X-ray Absorption Measurements Research Articles

Effect of surface oxidation on soft x-ray optical properties of ion beam sputter deposited amorphous AlN thin film

In the present study, structural and compositional analyses of reactive ion beam sputter deposited aluminum nitride (AlN) thin film of thickness 100 Å are carried out using x-ray reflectivity and x-ray photoelectron spectroscopy techniques. Soft x-ray optical response of the film is derived from energy dependent soft x-ray reflectivity measurements performed in photon energy region of 380–1700 eV. Optical constants (δ and β) obtained from the reflectivity spectra show features corresponding to absorption edges of the constituent elements. Observed fine features in the β profile are further confirmed from x-ray absorption (XAS) measurements carried out in the total electron yield mode. The measured XAS spectra are correlated with electronic and compositional properties of the AlN film. The effects of surface oxidation on soft x-ray optical properties of the AlN thin film are discussed.

The Local Structure of the BiS2 Layer in RE(O,F)BiS2 Determined by In-Plane Polarized X-ray Absorption Measurements

We have investigated the local structure of BiS2-based layered materials by Bi L3-edge extended X-ray absorption fine structure (EXAFS) measurements performed on single crystal samples with polarization of the X-ray beam parallel to the BiS2 plane. The results confirm highly instable nature of BiS2 layer, characterized by ferroelectric like distortions. The distortion amplitude, determined by the separation between the two in-plane (Bi-S1) bonds, is found to be highest in LaO0.77F0.23BiS2 with ΔR∼0.26 Å and lowest in NdO0.71F0.29BiS2 with ΔR∼0.13 Å. Among the systems with intrinsic doping, CeOBiS2 shows smaller distortion (ΔR∼0.15 Å) than PrOBiS2 (ΔR∼0.18 Å) while the highest distortion appears for EuFBiS2 revealing ΔR∼0.22 Å. It appears that the distortion amplitude is controlled by the nature of the RE(O,F) spacer layer in the RE(O,F)BiS2 structure. The X-ray absorption near edge structure (XANES) spectra, probing the local geometry, shows a spectral weight transfer that evolves systematically with the distortion amplitude in the BiS2-layer. The results provide a quantitative measurements of the local distortions in the instable BiS2-layer with direct implication on the physical properties of these materials.

Creatinine generation rate can detect sarcopenia in patients with hemodialysis.

Sarcopenia is strongly associated with long-term mortality in patients undergoing hemodialysis. The diagnostic modalities used to assess muscle mass, such as bioimpedance analysis and dual-energy X-ray absorption measurement, have limitations for application in patients on hemodialysis. Therefore, there is a need to establish a simple index for assessing muscle mass that can be universally performed in patients on hemodialysis. Patients on maintenance hemodialysis were included in this study. Laboratory tests, skeletal muscle mass measured by bioimpedance analysis, and clinical records were obtained retrospectively. The creatinine generation rate (CGR) was calculated from the pre- and postdialysis blood tests using a kinetic model as the index for whole-body muscle mass. Correlations between the CGR and skeletal muscle mass were investigated, and the cut-off value for muscle wasting was determined. Kaplan-Meier survival analysis was performed to investigate the feasibility of the CGR for predicting long-term survival. Among the 130 patients included, eight were diagnosed with sarcopenia by bioimpedance analysis. The CGR was positively correlated with skeletal muscle mass (r = 0.454, p < 0.001). Multiple linear regression analysis revealed that age and sex independently influenced the CGR. The patients were classified into two groups according to age- and sex-adjusted CGRs. During a median follow-up period of 32months, the Kaplan-Meier survival analysis showed that patients with low CGR showed significantly poor long-term prognosis (p = 0.002). The CGR is a simple index for muscle mass and can predict long-term mortality in patients on hemodialysis.

Electronic structure of a borophene layer in rare-earth aluminum/chromium boride and its hydrogenated derivative borophane

We studied electronic states of borophene in a crystal of rare-earth aluminum/chromium boride and the hydrogenated sheet, borophane, successfully prepared by ion exchange and liquid exfoliation of the crystal. The layer has a boron network with five-membered and seven-membered rings. Electronic structures of all the boron-derived layers are found to be gapless by soft x-ray absorption and emission spectroscopy measurements at the B K-shell absorption edge and density functional theory calculations. The present results support the existence of a Dirac nodal loop at the Fermi level in the borophane layer with five- and seven-membered rings, predicted recently by topological calculations.

Determination of the crystal field and nature of x-ray linear dichroism for Co-O with local octahedral, tetrahedral, and tetragonal symmetries

Cobalt oxides with multiple local Co-O coordination environments such as octahedral, tetrahedral, and tetragonal networks display versatile electronic and magnetic properties which have attracted great interest in many fields. Understanding the ground-state properties and determining the fundamental band gap remain challenges in cobalt-based compounds and thin films, which have been investigated here using synchrotron-based Co ${L}_{23}$-edge x-ray absorption measurements followed by configuration interaction cluster calculations. We focus on the detailed Co ${L}_{23}$-edge absorption spectral variations in different octahedral crystal fields as well as in the less investigated tetrahedral and tetragonal systems, taking into account Co ions with different valence states. From a quantitative comparison between the simulated spectrum and an accurately measured absorption spectrum of a specified compound, the crystal field value can be extracted from the Co ${L}_{23}$-edge absorption spectrum, which is complementary to the results obtained in optical measurements and other calculations. Furthermore, Co ${L}_{23}$-edge x-ray linear dichroism shows the same spectral evolutions as a result of either local ${\mathrm{CoO}}_{6}$ cluster with tetragonal symmetry or the magnetic exchange field, whereas both coexist in most antiferromagnetic cobalt oxide thin films. Detailed temperature and polarization-dependent Co ${L}_{23}$-edge absorption measurements have been proposed to distinguish both contributions, which show different spectral variations due to the specified modifications of the ground and final states at different temperatures. Our results offer theoretical guidance for understanding the multiplet structure of Co ${L}_{23}$-edge absorption spectrum, obtaining the precise crystal field value for cobalt oxides with versatile coordinations, and explaining the underlying mechanism of x-ray linear dichroism, as well as understanding the fundamental physical properties and their potential applicability of cobalt oxides and their thin films.

Probing the Spin State of Spin-Crossover Complexes on Surfaces with Vacuum Ultraviolet Angle-Resolved Photoemission Spectroscopy

Spin-crossover complexes in direct contact with substrates have sparked considerable interest, in particular, in view of their potential applications in molecular electronics. While a huge number of spin-crossover complexes is available, many of them are not robust enough to withstand the sample preparation and/or the interaction with the substrate. The techniques usually employed for these investigations, namely, near-edge X-ray absorption fine structure spectroscopy and low-temperature scanning tunneling microscopy, are not adapted for systematic studies because of the limited access to synchrotron-radiation facilities and complexity of the (indirect) spin determination, respectively. Here, we detail a methodology using a (more) commonly available technique, namely, vacuum ultraviolet (angle-resolved) photoemission spectroscopy, to determine the spin state of layers of three different spin-crossover complexes with thicknesses down to the submonolayer regime. We present an approach to determine the thicknesses of the investigated layers, relying on the inelastic mean free path of electrons determined from combined photoemission and X-ray absorption measurements. We report on the high-spin to low-spin relaxation dynamics of spin-crossover (SCO) layers and the influence of the ultraviolet light on these dynamics. While the observed relaxation processes occur on a timescale on the order of minutes, probing spin-state dynamics on the picosecond timescale is foreseeable with pump–probe photoemission spectroscopy.

A novel fuel cell design for operando energy-dispersive x-ray absorption measurements

A polymer electrolyte fuel cell has been designed to allow operando x-ray absorption spectroscopy (XAS) measurements of catalysts. The cell has been developed to operate under standard fuel cell conditions, with elevated temperatures and humidification of the gas-phase reactants, both of which greatly impact the catalyst utilisation. X-ray windows in the endplates of the cell facilitate collection of XAS spectra during fuel cell operation while maintaining good compression in the area of measurement. Results of polarisation curves and cyclic voltammograms showed that the operando cell performs well as a fuel cell, while also providing XAS data of suitable quality for robust XANES analysis. The cell has produced comparable XAS results when performing a cyclic voltammogram to an established in situ cell when measuring the Pt LIII edge. Similar trends of Pt oxidation, and reduction of the formed Pt oxide, have been presented with a time resolution of 5 s for each spectrum, paving the way for time-resolved spectral measurements of fuel cell catalysts in a fully-operating fuel cell.

Formation of an Artificial Mg2+-Permeable Interphase on Mg Anodes Compatible with Ether and Carbonate Electrolytes.

Rechargeable Mg-ion batteries typically suffer from either rapid passivation of the Mg anode or severe corrosion of the current collectors by halogens within the electrolyte, limiting their practical implementation. Here, we demonstrate the broadly applicable strategy of forming an artificial solid electrolyte interphase (a-SEI) layer on Mg to address these challenges. The a-SEI layer is formed by simply soaking Mg foil in a tetraethylene glycol dimethyl ether solution containing LiTFSI and AlCl3, with Fourier transform infrared and ultraviolet-visible spectroscopy measurements revealing spontaneous reaction with the Mg foil. The a-SEI is found to mitigate Mg passivation in Mg(TFSI)2/DME electrolytes with symmetric cells exhibiting overpotentials that are 2 V lower compared to when the a-SEI is not present. This approach is extended to Mg(ClO4)2/DME and Mg(TFSI)2/PC electrolytes to achieve reversible Mg plating and stripping, which is not achieved with bare electrodes. The interfacial resistance of the cells with a-SEI protected Mg is found to be two orders of magnitude lower than that with bare Mg in all three of the electrolytes, indicating the formation of an effective Mg-ion transporting interfacial structure. X-ray absorption and photoemission spectroscopy measurements show that the a-SEI contains minimal MgCO3, MgO, Mg(OH)2, and TFSI-, while being rich in MgCl2, MgF2, and MgS, when compared to the passivation layer formed on bare Mg in Mg(TFSI)2/DME.

Structural phase transition and its consequences for the optical behavior of LaV1−xNbxO4

We present the structural, electronic, vibrational, and photoluminescence properties of polycrystalline ${\mathrm{LaV}}_{1\ensuremath{-}x}{\mathrm{Nb}}_{x}{\mathrm{O}}_{4}$ $(x=0--0.2)$ samples at room temperature. The substitution of Nb at the V site shows the fascinating structural and optical behavior due to their isoelectronic character and larger ionic radii of ${\mathrm{Nb}}^{5+}$ as compared to the ${\mathrm{V}}^{5+}$. The Rietveld refinement of x-ray diffraction patterns demonstrate that the $x=0$ sample exists in a monoclinic $(P{2}_{1}/n)$ phase, whereas for the $x&gt;0$, both monoclinic and scheelite-tetragonal $(I{4}_{1}/a)$ phases coexist in a certain proportion. Interestingly, a monotonous enhancement in the Raman spectral intensity with Nb substitution is correlated with the substitution induced increase in the scheelite-tetragonal phase. The x-ray absorption measurements reveal that the La ions exist in a trivalent oxidation state, while V and Nb cations possess $5+$ oxidation state in tetrahedral coordination. Moreover, the Fourier-transform infrared (FTIR) spectra indicate that the Nb substitution give origin to some additional IR modes owing to the deformation of the ${\mathrm{VO}}_{4}^{3\ensuremath{-}}$ tetrahedra and mixing of monoclinic and tetragonal phases. The photoluminescence measurements on these samples exhibit broadband spectra and their deconvolution designate the availability of more than one electron-hole pairs recombination center.

Enhanced Photodegradation in Metal Oxide Nanowires with Co-Doped Surfaces under a Low Magnetic Field.

This work demonstrated the enhanced photodegradation (PD) resulting from Co-rich doping of ZnO nanowire (NW) surfaces (Co2+/ZnO NWs) prepared by combining Co sputtering on ZnO NWs and immersion in deionized water to exploit the hydrophilic-hydrophobic transitions on the ZnO surfaces resulting from Co atom diffusion. Because of the controllable spin-dependent density of states (DOS) induced by Co2+, the PD of methylene blue dye can be enhanced by approximately 90% (when compared with bare ZnO NWs) by using a conventional permanent magnet with a relatively low magnetic field strength of approximately 0.15 T. The reliability of spin polarization-modulation attained through surface doping, based on the magnetic response observed from X-ray absorption measurements and magnetic circular dichroism, provides an opportunity to create highly efficient catalysts by engineering surfaces and tailoring their spin-dependent DOS.

Thickness dependent electrical resistivity modulation in tensile-strained epitaxial thin films of calcium manganese oxide

We report our studies of the thickness dependence of electrical resistivity and lattice constants in strained epitaxial thin films of calcium manganese oxide. Our results indicate the potential of bi-axial lattice mismatch strain as a handle for modulating electrical resistivity. We observe thickness dependence of lattice constants consistent with what is expected for strain relaxation for films thicker than 400 Å. At lower thickness values, anomalies are observed suggestive of reduced oxygen stoichiometry. We observe a remarkable decrease in electrical resistivity with decreasing film thickness. The resistivity of our thinnest films (5–7 nm) is about three orders of magnitude lower than the resistivity of bulk CaMnO3. Resistivity increases as the film thickness increases, along with the progression of strain relaxation. It is noteworthy that the thickness dependence of resistivity we observe in CMO thin films is the opposite of what has been reported for their hole-doped rare earth manganite counterpart La0.67Ca0.33MnO3 (LCMO), where tensile lattice mismatch strain suppresses metallicity, leading to the increase in resistivity with film thickness. We believe that the enhanced conductivity in our thinnest films is related to the possible oxygen deficiency promoted by tensile strain. Recent x-ray absorption measurements have revealed reduced oxygen content and associated changes in Mn valence states in tensile-strained CMO thin films, as also predicted by density functional theory calculations. This report is the first observation of electrical transport behavior possibly indicative of strain–oxygen stoichiometry coupling.

Carbon-supported layered double hydroxide nanodots for efficient oxygen evolution: Active site identification and activity enhancement

In this study, we developed a novel confinement-synthesis approach to layered double hydroxide nanodots (LDH-NDs) anchored on carbon nanoparticles, which formed a three-dimensional (3D) interconnected network within a porous carbon support derived from pyrolysis of metal-organic frameworks (C-MOF). The resultant LDH-NDs@C-MOF nonprecious metal catalysts were demonstrated to exhibit super-high catalytic performance for oxygen evolution reaction (OER) with excellent operation stability and low overpotential (∼230 mV) at an exchange current density of 10 mAcm−2. The observed overpotential for the LDH-NDs@C-MOF is much lower than that of large-sized LDH nanosheets (321 mV), pure carbonized MOF (411 mV), and even commercial RuO2 (281 mV). X-ray absorption measurements and density functional theory (DFT) calculations revealed partial charge transfer from Fe3+ through an O bridge to Ni2+ at the edge of LDH-NDs supported by C-MOF to produce the optimal binding energies for OER intermediates. This, coupled with a large number of exposed active sides and efficient charge and electrolyte/reactant/product transports associated with the porous 3D C-MOF support, significantly boosted the OER performance of the LDH-ND catalyst with respect to its nanosheet counterpart. Apart from the fact that this is the first active side identification for LDH-ND OER catalysts, this work provides a general strategy to enhance activities of nanosheet catalysts by converting them into edge-rich nanodots to be supported by 3D porous carbon architectures.

Mn substitution effect on the local structure of La(Fe1−x Mn x )AsO studied by temperature dependent x-ray absorption measurements

The local structure of La(Fe1−x Mn x )AsO has been investigated using temperature dependent Fe K-edge extended x-ray absorption fine structure (EXAFS) measurements. The EXAFS data reveal distinct behavior of Fe–As and Fe–Fe atomic displacements with a clear boundary between x ⩽ 0.02 and x > 0.02. The Fe–As bondlength shows a gradual thermal expansion while the Fe–Fe bond manifests a temperature dependent anomaly at ∼180 K for x > 0.02. It is interesting to find characteristically different nature of Fe–As and Fe–Fe bondlengths shown by the temperature dependent mean square relative displacements. Indeed, the Fe–As bond, stiffer than that of the Fe–Fe, gets softer for x ⩽ 0.02 and hardly shows any change for x > 0.02. On the other hand, Fe–Fe bond tends to be stiffer for x ⩽ 0.02 followed by a substantial softening for x > 0.02. Such a distinction has been seen also in the As K-edge x-ray absorption near edge structure, probing local geometry around As atom together with the valence electronic structure. The results suggest that local atomic displacements by Mn substitution inducing increased iron local magnetic moment that should be the main reason for its dramatic effect in iron-based superconductors.

ZnO nanoparticles doping with transition metal elements in polymeric and biomacromolecular matrix and their optical evolution

Abstract The 5% Cu doped zinc oxide nanoparticles in polyvinylpyrrolidone matrix and 5% Fe doped zinc oxide nanoparticles in biotin matrix were prepared and the effect of dopants and stabilizers on different properties were investigated. Surfactant controlled particle sizes and dopants induced changes in optical properties were reported as evident from X-ray diffraction data analysis and absorption measurements. High resolution transmission electron microscopy results of Cu doped ZnO nanoparticles are close to the XRD results. The reduced band gaps are estimated to be 2.90 eV and 2.37 eV for Cu and Fe doped ZnO respectively from absorption measurements. Photoluminescence measurements show how the dopants and surfactant can alter the excitonic and defect related emission in the doped ZnO nanoparticles. Raman spectroscopy of Cu doped ZnO nanoparticles shows characteristics of Cu in to ZnO lattice and new phonon scattering mode. The room temperature ferromagnetism in Fe doped ZnO and its correlation with defects were discussed.

Experimental and theoretical evidence of the temperature-induced wurtzite to rocksalt phase transition in GaN under high pressure

The $p\text{\ensuremath{-}}T$ conditions of the solid-solid phase transition from the wurtzite to rocksalt structure in GaN are determined both experimentally and by ab initio calculations. Experimental evaluation was based on the x-ray absorption measurements in a laser-heated diamond anvil cell. At 300 K, the transition was observed near 47 GPa. At lower pressures, the wurtzite to rocksalt transition has been induced by high temperature: 1420 K at 42 GPa and about 2100 K at 37 GPa. Thus the slope of the wurtzite-rocksalt borderline could be evaluated as negative and nonlinear. On the part of the theory, the $p\text{\ensuremath{-}}T$ borderline was determined from a comparative analysis of the temperature dependences of the Gibbs potential of the wurtzite and rocksalt structures for different pressure. The Gibbs potentials were calculated within the quasiharmonic approximation and the self-consistent phonon approach. The results obtained with the self-consistent phonon approach show that the inclusion of the anharmonic phonon effects is indispensable to obtain a very good agreement with the experimental data. Possible consequences of the observed anharmonicity for the still unknown melting behavior of GaN are discussed. In particular, it is suggested that the melting temperature of the rocksalt-GaN, at pressure around 37 GPa, is not much higher than 2100 K.

Relationship between the microstructure, local magnetism and coercivity in Ga-containing Nd-Fe-B sintered magnets

The crystalline phases that comprise the bulk microstructure of an isotropic Ga-containing Nd-Fe-B sintered magnet are identified by in situ elevated-temperature x-ray diffraction for temperatures between 25 and 800∘C. Comparing the temperature-dependent volume fractions of the crystalline phases with the coercivity as a function of annealing temperature reveals that the large coercivity enhancements are remarkably well-correlated with the existence of a crystalline Nd6(Fe,Ga)14 phase. Scanning soft x-ray absorption microscopy measurements are used to directly observe the distribution of Fe and Nd in anisotropic as-sintered and optimally-annealed samples and demonstrate that the surface microstructure is similar to the bulk. Fe L3-edge x-ray magnetic circular dichroism measurements are used to directly map the demagnetization process in the fractured surfaces of anisotropic as-sintered and optimally-annealed samples. In the as-sintered sample, the demagnetization curves of compositionally different regions all have the same shape but with a maximum magnetic signal that only depends on the Fe content within the probing depth of the x-ray absorption measurements. In the optimally-annealed sample, the demagnetization curves from compositionally different regions have rather different shapes and the exposed Nd2Fe14B grains without any grain boundary coverage have much lower coercivity than those with. This provides evidence that the grain boundary phase that forms upon annealing is able to protect the Nd2Fe14B grains from magnetization reversal by exchange-decoupling the Nd2Fe14B grains.

Mapping the structural, magnetic and electronic behavior of (Eu1− x Ca x )2Ir2O7 across a metal–insulator transition

In this study, we employ bulk electronic properties characterization and x-ray scattering/spectroscopy techniques to map the structural, magnetic and electronic properties of (Eu1−x Ca x )2Ir2O7 as a function of Ca-doping. As expected, the metal-insulator transition temperature, T MIT, decreases with Ca-doping until a metallic state is realized down to 2 K. In contrast, T AFM becomes decoupled from the MIT and (likely short-range) AFM order persists into the metallic regime. This decoupling is understood as a result of the onset of an electronically phase separated state, the occurrence of which seemingly depends on both synthesis method and rare earth site magnetism. PDF analysis suggests that electronic phase separation occurs without accompanying chemical phase segregation or changes in the short-range crystallographic symmetry while synchrotron x-ray diffraction confirms that there is no change in the long-range crystallographic symmetry. X-ray absorption measurements confirm the J eff = ½ character of (Eu1−x Ca x )2Ir2O7. Surprisingly these measurements also indicate a net electron doping, rather than the expected hole doping, indicating a compensatory mechanism. Lastly, XMCD measurements show a weak Ir magnetic polarization that is largely unaffected by Ca-doping. Keywords: term, term, term.

Development of Measurement Tools for High-Throughput Experiments of Synchrotron Radiation XRD and XAFS on Powder Libraries.

We propose to minimize the sampling time for high-throughput measurements of powder X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) in synchrotron radiation. The conventional synchrotron radiation powder X-ray diffraction method requires filling of a capillary tube, but a structure-refining diffraction pattern could be obtained by transferring the crushed powder to a tape and rotating the cassette-tape tool by ±5° around the sample position. XAFS spectra could also be measured with the sample attached to the tape. The time required for sample preparation was greatly reduced, which made high-throughput experiments with powders in synchrotron radiation experiments more accessible.

Fluoride-ion Conductivity Analysis of Yb-F-S Multiple-anion Compounds

Abstract The mixed-anion fluorosulfide Yb3F4S2 was examined as a solid electrolyte for all-solid-state fluoride-ion batteries. The synthesized Yb3F4S2 compound by solid-state reaction under vacuum contained Yb2O2S impurities, which originated from the starting materials. The conduction properties of Yb3F4S2 are discussed herein based on the electrochemical impedance and DC blocking measurements, which indicate mixed ionic and electrical conduction of Yb3F4S2. Yb L3-edge X-ray absorption measurements demonstrate the mixed valence state of ytterbium ion.

Revealing Interplay of Defects in SnO2 Quantum Dots for Blue Luminescence and Selective Trace Ammonia Detection at Room Temperature.

Defect chemistry in SnO2 is well established for resistive sensors but remains to be elusive for photoluminescence (PL) sensors. It demands a comprehensive understanding of the role of cationic and oxygen defects as well as the creation of abundant such defects to provide a selective PL signal. To accomplish it, SnO2 quantum dots (QDs ∼ 2.4 nm) are prepared without a capping agent along with other dimensions. Then, the relationship of defects with the blue-emission PL is unfolded by electron energy loss spectroscopy, lifetime measurements, X-ray absorption, and Raman spectroscopic measurements. The defects acting as Lewis acid sites are utilized for selective ammonia detection. Huge enhancements of the obscured blue luminescence at 2.77 and 2.96 eV from the SnO2 QDs are observed because of interaction with ammonia. The linear variation of PL intensities with analyte concentrations and the recovery of the sensor are elaborated with detection up to 5 ppm. The interplay of defects in SnO2 is further established theoretically for site-specific interactions with ammonia by density functional theory (DFT) calculations. Thus, the unique mechanism revealed for the superlative performance of the PL sensor with uncapped SnO2 QDs provides a novel platform for defect-engineering-based optoelectronic applications.