Transmission measurements of soft X-ray absorption fine structure in solids by a new scintillation technique

Transmission measurements of the extended X-ray absorption fine structure above the oxygen K-edge have been made by using a new scintillation detection technique. The absorption spectrum is in close resemblance with the total electron yield spectrum recorded at the same time. This new technique is of interest for studies of soft X-ray absorption spectroscopy for thin films of solid materials.     

Resonant inelastic X-ray scattering (RIXS) spectroscopy at the Mn K absorption pre-edge—a direct probe of the 3d orbitals

A study of the Mn K absorption pre-edges in oxides using resonant inelastic X-ray scattering (RIXS) spectroscopy is presented. The energy transfer dimension enhances the separation of the pre-edge (predominantly 1s to 3d transitions) from the main K-edge and a detailed analysis is thus possible. The RIXS spectra are sensitive to the Mn spin state. The technique thus yields detailed information on the electronic structure that is not accessible in conventional K-edge absorption spectroscopy. The line splittings can be understood within a ligand field multiplet model, showing the importance of (2p,3d) two-electron interactions that give rise to the spin-sensitivity.     

Cooperative Jahn-Teller phase transition in LaMnO3 studied by X-ray absorption spectroscopy

The local structure of LaMnO3 across the Jahn-Teller (JT) transition at T(JT)=750 K was studied by means of x-ray absorption near edge structure and extended x-ray absorption fine structure at the Mn K-edge. Our results indicate a similar electronic local structure for Mn atoms above and below T(JT) and a dynamical tetragonal JT distortion of MnO6 octahedra above T(JT). The structural transition is originated by the ordering of tetragonally distorted octahedra. The entropy content of the transition is analyzed within the framework of the three-state Potts model with nearest neighbor antiferrodistortive coupling.     

Atomic structure of nickel phthalocyanine probed by X-ray absorption spectroscopy and density functional simulations

The local atomic structure of Ni in nickel phthalocyanine was studied by K-edge X-ray absorption fine structure spectroscopy. The obtained inter atomic nickel-nitrogen distance differs from the reference X-ray diffraction data so an additional study was performed within density functional theory framework. The justification of the used theoretical approach was provided by a comparison of theoretical free electron densities of states with experimental Ni K-edge X-ray absorption near edge spectra. The refined Ni local environment retain the reference structure of the molecule except for the length of Ni-N bond which increases to 1.90 Å.     

在硅酸盐矿物,玻璃和熔体中Si和Al的配位与局部结构：K—边 …

本文采用步辐射的ＳｉＫ－边Ｘ－射线吸收近边结构（ＸＡＮＥＳ）谱研究了Ｓｉ在ＳｉＯ２－Ｐ２Ｏ５和Ｎａ２Ｏ－ＳｉＯ２－Ｐ２Ｏ５的低压磷硅酸盐玻璃中结构与配位,以及Ｓｉ的配位几何随玻璃中Ｐ２Ｏ５含量而变化：同步辐射的Ａｌ Ｋ－边ＸＡＮＥＳ谱研究了Ａｌ在铝硅酸盐成分为ＮａＡｌＳｉ２Ｏ６－ＮａＡｌＳｉ３Ｏ８的玻璃和熔体中的配位和局部结构,并提供了直接的实验证据该成分的玻璃体系中由于压力的变化所诱导Ａｌ配位的     

Scattering of F atoms and anions on a TiO2(1 1 0) surface

Results of a study of energy losses and electron transfer processes for grazing scattering of fluorine atoms and anions scattering along different azimuthal orientations of the TiO₂ crystal are presented. We observe strong variations in the overall intensity of scattered particles which are due to channelling effects. The energy losses do not show strong variations as a function of crystal azimuth except for the case of scattering along the (0 0 1) direction between the bridging oxygen atom rows, where we also observe differences in the energy losses of scattered ions and neutrals. We attribute this to the fact that larger F⁻ survival occurs for trajectories staying farther from the surface, when also the energy losses remain small. The overall characteristics of energy losses are attributed mainly to trajectory effects due to scattering in regions of different electron density. Measurements of the ratio of scattered ions to the total scattered flux, i.e. the ion fractions which reflect electron capture and loss processes, show that these are not the same for incident anions and atoms. A strong difference for scattering along the (0 0 1) direction is observed, where at low incident energies a strong survival of incident ions occurs. These results are tentatively discussed in terms of non resonant electron capture at lattice O⁻ sites and electron loss into the conduction band or by collisional detachment with bridging O atoms.     

纤锌矿结构Zn1-xMgxO电子结构及吸收光谱的第一性原理研究

采用第一性原理计算方法,计算了纤锌矿结构Zn_1-xMg_xO(x=0,00625,0125,025)的电子结构及吸收光谱. 计算结果表明,Mg的掺入使ZnO的电子结构发生了较大的改变,与Mg邻近的O原子得到电子的数目明显增大,进而O原子返回部分电子给邻近Zn原子. Zn-O间相互作用减弱,禁带宽度变大,这也从同一合金中Zn4s上移的程度得到证实. 其吸收光谱也随着Mg的掺入出现蓝移现象,其吸收边对应波长分别为379, 关键词： 第一性原理计算 电子结构 吸收光谱 纤锌矿结构ZnO     

Collective modes and the far-infrared absorption of the two-dimensional electron gas in a periodic quantizing magnetic field

We investigate the far-infrared (FIR) absorption of a two-dimensional electron gas in a periodically modulated quantizing magnetic field. The magnetic field varies along only one spatial direction and the external time-dependent electric field is linearly polarized along that axis. The mutual Coulomb interaction of the electrons is treated self-consistently in the ground state and in the absorption calculation within the Hartree approximation. The effects of the magnetic material on top of the heterostructure as a grating coupler is included in the time-dependent incident FIR electric field. We show that, similar to an electric modulation, the absorption can be directly correlated to the underlying electronic energy bands. In addition, the magnetic modulation leads to absorption spectra with a richer structure due to the quite different static response of the electron density to the modulation.     

Charge compensation and capacity fading in LiCoO_2 at high voltage investigated by soft x-ray absorption spectroscopy

In order to obtain an in-depth insight into the mechanism of charge compensation and capacity fading in LiCoO_2, the evolution of electronic structure of LiCoO_2 at different cutoff voltages and after different cycles are studied by soft x-ray absorption spectroscopy in total electron(TEY) and fluorescence(TFY) detection modes, which provide surface and bulk information, respectively. The spectra of Co L2,3-edge indicate that Co contributes to charge compensation below 4.4 V.Combining with the spectra of O K-edge, it manifests that only O contributes to electron compensation above 4.4 V with the formation of local O 2 p holes both on the surface and in the bulk, where the surficial O evolves more remarkably. The evolution of the O 2 p holes gives an explanation to the origin of O_2~-or even O_2. A comparison between the TEY and TFY of O K-edge spectra of LiCoO_2 cycled in a range from 3 V to 4.6 V indicates both the structural change in the bulk and aggregation of lithium salts on the electrode surface are responsible for the capacity fading. However, the latter is found to play a more important role after many cycles.     

Total-reflection inelastic X-ray scattering from a 10-nm thick La0.6Sr0.4CoO3 thin film

To study equilibrium changes in composition, valence, and electronic structure near the surface and into the bulk, we demonstrate the use of a new approach, total-reflection inelastic x-ray scattering, as a sub-keV spectroscopy capable of depth profiling chemical changes in thin films with nanometer resolution. By comparing data acquired under total x-ray reflection and penetrating conditions, we are able to separate the O K-edge spectra from a 10 nm La0.6Sr0.4CoO3 thin film from that of the underlying SrTiO3 substrate. With a smaller wavelength probe than comparable soft x-ray absorption measurements, we also describe the ability to easily access dipole-forbidden final states, using the dramatic evolution of the La N4,5 edge with momentum transfer as an example.     

XAFS spectra from X-ray fluorescence Kβ line using conventional energy-discriminating detector

X-ray fluorescence spectra of copper (Cu) metal, copper monoxide (CuO), and potassium chromate (K₂CrO₄) were recorded as a function of incident X-ray energy near the Cu K-edge and chromium (Cr) K-edge, respectively, using a conventional silicon drift detector. The spectra contained components due to elastic, inelastic, and multiple scattering, in addition to the Kα and Kβ lines. Cu and Cr K-edge X-ray absorption fine structure (XAFS) spectra of Cu, CuO, and K₂CrO₄ were obtained by an intensity analysis of the Kα and Kβ lines. The intensity of the Kβ line for the different incident photon energies was obtained by numerically removing the additional scattering components using the MUSCAT program. These spectra exhibited a jump near the K absorption edges, which reproduced the spectral features obtained in transmission mode for both Cu, CuO, and K₂CrO₄. A chemical shift was also clearly identified in the X-ray absorption near edges structure using the X-ray fluorescence Kβ line. In addition, the Cr K-edge extended XAFS spectrum of K₂CrO₄ was clearly observed using the Cr Kβ fluorescent line. The XAFS measurements on the Kα and Kβ lines are possible, and they carry equally valuable information.     

Total electron yield XANES of zinc-blende MnTe

The electronic structure and chemical bond of zinc-blende (zb) MnTe have been studied by using total-electron-yield (TEY) X-ray absorption near-edge structure (XANES) spectroscopy. Close resemblances of the shape of Mn K-edge XANES in zb-MnTe and in Zn_1−xMn_xTe [A. Titov, X. Biquard, D. Halley, S. Kuroda, E. Bellet-Amalric, H. Mariette, J. Cibert, A.E. Merad, G. Merad, M.B. Kanoun, E. Kulatov, Yu.A. Uspenskii, Phys. Rev. B 72 (2005) 115209] indicated predominant influence of the 1st coordination shell. In particular, identical single-peak pre-edge structure for both cases was mainly ascribed to the Mn 1s-3d/4p weakly allowed dipole transitions. The quantitative analysis of XANES in zb-MnTe concerned the observed chemical shift of Mn K-edge threshold energy and a magnitude of the relevant cation-anion charge transfer (or effective cation charge), q(Mn-Te) [calculated after M. Kitamura, H. Chen, J. Phys. Chem. Solids 52 (1991) 731]. It also provided a comparison with our earlier X-ray absorption studies of Zn_1−xMn_xB alloys (B = S, Se). The estimated charge transfer within the chemical bond of zb-MnTe enabled us to complete the q(Mn-B) versus chalcogen ligand (B = S, Se, Te) dependence and to interpret it in terms of p-d hybridization and a contribution of Mn 3d electrons to the overall charge transfer.     

Electronic Absorption Spectra of Two 3-Aryl-pyridazinium-2,4,6-picryl-benzoyl-methylids

The visible electronic absorption spectra of two carbanion disubstituted cycloimmonium ylids having a 3-aryl-pyridazinium derivative as cation and a common disubstituted carbanion (-2,4,6-picryl-benzoyl) were studied in solvents with different physical and chemical properties. The visible electronic absorption band of 3-aryl-pyridazinium ylids is attributed to an electron charge transfer from the carbanion toward the heterocycle. The solvent effects on the visible electronic band of the studied ylids were described both by empirical parameters defined by Kosower and by using the theory of a dielectric homogeneous solution. Some remarks about the nature of the molecular interactions in the 3-aryl-phthalazinium-2,4,6-picryl-benzoyl methylid solutions are made in this paper on the basis of solvatochromic study.     

Unraveling the symmetry of the hole states near the Fermi level in the MgB2 superconductor

We use x-ray absorption spectroscopy (XAS) and electron energy loss spectroscopy (EELS) to study the fine structure at the K edge of boron in MgB(2). We observe in XAS a peak of width 0.7 eV at the edge threshold, signaling a narrow energy region with empty boron p states near the Fermi level. The changes in the near edge structure observed in EELS with direction of the momentum transfer imply that these states have p(x)p(y) symmetry. Our observations are consistent with electronic structure calculations indicating a narrow energy window of empty p(x)p(y) states that falls to zero at 0.8 eV above the Fermi level. The disappearance of the p(x)p(y) feature in EELS at grain boundaries suggests that this signature may become powerful in probing superconductivity at nanoscale.     

Three Dimensionality and Orbital Characters of the Fermi Surface in (Tl,Rb)_{y}Fe_{2-x}Se_{2}

We report a comprehensive angle-resolved photoemission spectroscopy study of the tridimensional electronic bands in the recently discovered Fe selenide superconductor (Tl,Rb)_{y}Fe_{2-x}Se_{2} (T_{c}=32 K). We determined the orbital characters and the k_{z} dependence of the low energy electronic structure by tuning the polarization and the energy of the incident photons. We observed a small 3D electron Fermi surface pocket near the Brillouin zone center and a 2D like electron Fermi surface pocket near the zone boundary. The photon energy dependence, the polarization analysis and the local-density approximation calculations suggest a significant contribution from the Se 4p_{z} and Fe 3d_{xy} orbitals to the small electron pocket. We argue that the emergence of Se 4p_{z} states might be the cause of the different magnetic properties between Fe chalcogenides and Fe pnictides.     

The near edge structure of cubic boron nitride

We compare the near edge structure (NES) of cubic boron nitride (cBN) measured using both electron energy loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) with that calculated using three commonly used theoretical approaches. The boron and nitrogen K-edges collected using EELS and XAS from cBN powder were found to be nearly identical. These experimental edges were compared to calculations obtained using an all-electron density functional theory code (WIEN2k), a pseudopotential density functional theory code (CASTEP) and a multiple scattering code (FEFF). All three codes were found to reproduce the major features in the NES for both ionisation edges when a core-hole was included in the calculations. A partial core hole (1/2 of a 1s electron) was found to be essential for correctly reproducing features near the edge threshold in the nitrogen K-edge and to correctly obtain the positions of all main peaks. CASTEP and WIEN2k were found to give almost identical results. These codes were also found to produce NES which most closely matched experiment based on χ² calculations used to qualitatively compare theory and experiment. This work demonstrated that a combined experimental and theoretical approach to the study of NES is a powerful way of investigating bonding and electronic structure in boron nitride and related materials.     

Investigation of the structural distortion in FeSex crystals by X-ray absorption near edge structures (XANES) spectroscopy

Crystals of the new superconductor FeSe were investigated by X-ray absorption near edge structures spectroscopy (XANES) in the temperature range 300-77 K. Crystals with Se content varying from x=1-0.8 were used. The Fe K-edge spectra show a structure distortion and increase in hole content as x decreases. The Fe K-edge spectra also show changes when the crystals are cooled to 100 K which may be related to the orthorhombic distortion reported in these crystals. The data is examined in conjunction with XRD measurements on the crystals to seek a correlation.     

苝四甲酸二酐薄膜电子结构的同步辐射共振光电子能谱研究

利用基于同步辐射的近边X射线吸收精细结构谱(NEXAFS)和共振光电子谱(RPES)研究了苝四甲酸二酐分子(PTCDA)薄膜的电子结构.碳K边NEXAFS谱中能量小于290 eV的四个峰对应于PTCDA分子不同化学环境碳原子1s电子到未占据分子轨道的共振跃迁.RPES谱中观察到共振光电子发射和共振俄歇电子发射导致的共振峰结构,以及二次谐波激发的碳1s信号.根据电子动能对入射光能量的依赖性分别对三类峰结构进行了归属.同时,发现PTCDA分子轨道共振光电子峰的强度具有光子能量依赖性.这种能量选择性共振增强效应是由于PTCDA分子轨道空间分布差异导致的.共振俄歇峰主要源于高结合能(4.1 eV)分子轨道能级电子参与的退激发过程.明确RPES实验谱图中各个峰结构的起源有助于准确利用基于RPES的芯能级空穴时钟谱技术定量估算有机分子/电极异质界面处电子从分子未占据轨道到电极导带的超快转移时间.     

Oxygen contaminants affecting on the electronic structures of the carbon nano tubes grown by rapid thermal chemical vapor deposition

Oxygen-related electronic structures of CNTs (carbon nanotubes) grown by rapid thermal chemical vapor deposition (RT-CVD) have been investigated by using partial electron yield near edge X-ray absorption spectroscopy (PEY-NEXAFS) and X-ray photoelectron spectroscopy (XPS). On the CNT surface with increased oxygen resulting from e-beam irradiation under the O₂ gas environment, C k-edge NEXAFS spectra showed an increase of the oxygen-related resonance peaks ranging from 287 to 289 eV whereas the sp² related peak at 285.4 eV was nearly unchanged. After the complete removal process of the oxygen atom on the surface by annealing the sample at 500 °C for 30 min, C K-edge spectra showed an abrupt decrease of the oxygen-related resonance peaks in 287-289 eV and an increase of the sp² related peak at 285.4 eV, indicating that the degree of crystallinity in the CNT sample was improved.     

Simulating the oxygen K-edge spectrum from grain boundaries in ceramic oxides using the multiple scattering methodology

In this paper we demonstrate the use of the multiple scattering methodology to interpret oxygen K-edge spectra from both the bulk and grain boundaries in a variety of ceramic oxides. The experimental electron energy loss spectra (EELS) used in this study, were obtained from a dedicated scanning transmission electron microscope (STEM). Using the STEM to obtain the spectra has the advantage that each spectrum can be acquired with atomic spatial resolution. While the energy resolution is limited to approximately 0.8 eV, and the angular integration in the microscope apertures precludes momentum resolved spectroscopy, this unprecedented spatial resolution allows the electronic structure at individual defect sites to be determined. Additionally, as the microscope can also provide an atomic resolution image of the defect, the relationship between the atomic structure of the defect and its local electronic structure can be determined. In practice, this is achieved by using the structure observed in the image to build the real space atomic cluster for multiple scattering simulations. Detailed interpretation of the simulations of oxygen K-edge spectra from bulk MgO, CaO, SrTiO3, TiO2, MnO2, Mn3O4, Mn2O3 and MnO are presented. In addition, the simulations from grain boundaries in TiO2 (undoped) and SrTiO3 (undoped and Mn doped) are discussed in relation to quantifying the changes in the local electronic structure that are a direct consequence of the defect structure. The simulations are used to make interpretations of the structure-property relationships at these grain boundaries.