone-center (k=0) one-magnon energy, so that the low-energy peak is attributed to the pure exci…

The influence of Zn$^{2+}$ ions on the local structure and thermochromic properties of Cu$_{1-x}$Zn$_x$MoO$_4$ solid solutions

I. P., A. K. and A. K. would like to thank the support of the Latvian Council of Science project No. lzp-2019/1-0071. I.P. acknowledges the L‘OREAL Baltic “For Women In Science” Program with the support of the Latvian National Commission for UNESCO and the Latvian Academy of Sciences. The experiment at the PETRA III synchrotron was performed within project No. I-20190277 EC. The synchrotron experiments have been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2…

Atomic structure relaxation in nanocrystalline NiO studied by EXAFS spectroscopy: Role of nickel vacancies

Nanocrystalline NiO samples have been studied using the Ni K-edge extended x-ray absorption fine structure (EXAFS) spectroscopy and recently developed modeling technique, combining classical molecular dynamics with ab initio multiple-scattering EXAFS calculations (MD-EXAFS). Conventional analysis of the EXAFS signals from the first two coordination shells of nickel revealed that (i) the second shell average distance R(Ni–Ni2) expands in nanocrystalline NiO compared to microcrystalline NiO, in agreement with overall unit cell volume expansion observed by x-ray diffraction; (ii) on the contrary, the first shell average distance R(Ni–O1) in nanocrystalline NiO shrinks compared to microcrystall…

PATTERNED LASER CRYSTALLIZATION OF a-Si

PATTERNED LASER CRYSTALLIZATION OF a-SiThin films of amorphous Si on glass were crystallized by pulsed nano- and picosecond lasers. Two methods for creating the desired patterns of crystallized regions were used. In the former, the pattern is produced by a focused laser beam, and in the latter it is made using a prefabricated mask. The electric conductivity of crystallized films increases by more than 4 orders of magnitude in comparison with untreated amorphous films.