We present an x-ray absorption study of the oxidation states of transition-metal-ions of LiMnO2 and its related materials, widely used as cathodes in Li-ion batteries. The comparison between the obtained spectrum and the configuration-interaction cluster-model calculations showed that the Mn3+ in LiMnO2 is a mixture of the high-spin and low-spin states. We found that Li deficiencies occur in the case of Cr substitution, whereas there are no Li deficiencies in the case of Ni substitution. We conclude that the substitution of charge-transfer-type Ni or Cu is effective for LiMnO2 battery materials.
The photoinduced valence dynamics of EuNi$_2$(Si$_{0.21}$Ge$_{0.79}$)$_2$ are investigated using time-resolved X-ray absorption spectroscopy for Eu $M_5$-edge. Through the pump-probe technique with synchrotron X-ray and Ti:sapphire laser pulse, a photoinduced valence transition is observed from Eu$^{3+}$ to Eu$^{2+}$. Because the lifetime of a photoinduced state can be up to 3 ns, a metastable state is considered to be realized. By comparing the experimental results with the theoretical calculations, the photoinduced valence transition between Eu 4$f$ and conduction electrons is quantitatively…
The effect of quantum lattice fluctuations on the optical-absorption spectra in the ground state of halogen-bridged mixed-valence transition-metal linear-chain complexes is studied by using a one-dimensional extended Peierls-Hubbard model. The nonadiabatic effects due to finite phonon frequency $ω_π>0$ are treated through an energy-dependent electron-phonon scattering function $δ(k^{\prime},k)$ introduced by means of an unitary transformation. The calculated optical-absorption spectra do not have the inverse-square-root singularity, but they have a peak above the gap edge and there exists a si…
We study resonant inelastic x-ray scattering (RIXS) peaks corresponding to low energy particle-hole excited states of metallic FeTe and semi-metallic TiSe$_2$ for photon incident energy tuned near the $L_{3}$ absorption edge of Fe and Ti respectively. We show that the cross section amplitudes are well described within a renormalization group theory where the effect of the core electrons is captured by effective dielectric functions expressed in terms of the the atomic scattering parameters $f_1$ of Fe and Ti. This method can be used to extract the dynamical structure factor from experimental R…
We study the mixed valence transition ($T$$_{v}$ $\sim$80 K) in EuNi$_{2}$(Si$_{0.2}$Ge$_{0.8}$)$_{2}$ using Eu 3$d-4f$ X-ray absorption spectroscopy (XAS) and resonant photoemission spectroscopy (RESPES). The Eu$^{2+}$ and Eu$^{3+}$ main peaks show a giant resonance and the spectral features match very well with atomic multiplet calculations. The spectra show dramatic temperature ($T$)-dependent changes over large energies ($\sim$10 eV) in RESPES and XAS. The observed non-integral mean valencies of $\sim$2.35 $\pm$ 0.03 ($T$ = 120 K) and $\sim$2.70 $\pm$ 0.03 ($T$ = 40 K) indicate homogeneous…
By means of photoemission and x-ray absorption spectroscopy, we have studied the electronic structure of (Ni,Zn,Fe,Ti)$_{3}$O$_{4}$ thin films, which exhibits a cluster glass behavior with a spin-freezing temperature $T_f$ of $\sim 230$ K and photo-induced magnetization (PIM) below $T_f$. The Ni and Zn ions were found to be in the divalent states. Most of the Fe and Ti ions in the thin films were trivalent (Fe$^{3+}$) and tetravalent (Ti$^{4+}$), respectively. While Ti doping did not affect the valence states of the Ni and Zn ions, a small amount of Fe$^{2+}$ ions increased with Ti concentrati…
X-ray absorption spectroscopy (XAS) is one of the most widely used experimental techniques to study the electronic and spatial structure of materials. Fluorescence yield mode is bulk-sensitive, but has several serious problems coming from saturation effects. In this study, we show the usefulness of partial fluorescence yields in addressing these problems. We discuss the different behaviors of La2NiMnO6 and LiMnO2 at the Mn 2p absorption edges. The total fluorescence yield produces misleading spectra for LiMnO2 due to the absence of high-Z (Z: atomic number) elements. We conclude that the measu…
Revealing fingerprints of valence excitons in x-ray absorption spectra with the Bethe-Salpeter equation
Universität Hamburg（汉堡大学）；The Hamburg Centre for Ultrafast Imaging (CUI)（汉堡超快成像中心）；Brandenburg University of Technology Cottbus-Senftenberg（勃兰登堡工业大学科特布斯-森夫滕贝格分校）
The valence and spin state evolution of Mn and Co on TbMn$_{\rm 1-x}$Co$_{\rm x}$O$_3$ series is precisely determined by means of soft and hard x-ray absorption spectroscopy (XAS) and K$β$ x-ray emission spectroscopy (XES). Our results show the change from Mn$^{3+}$ to Mn$^{4+}$ both high-spin (HS) together with the evolution from Co$^{2+}$ HS to Co$^{3+}$ low-spin (LS) with increasing $\rm x$. In addition, high energy resolution XAS spectra on the K pre-edge region are interpreted in terms of the strong charge transfer and hybridization effects along the series. These results correlate well w…
X-ray absorption spectroscopy was used to determine the valence state in La$_2$Co$_{1-x}$Mn$_{1+x}$O$_6$ ($x\approx 0.23$) thin films. We found that in spite of the non-stoichiometry, Co is in a divalent state while Mn ions show a mixed valence state. The relation of this finding with the magnetic properties of the films is discussed. X-ray magnetic circular dichroism measurements prove that magnetic anisotropy originates from Co spin-orbit coupling and it is strain-dependent: a strong increase of the angular contribution to the magnetic moment is found when in-plane (out-of-plane) and cell pa…
The Fe K X-ray absorption near edge structure (XANES) of BaFe2-xCoxAs2 superconductors was investigated. No appreciable alteration in shape or energy position of this edge was observed with Co substitution. This result provides experimental support to previous ab initio calculations in which the extra Co electron is concentrated at the substitute site and do not change the electronic occupation of the Fe ions. Superconductivity may emerge due to bonding modifications induced by the substitute atom that weakens the spin-density-wave ground state by reducing the Fe local moments and/or increasin…
Here we employ both Fe K and L2,3 edge x-ray absorption near-edge structure (XANES) spectroscopy techniques to clarify that iron in the B-site ordered double-perovskite halfmetal, Sr2FeMoO6.0, possesses a mixed-valence state, FeII/III, and accordingly molybdenum a mixed MoV/VI valence state. A reliable interpretation of the spectral features has been made possible by using a series of samples of the Sr2Fe(Mo,W/Ta)O6.0 system. Replacing MoV/VI gradually with WVI causes increasing amount of Fe to adopt the FeII state, whereas TaV substitution shifts the valence of iron towards FeIII. As the vale…
The reversible heat in lithium-ion batteries (LIBs) due to entropy change is fundamentally important for understanding the chemical reactions in LIBs and developing proper thermal management strategies. However, the direct measurements of reversible heat are challenging due to the limited temperature resolution of applied thermometry. In this work, by developing an ultra-sensitive thermometry with a differential AC bridge using two thermistors, the noise-equivalent temperature resolution we achieve (10 uK) is several orders of magnitude higher than previous thermometry applied on LIBs. We dire…
Harnessing X-ray Absorption Spectroscopy Data through Multimodal Mining of Battery Literature
Argonne National Laboratory（阿贡国家实验室）；NVIDIA（英伟达）；University of California, Berkeley（加州大学伯克利分校）；Lawrence Berkeley National Laboratory（劳伦斯伯克利国家实验室）；The University of Chicago（芝加哥大学）
Ti K-edge x-ray absorption near edge spectroscopy (XANES) was used to explore the Ti valence and coordination in Ti-activated sodium alanate. An empirical relationship was established between the Ti valence and the Ti K-edge onset based on a set of standards. This relationship was used to estimate oxidation states of the titanium catalyst in 2 mol% and 4 mol% Ti-doped NaAlH4. These results demonstrate that the formal titanium valence is zero in doped sodium alanate and nearly invariant during hydrogen cycling. A qualitative comparison of the edge fine structure suggests that the Ti is present …
Few-femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy, performed with optical 500-1000 nm supercontinuum and broadband XUV pulses (30-50 eV), simultaneously probes dynamics of photoexcited carriers in WS$_{2}$ at the W O$_3$ edge (37-45 eV) and carrier-induced modifications of core-exciton absorption at the W N$_{6,7}$ edge (32-37 eV). Access to continuous core-to-conduction band absorption features and discrete core-exciton transitions in the same XUV spectral region in a semiconductor provides a novel means to investigate the effect of carrier excitation on core-exciton…
X-ray absorption spectroscopy was used to study the microscopic origin of conductance and resistive switching in chromium doped strontium titanate (Cr:SrTiO3). Differences in the x-ray absorption near edge spectroscopy (XANES) at the Cr K-edge indicate that the valence of Cr changes from 3+ to 4+ underneath the anode of our sample device after the application of an electric field. Spatially resolved x-ray fluorescence microscopy ($μ$-XRF) maps show that the Cr4+ region retracts from the anode-Cr:SrTiO3 interface after a conducting state has been achieved. This interface region is studied with …
In2O3 is a prototype wide-band-gap semiconductor that exhibits metallic conductivity when highly doped with Sn while retaining a high degree of transparency to visible light. It is widely used as a transparent window/electrode in solar cells and LEDs. The functionality of In2O3 would be greatly extended if p-type conductivity could also be achieved. Using electronic structure calculations, we show that adding Bi to In2O3, in the form of dilute (In_{1-x}Bi_{x})_2O3} alloys, leads to a new valence band that is sufficiently higher in energy than the original O-2p valence band to allow for p-type …
Iron resonant valance band photoemission spectra of Sr substituted LaFe0.75Ni0.25 O3-δ have been recorded across the Fe 2p - 3d absorption threshold to obtain Fe specific spectral information on the 3d projected partial density of states. Comparison with La1-xSrxFeO3 resonant VB PES literature data suggests that substitution of Fe by Ni forms electron holes which are mainly O 2p character. Substitution of La by Sr increases the hole concentration to an extent that the eg structure vanishes. The variation of the eg and t2g structures is paralleled by the changes in the electrical conductivity.
Multiferroic bismuth ferrite (BiFeO3) thin films were prepared by pulsed laser deposition (PLD) technique. Electronic structures of the film have been studied by in situ photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS). Both the Fe 2p PES and XAS spectra show that Fe ion is formally in +3 valence state. The Fe 2p and O K edge XAS spectra indicate that the oxygen octahedral crystal ligand field splits the unoccupied Fe 3d state to t2g and eg states. Valence band Fe 2p-3d resonant photoemission results indicate that hybridization between Fe 3d and O 2p plays important rol…
The electronic structures of multiferroic oxides of Ba(1-x)Bi(x)Ti(0.9)Fe(0.1)O(3) (0 < x < 0.12) have been investigated by employing photoemission spectroscopy and soft x-ray absorption spectroscopy (XAS). The measured Fe and Ti 2p XAS spectra show that Ti ions are in the Ti4+ states for all x and that Fe ions are Fe2+-Fe3+ mixed-valent for x > 0. The valence states of Fe ions are found to be nearly trivalent for x=0, and decreases with increasing x from being nearly trivalent (v(Fe)~ 3) for x=0 to v(Fe)~ 2.6 for x=0.12. The valence states of both Ti and Ba ions do not change for all x < 0.12…
Perovskite-type BiNiO$_3$ is an insulating antiferromagnet in which a charge disproportionation occurs at the Bi site. La substitution for Bi suppresses the charge disproportionation and makes the system metallic. We have measured the photoemission and x-ray absorption (XAS) spectra of Bi$_{1-x}$La$_{x}$NiO$_{3}$ to investigate how the electronic structure changes with La doping. From Ni $2p$ XAS, we observed an increase of the valence of Ni from 2+ toward 3+. Combined with the core-level photoemission study, it was found that the average valence of Bi remains $\sim 4+$ and that the Ni valence…
Soft-X-ray emission and absorption spectroscopies with their elemental specificity are used to determine the local electronic structure of N atoms in Ga(In)AsN diluted semiconductor alloys (N concentrations about 3%) in view of applications of such materials in optoelectronics. Deviations of the N local electronic structure in Ga(In)AsN from the crystalline state in GaN are dramatic in both valence and conduction bands. In particular, a depletion of the valence band maximum in the N local charge, taking place at the N impurities, appears as one of the fundamental origins of reduced optical eff…
We report on the valence fluctuation of Ce in CeMo$_{2}$Si$_{2}$C as studied by means of magnetic susceptibility $χ(T)$, specific heat $C(T)$, electrical resistivity $ρ(T)$ and x-ray absorption spectroscopy. Powder x-ray diffraction revealed that CeMo$_{2}$Si$_{2}$C crystallizes in CeCr$_{2}$Si$_{2}$C-type layered tetragonal crystal structure (space group \textit{P4/mmm}). The unit cell volume of CeMo$_{2}$Si$_{2}$C deviates from the expected lanthanide contraction, indicating non-trivalent state of Ce ions in this compound. The observed weak temperature dependence of the magnetic susceptibili…
The electronic structure of LiNiO$_2$, a promising Li-ion battery cathode material, has remained a challenge to understand due to its highly covalent yet correlated nature. Here we elucidate the electronic structure in LiNiO$_2$ and the related compound NaNiO$_2$ using x-ray absorption spectra (XAS) and quantum many-body calculations. Notably, we use inverse partial fluorescence yield to correctly measure the Ni $L$-edge XAS, which is inaccurate using conventional methods. We show that the XAS are indicative of a strong Jahn-Teller effect in NaNiO$_2$ and a bond disproportionated state in LiNi…
An experimental technique of x-ray fluorescence holography for investigating valence-selective local structures was established by employing the incident x-ray energy at a characteristic one near an x-ray absorption edge, and it was adopted to discriminate environments around Yb2+ and Yb3+ ions in a YbInCu4 valence transition material below and above the transition temperature of 42 K. The reconstructed images of the neighboring atoms around Yb3+ show a fcc structure as observed by diffraction experiments, whereas those around Yb2+ have curious cross (+) features, indicating a positional shift…
To investigate the x-ray absorption (XAS) branching ratio from the core 4d to valence 5f states, we set up a theoretical framework by using a combination of density functional theory in the local density approximation and Dynamical Mean Field Theory (LDA+DMFT), and apply it to several actinides. The results of the LDA+DMFT reduces to the band limit for itinerant systems and to the atomic limit for localized f electrons, meaning a spectrum of 5f itinerancy can be investigated. Our results provides a consistent and unified view of the XAS branching ratio for all elemental actinides, and is in go…
Mixed-valence compound Pb3O4 (minium) has been studied using X-ray absorption near-edge structure (XANES) spectroscopy and DFT calculations. In spite of presence of two valence states of lead [Pb(II) and Pb(IV)], the XANES spectrum of studied system is corresponding to apparently unified, an intermediate valence state of Pb. On the other hand, the 207Pb NMR spectra definitely show two different spectral bands corresponding to different Pb2+ and Pb4+ ions in Pb3O4 crystal structure. The explanation of this contradiction is related to the basics of XANES and NMR spectroscopy.
We present an experimental study of the electronic structure of MnSi. Using X-ray Absorption Spectroscopy, X-ray photoemission and X-ray fluorescence we provide experimental evidence that MnSi has a mixed valence ground state. We show that self consistent LDA supercell calculations cannot replicate the XAS spectra of MnSi, while a good match is achieved within the atomic multiplet theory assuming a mixed valence ground state. We discuss the role of the electron-electron interactions in this compound and estimate that the valence fluctuations are suppressed by a factor of 2.5, which means that …
In order to probe the changes in the valence state and magnetic properties of Eu metal under extreme pressure, x-ray absorption near-edge spectroscopy, x-ray magnetic circular dichroism and synchrotron Mössbauer spectroscopy experiments have been carried out. The Mössbauer isomer shift exhibits an anomalous pressure dependence, passing through a maximum near 20 GPa. Density functional theory has been applied to give insight into the pressure-induced changes in both Eu's electronic structure and Mössbauer isomer shift. Contrary to previous reports, Eu is found to remain nearly divalent to the h…
The crystal structures and the physical (magnetic, electrical transport and thermodynamic) properties of the ternary compounds CeRhSi2 and Ce2Rh3Si5 (orthorhombic CeNiSi2- and U2Co3Si5-type structures, respectively) were studied in wide ranges of temperature and magnetic field strength. The results revealed that both materials are valence fluctuating systems, in line with previous literature reports. Direct evidence for valence fluctuations was obtained by means of Ce LIII-edge x-ray absorption spectroscopy and Ce 3d core-level x-ray photoelectron spectroscopy. The experimental data were confr…
The local electronic structure of N atoms in a diluted GaAs1-xNx (x=3%) alloy, in view of applications in optoelectronics, is determined for the first time using soft-X-ray absorption (SXA) and emission (SXE). Deviations from crystalline GaN, in particular in the conduction band, are dramatic. Employing the orbital character and elemental specificity of the SXE/SXA spectroscopies, we identify a charge transfer from the N atoms at the valence band maximum, reducing the overlap with the wavefunction in conduction band minimum, as the main factor limiting the optical efficiency of GaAs1-xNx alloy…
We use x-ray absorption spectroscopy to investigate the local structure and electronic properties of bulk La$_{1-y}$Sr$_{y}$Co$_{1-x}$Nb$_x$O$_3$ ($y=$ 2$x$ as LSCNO and $y=$ 0 as LCNO) samples. The x-ray absorption near-edge spectra (XANES) of LSCNO at Co K-edge affirm the valence state of Co in 3+. However, in the case of the LCNO, a subtle variation in the valence state of Co ions from 3+ to 2+ is evident with Nb substitution. The detailed analysis of the Fourier transform (FT) of the extended x-ray absorption fine structure (EXAFS) for the LSCNO samples exhibit the two groups of the bond-l…
We have investigated the evolution of the electronic properties of La1-xSrxCrO3 (for the full range of x) epitaxial films deposited by molecular beam epitaxy (MBE) using x-ray diffraction, x-ray photoemission spectroscopy, Rutherford backscattering spectrometry, x-ray absorption spectroscopy, electrical transport, and ab initio modeling. LaCrO3 is an antiferromagnetic insulator whereas SrCrO3 is a metal. Substituting Sr2+ for La3+ in LaCrO3 effectively dopes holes into the top of valence band, leading to Cr4+ (3d2) local electron configurations. Core-level and valence-band features monotonical…
For the orthorhombic intermetallic semiconductor Al$_2$Ru, the bandstructure, valence charge density, zone center optical phonon frequencies, and Born effective charge and electronic dielectric tensors are calculated using variational density functional perturbation theory with {\em ab initio} pseudopotentials and a plane wave basis set. Good agreement is obtained with recent measurements on polycrystalline samples which showed anomalously strong far IR absorption by optical phonons, while analysis of the valence charge density shows that the static ionic charges of Al and Ru are negligible. H…
We have studied the electronic structure of epitaxially grown thin films of La$_{1-x}$Sr$_x$FeO$_3$ by {\it in-situ} photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS) measurements. The Fe 2$p$ and valence-band PES spectra and the O $1s$ XAS spectra of LaFeO$_3$ have been successfully reproduced by configuration-interaction cluster-model calculation and, except for the satellite structure, by band-structure calculation.From the shift of the binding energies of core levels, the chemical potential was found to be shifted downward as $x$ was increased. Among the three peaks …
We present an x-ray absorption study of the dependence of the V oxidation state on the thickness of LaVO$_3$ (LVO) and capping LaAlO$_3$ (LAO) layers in the multilayer structure of LVO sandwiched between LAO. We found that the change of the valence of V as a function of LAO layer thickness can be qualitatively explained by a transition between electronically reconstructed interfaces and a chemical reconstruction. The change as a function of LVO layer thickness is complicated by the presence of a considerable amount of V$^{4+}$ in the bulk of the thicker LVO layers.
We have studied the electronic structure of Li$_{1+x}$[Mn$_{0.5}$Ni$_{0.5}$]$_{1-x}$O$_2$ ($x$ = 0.00 and 0.05), one of the promising cathode materials for Li ion battery, by means of x-ray photoemission and absorption spectroscopy. The results show that the valences of Mn and Ni are basically 4+ and 2+, respectively. However, the Mn$^{3+}$ component in the $x$ = 0.00 sample gradually increases with the bulk sensitivity of the experiment, indicating that the Jahn-Teller active Mn$^{3+}$ ions are introduced in the bulk due to the site exchange between Li and Ni. The Mn$^{3+}$ component gets neg…
$Li_{2}RuO_{3}$ with a honeycomb structure undergoes a drastic transition from a regular honeycomb lattice with the $C2/m$ space group to a valence bond solid state of the $P2_{1}/m$ space group with an extremely strong dimerization at 550 K. We synthesized $Li_{2}Ru_{1-x}Mn_{x}O_{3}$ with a full solid solution and investigated doping effects on the valence bond solid state as a function of Mn content. The valence bond solid state is found to be stable up to $x = 0.2$, based on our extensive experiments: structural studies, resistivity, and magnetic susceptibility. On the other hand, the exten…
Using circularly polarised radiation and a combination of bulk-sensitive hard X-ray photoelectron spectroscopy and X-ray-absorption spectroscopy (XAS) we studied the electronic and magnetic structure of epitaxial Mn$_{1.8}$Co$_{1.2}$Ga thin films. Spin resolved Bloch spectral functions, density of states as well as charge and magnetisation densities were investigated by a first-principles analysis of full potential, fully relativistic Korringa--Kohn--Rostoker calculations of the electronic structure. The valence states were experimentally investigated by using linear dichroism in the angular d…
Time-dependent density functional theory (TDDFT) simulations of transient core-level spectroscopies require a balanced treatment of both valence- and core-electron excitations. To this end, tuned range-separated hybrid exchange-correlation functionals within the generalized Kohn-Sham scheme offer a computationally efficient means of simultaneously improving the accuracy of valence and core excitation energies in TDDFT by mitigating delocalization errors across multiple length-scales. In this work range-separated hybrid functionals are employed in conjunction with the velocity-gauge formulation…
The electronic structure of (Ce,Yb)CoIn5 has been studied by a combination of photoemission, x-ray absorption and bulk property measurements. Previous findings of a Ce valence near 3+ for all x and of an Yb valence near 2.3+ for x>0.3 were confirmed. One new result of this study is that the Yb valence for x<0.2 increases rapidly with decreasing x from 2.3+ toward 3+, which correlates well with de Haas van Alphen results showing a change of Fermi surface around x=0.2. Another new result is the direct observation by angle resolved photoemission Fermi surface maps of about 50% cross sectional are…
We present a combined experimental and theoretical study of the electronic structure of the intermetallic compound TiGePt by means of photoelectron spectroscopy, x-ray absorption spectroscopy and fullpotential band structure calculations. It was recently shown that TiGePt undergoes a structural phase transition by heating which is accompanied by a large volume contraction and a drastic change of physical properties, in particular a large decrease of the electrical resistivity. The present study revealed substantial differences in the electronic structure for the two TiGePt modifications, altho…
The electronic structure of pulsed laser deposited Mo1-xFexO2 (x=0, 0.02 and 0.05) thin films has been investigated using resonant photoemission spectroscopy near Mo-4p absorption edge. In all the samples a broad Fano- like resonance peak at ~46 eV is observed in the whole area of the valence band which indicates the contribution of the Mo-4d states in the entire valence band region. The doping of Fe in these films leads to decrease in Mo 4d states contributing to electronic states at lower binding energy region. In addition to this, we also observe a shoulder at 4.9 eV in the valence band spe…
We report a novel mechanism, consisting of redistribution of valence electrons near the Fermi level, during interactions of intense femtosecond X-ray pulses with a Co/Pd multilayer. The changes in Co 3d valence shell occupation were directly revealed by fluence-dependent changes of the Co L$_3$ X-ray absorption and magnetic circular dichroism spectra near the excitation threshold. The valence shell redistribution arises from inelastic scattering of high energy Auger electrons and photoelectrons that lead to transient holes below and electrons above the Fermi level on the femtosecond time scale…
X-ray absorption spectroscopy measurements in Pr0.5Ca0.5CoO3 and (Pr,Y)0.55Ca0.45CoO3 compositions reveal that the valence of praseodymium ions is stable and essentially +3 (Pr [4f 2]) in the metallic state, but abruptly changes when carriers localize approaching the oxidation state +4 (Pr [4f 1]). This mechanism appears to be the driving force of the metal-insulator transition. The ground insulating state of Pr0.5Ca0.5CoO3 is an homogeneous Co3.5-d state stabilized by a charge transfer from Pr to Co sites: 1/2Pr3+ + Co3.5 \to 1/2Pr3+2d + Co3.5-d, with 2d \approx 0.26 e-.
Na-ion conduction, and correlations between Na-ion conduction pathways and crystal structure have been investigated as a function of temperature in the layered battery material Na2Ni2TeO6 by impedance spectroscopy and neutron diffraction, respectively. The impedance data reveal an ionic conductivity 2x10-4 S/m at 323 K which strongly enhances with increasing temperature and attains a high value of ~ 0.03 S/m at 423 K. The temperature dependent conductivity data show an Arrhenius type behavior with average activation energy (Ea) of ~ 0.58(3) eV for T > 383 K. By employing soft-bond valence sum …
X-ray Computed Tomography (X-ray CT) is a well-known non-destructive imaging technique where contrast originates from the materials' absorption coefficients. Novel battery characterization studies on increasingly challenging samples have been enabled by the rapid development of both synchrotron and laboratory-scale imaging systems as well as innovative analysis techniques. Furthermore, the recent development of laboratory nano-scale CT (NanoCT) systems has pushed the limits of battery material imaging towards voxel sizes previously achievable only using synchrotron facilities. Such systems are…
We have investigated the electronic and optical properties of epitaxial La1-xSrxFeO3 for x from 0 to 1 prepared by molecular beam epitaxy. Core-level and valence-band x-ray photoemission features monotonically shift to lower binding energy with increasing x, indicating downward movement of the Fermi level toward to the valence band maximum. Both Fe 2p and O 1s spectra broaden to higher binding energy with increasing x, consistent with delocalization of Sr-induced holes in the Fe 3d/O 2p hybridized valence band. Combining X-ray valence band photoemission and O K-edge x-ray absorption data, we m…
Band gap engineering in SrTiO${}_{3}$ and related titanate perovskites has long been explored due to the intriguing properties of the materials for photocatalysis and photovoltaic applications. A popular approach in the materials chemistry community is to substitutionally dope aliovalent transition metal ions onto the B site in the lattice to alter the valence band. However, in such a scheme there is limited control over the dopant valence, and compensating defects often form. Here we demonstrate a novel technique to controllably synthesize Fe$^{2+}$- and Fe$^{3+}$-doped SrTiO${}_{3}$ thin fil…
X-ray absorption and resonant inelastic x-ray scattering measurements are carried out on lithium nitrate LiNO$_3$. The $σ$ orbitals around the nitrogen atoms exhibit a large lifetime effect. Experimentally, this is manifest as an apparent weakening of the x-ray emission signal from these states, but a closer examination shows that instead it is due to extreme broadening. This echos previous studies on ammonium nitrate, which, despite large differences in the cation and space group, showed a similar effect associated with the nitrate. Using first-principles $GW$ self-energy and Bethe-Salpeter e…
We performed a systematic study of soft X-ray absorption spectroscopy in various manganese oxides and fluorides. Both Mn L-edges and ligand (O and F) K-edges are presented and compared with each other. Despite the distinct crystal structure and covalent/ionic nature in different systems, the Mn-L spectra fingerprint the Mn valence and spin states through spectral lineshape and energy position consistently and evidently. The clear O- and F- K pre-edge features in our high resolution spectra enable a quantitative definition of the molecular orbital diagram with different Mn valence. In addition,…
Temperature dependence of the X-ray absorption near-edge structure (XANES) spectra at the Pr $L_{3}$- and Tb $L_{3}$-edges was measured for the (Pr$_{1-y}$Tb$_{y})_{0.7}$Ca$_{0.3}$CoO$_{3}$ system, in which a metal-insulator (MI) and spin-state (SS) transition took place simultaneously at a critical temperature $T_{\rm MI}$. A small increase in the valence of the terbium ion was found below $T_{\rm MI}$, besides the enhancement of the praseodymium valence; the trivalent states, which are stable at room temperature, change to a 3+/4+ ionic mixture at low temperatures. In particular for the $y$=…
