XANES and EXAFS in Cu-Ti and Ni-Zr glasses

X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements have been done at the K-edge of Cu in Cu-Ti glasses and on the K-edges of Ni and Zr in Ni-Zr glasses using a synchrotron radiation source. The results are discussed in terms of the shape shift and intensity of the absorption edge as well as the principal absorption maximum. The values of bondlength calculated by the one-electron multiple scattering XANES theory as well as the graphical analysis EXAFS technique show good agreement.     

Local structure of Mn in (Ga,Mn)As probed by X-ray absorption spectroscopy

Local structure of Mn atoms in Ga_1−xMn_xAs epilayers was studied using the X-ray absorption fine structure (XAFS) at Mn K-edge. X-ray near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) techniques were used. XAFS spectra for different Mn sites has been calculated and compared with the experimental data. Multi-parameter fitting of the EXAFS data indicates that 15-25% of Mn atoms are in interstitial sites in the as grown films. The Mn-As bond length has been found longer than Ga-As bond length in GaAs for both substitutional (Mn_Ga) and interstitial (Mn_I) sites.     

Structural characterization study of nickel ferrite particles dispersed in a corrosion product deposit layer

Using X-ray absorption fine structure spectroscopy, both EXAFS and XANES, the cation distributions in NiFe₂O₄ particles dispersed in a corrosion product deposit layer have been studied. The specimen was obtained from a selected fuel rod used in a commercial boiling water reactor plant. EXAFS data allowed the quantitative determination of specific site distributions for all transition metal cations in Ni-ferrite deposits. The results show that the analyzed NiFe₂O₄ particles do not have a totally inverted spinel structure. The relative occupancy of iron and nickel cations in the tetrahedral and octahedral sites of the spinel lattice is determined from the measured data.     

Icosahedral order in Cu-Zr amorphous alloys studied by means of X-ray absorption fine structure and molecular dynamics simulations

We have used the X-ray absorption fine structure method and molecular dynamics (MD) simulations to characterize atomic order in Cu-Zr metallic glasses (MGs). The microstructure of these MGs is described in terms of interconnected icosahedral-like clusters (superclusters) which are basic building units reproducing the stoichiometry of the system. The equilibrium MD configurations are used as an input for ab initio calculations of the extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectra. The theoretical EXAFS and XANES spectra are compared with those measured for rapidly quenched glassy Cu-Zr alloys. We demonstrate that the experimental results are well reproduced by EXAFS modeling of the population of the superclusters derived from the MD configuration. The average local structural motif can be approximated by Cu-centered icosahedral-like cluster satisfying the condition of maximal local packing efficiency and approximating the system stoichiometry. The simulated XANES exhibits good agreement with experiment, indicating that the atomic order of the MD configuration is consistent with that of the real alloy structure over distances of about 1?nm.     

Structural study of Co/Pd(1 1 1) and CO/Co/Pd(1 1 1) by surface X-ray absorption fine structure spectroscopy

The structure of the Co thin films on Pd(1 1 1) and the effect of the CO adsorption on Co thin films were studied by Co K-edge surface X-ray absorption fine structure (XAFS). The polarization dependences of the X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra indicate that Co thin films grow in the fcc stacking mode on Pd(1 1 1) up to 12 ML. The analysis of the nearest neighbor shell shows little mechanical strain at the interface, indicating that Co atom does not grow pseudomorphically on Pd(1 1 1). There is no alloy-like structure at the interface. CO adsorption causes no structural change of the Co thin films but modifies the Co surface electronic state. These structural studies provide deep insight in the magnetic property of the Co thin films on Pd(1 1 1).     

On the state of iron in a clinoptilolite

The characterization of an iron-containing natural zeolitic sample from the deposit of Tasajeras (Cuba) has been carried out by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS),⁵⁷Fe Mössbauer spectroscopy and Fe K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). The results show that iron is mainly located (ca. 96%) as Fe³⁺ in an octahedral site of the clinoptilolite framework. No evidence of tetrahedrally coordinated Fe³⁺ was found. The remaining 4% Fe is located as Fe²⁺ in an extraframework octahedral site, probably as a solvated ion, within the clinoptilolite structure.     

XRD AND EXAFS INVESTIGATION OF THE DECOMPOSITION OF Co-Cu SOLID SOLUTION PREPARED BY MELT SPINING

High solid-solubility Co₁₅Cu₈₅ alloys were prepared by melt spining and then submitted to isothermal and anisothermal annealing to obtain granular alloys. The synchrotron radiation X-ray diffraction patterns and extended X-ray absorption fine structure (EXAFS) spectra were measured to investigate the decomposition of supersaturated solid solution upon annealing. Experimental results indicated the precipitation of ultrafine Co-rich particles occurred at about 500℃ and the annealing had a great influence on the middle-range order of Co atoms. While the fitted EXAFS spectra showed that the interfaces of Co precipitates seem to be enriched with vacancy-type defects, leading to distorted interfaces.     

Influence of synthesis method on structural and magnetic properties of cobalt ferrite nanoparticles

The Co–ferrite nanoparticles having a relatively uniform size distribution around 8 nm were synthesized by three different methods. A simple co-precipitation from aqueous solutions and a co-precipitation in an environment of microemulsions are low temperature methods (50 °C), whereas a thermal decomposition of organo-metallic complexes was performed at elevated temperature of 290 °C. The X-ray diffractometry (XRD) showed spinel structure, and the high-resolution transmission electron microscopy (HRTEM) a good crystallinity of all the nanoparticles. Energy-dispersive X-ray spectroscopy (EDS) showed the composition close to stoichiometric (~CoFe₂O₄) for both co-precipitated nanoparticles, whereas the nanoparticles prepared by the thermal decomposition were Co-deficient (~Co_0.6Fe_2.4O₄). The X-ray absorption near-edge structure (XANES) analysis showed Co valence of 2+ in all the samples, Fe valence 3+ in both co-precipitated samples, but average Fe valence of 2.7+ in the sample synthesized by thermal decomposition. The variations in cation distribution within the spinel lattice were observed by structural refinement of X-ray absorption fine structure (EXAFS). Like the bulk CoFe₂O₄, the nanoparticles synthesized at elevated temperature using thermal decomposition displayed inverse spinel structure with the Co ions occupying predominantly octahedral lattice sites, whereas co-precipitated samples showed considerable proportion of cobalt ions occupying tetrahedral sites (nearly 1/3 for the nanoparticles synthesized by co-precipitation from aqueous solutions and almost 1/4 for the nanoparticles synthesized in microemulsions). Magnetic measurements performed at room temperature and at 10 K were in good agreement with the nanoparticles’ composition and the cation distribution in their structure. The presented study clearly shows that the distribution of the cations within the spinel lattice of the ferrite nanoparticles, and consequently their magnetic properties are strongly affected by the synthesis method used.     

Structural evolution of FexCo1−x/NM (NM=Ag, Cu, Al2O3) discontinuous multilayers by XAS

We discuss the specific features of the K-edge X-ray absorption spectroscopy (XAS) at the Fe and Co K-edges in Fe_xCo_1−x/NM discontinuous multilayers with NM=Ag, Cu, and Al₂O₃. Thermal treatments lead to the breakup of the layers forming a heterogeneous alloy with magnetic clusters of the FeCo embedded in a nonmagnetic (NM) matrix. Stabilization of the BCC phase of the FeCo alloy is directly evidenced by XAS. Differences among Fe and Co K-edge signatures indicate a strong dependence on the chemical nature of the absorbing atom for annealed samples. The amplitude of the extended X-ray absorption fine structure signal higher at the Co K-edge than at the Fe one reflect a smaller structural disorder in the Co environment. This behavior depends neither on the composition of the alloy nor on the NM material. In the case of Al₂O₃ a higher disorder around Fe atoms is observed also in the as-deposited sample. All these results indicate that the Fe segregates at the interface of the magnetic clusters/NM matrix after thermal annealing.     

X‐ray absorption spectroscopy analysis of Ru in La2RuO5

The compound La₂RuO₅ was examined by the x‐ray absorption spectroscopy (XAS) methods, x‐ray absorption near edge structure (XANES) and extended x‐ray absorption fine structure (EXAFS). XANES technique was used to probe directly the average valence of Ru atoms in the compound. The energy shift of the Ru K‐edge in the XANES signal gave the average Ru valence state as 4.0 ± 0.1. EXAFS analysis provided, by yielding directly the interatomic distances and coordination numbers, the first information on the Ru atom neighborhood, on which the model for the Rietveld refinement of the unit cell of the new compound was devised. Finally, the local structure around the Ru atoms from the refinement was used in the FEFF6 code for a model EXAFS spectrum. The very good quantitative agreement with the measured spectrum proves that the refined crystal structure contains no systematic defects in the vicinity of Ru atoms. This result, together with the valence obtained from XANES, strongly confirms the proposed La₂RuO₅ stoichiometry. Copyright © 2007 John Wiley & Sons, Ltd.     

Local structure and optical absorption characteristic investigation on Fe doped TiO_2 nanoparticles

The local structures and optical absorption characteristics of Fe doped Ti O2 nanoparticles synthesized by the sol-gel method were characterized by X-ray diffraction(XRD), X-ray absorption fine structure spectroscopy(XAFS) and ultraviolet-visible absorption spectroscopy(UV-Vis). XRD patterns show that all Fe-doped Ti O2 samples have the characteristic anatase structure. Accurate Fe and Ti K-edge EXAFS analysis further reveal that all Fe atoms replace Ti atoms in the anatase lattice. The analysis of UV-Vis data shows a red shift to the visible range. According to the above results, we claim that substitutional Fe atoms lead to the formation of structural defects and new intermediate energy levels appear, narrowing the band gap and extending the optical absorption edge towards the visible region.     

The novel YMn2D6 deuteride synthesized under high pressure of gaseous deuterium

The novel intermetallic deuteride YMn₂D₆ was synthesized under high deuterium pressure. In order to identify the structure and characterize the magnetic properties of this deuteride the powder X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Mn X-ray absorption near edge structure (XANES) and magnetization measurement (SQUID) were carried out. The crystal structure, the chemical state of Mn and the magnetic properties of this novel deuteride were examined and discussed. It should be noted that the structure of YMn₂D₆ (F-43m) differs dramatically from C15 symmetry of the parent material. Such a great rearrangement of the metal lattice due to deuterium absorption is rather exceptional for C15 Laves phase.     

Structural and magnetic properties of FeB microfibers

Structural and magnetic properties of FeB microfibers, obtained by electroless deposition on cellulose fibers, were investigated. X-ray diffraction (XRD) showed the presence of an amorphous phase. Extended X-ray absorption fine structure spectroscopy (EXAFS) studies confirmed an amorphous-like structure with the nearest coordination numbers around Fe atom to be 8.7 for Fe and 3.5 for B. The magnetic moment of 2.12 Bohr magnetons/Fe atom is consistent with composition obtained from EXAFS measurements. PACS 61.43.Dq; 61.10.Ht; 75.70.-i; 61.10.Eq; 81.15.Pq     

A new technique to measure the differential XAFS spectrum

A new technique has been developed for direct measurement of the differential X-ray absorption fine structure(XAFS) spectrum by the energy-modulation method. To acquire the energy-oscillating incident X-ray beam, a piezoelectric actuator is used to control the double-crystal monochromator. A logarithmic converter circuit and a lock-in amplifier are used to extract the modulated signals. The normal and differential XAFS spectra of the Mn K-edge of Li2 Mn O3 have been collected. The X-ray-absorption near-edge-structure(XANES) spectra verify that the signal-to-noise ratio has been greatly improved by the new technique, and the extended X-ray absorption fine structure(EXAFS) spectra demonstrate that this new technique can efficiently enhance the signals of the backscattering atoms.     

Alternative difference analysis scheme combining R‐space EXAFS fit with global optimization XANES fit for X‐ray transient absorption spectroscopy

Time‐resolved X‐ray absorption spectroscopy (TR‐XAS), based on the laser‐pump/X‐ray‐probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR‐XAS data analysis is generally performed on the laser‐on minus laser‐off difference spectrum. Here, a new analysis scheme is presented for the TR‐XAS difference fitting in both the extended X‐ray absorption fine‐structure (EXAFS) and the X‐ray absorption near‐edge structure (XANES) regions. R‐space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non‐derivative optimization algorithm and optimizes the local structure change in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR‐XAS difference analysis of Fe(phen)₃ spin crossover complex and yielded reliable distance change and excitation population.     

Double flourescence detection of XANES and EXAFS signals from dilute species in competing fluorescent matrices

A double flourescence scheme for detecting XANES (X-ray absorption near-edge structure) and EXAFS (extended X-ray absorption fine structure) signals from a dilute species in a bulk competing flourescent matrix is reported. The new scheme has been demonstrated for the case of a Western Australian mineral specimen containing ～ 900 ppm of Au, and is particularly suitable for chemical and structural investigation of low concentration species in a matrix of similar, but slightly lower atomic number(s). The technique has the advantage of largely eliminating unwanted background arising from the bulk matrix.     

Electrochemical and structural properties of HT-LiCoO2 and LT-LiCoO2 prepared by the citrate sol-gel method

LT-LiCoO₂ has a slightly modified structure but significantly different electrochemical properties compared to LiCoO₂ prepared at high temperature. In this study, the structure and electrochemical properties of LT-LiCoO₂ have been evaluated using Raman spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), and electrochemical methods. According to the structural analysis, LT-LiCoO₂ has an intermediate structure between a layered and a spinel structure. The first discharge capacity of LT-LiCoO₂ is 80 mAh/g (100 μA/cm²).     

The characterization of EuO nanocrystals using synchrotron light

We have studied the physical structure, optical property, electronic band structure and atomic structure of europium oxide (EuO) nanocrystals. The physical structures of nanocrystals are confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The optical property and electronic band structure are studied by X-ray absorption near-edge structure (XANES) measurement. We have also investigated the L₃-edge energy of europium(II) ion by extended X-ray absorption fine structure (EXAFS) measurement, which clarified the atomic structure of europium oxide nanocrystals.     

Structure of manganese zinc ferrite spinel nanoparticles prepared with co-precipitation in reversed microemulsions

The structure of Mn_0.5Zn_0.5Fe₂O₄ spinel ferrite nanoparticles is studied as a function of their size and the experimental conditions of their synthesis using X-ray absorption spectroscopy. The nanoparticles of different sizes down to approximately 2 nm and with a narrow size distribution were synthesized using co-precipitation in reverse microemulsions. Simultaneous refinement of the X-ray absorption fine structure (EXAFS) of three constituting metals shows a migration of Mn and Zn ions to the octahedral site of the spinel lattice compensated by the corresponding migration of the Fe ions. To a smaller extent, Mn ions switch the occupation site already in bulk and in larger nanoparticles, while a sporadic migration of Zn is detected only in the nanoparticles with sizes below approximately 5 nm. X-ray absorption near edge structure (XANES) reveals considerable variations in the position of the Mn K edge, suggesting the average Mn valence in the nanoparticles to be higher than 3+. Annealing at 500 °C relaxes the structure of as-synthesized nanoparticles toward the structure of the ceramic bulk standard. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Phase decomposition in nominal LaxCuO4 (x≤2.00) determined by extended x-ray absorption fine structure

Cu K-edge and La L₃-edge X-ray absorption spectra have been measured on a series of nominal La_xxCuO₄ samples with x≤2.00. The extended X-ray absorption fine structure (EXAFS) results show that the x<2.0 samples always consist of stoichiometric (La/Cu=2/1) La₂CuO₄ and CuO. The number of La vacancies in the La₂CuO₄ structure, if any, should be very small. The sensitivity of the EXAFS technique to impurity phases under favorable conditions is demonstrated.