Turkey red is a traditional pigment for textile dyeing and its use has been proven for various cultures within the last three millennia. The pigment is a dye-mordant complex consisting of Al and an extract from R. tinctorum that contains mainly the anthraquinone derivative alizarin. The chemical structure of the complex has been analyzed by various spectroscopic and crystallographic techniques for extractions from textiles or directly in solution. We present an in-situ study of Turkey red by means of μ-XRF mapping and NEXAFS spectroscopy on textile fibres dyed according to a traditional process to gain insight into the coordination chemistry of the pigment in realistic matrix. We find an octahedral coordination of Al that corresponds well to the commonly accepted structure of the Al alizarin complex derived from ex-situ studies.

ABSTRACT We have investigated the effect of thermal annealing on the structure of single and stacked phase change memory films based on SnSe and GaSb. Samples were prepared by pulsed laser deposition and investigated by X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) methods. Electrical resistance versus temperature investigations showed crystallisation temperatures of 292°C and 198°C for SnSe and GaSb single films, respectively. Above the transition temperature, GaSb crystallises into a face-centered cubic structure, whereas SnSe has an orthorhombic arrangement. Annealing at three temperatures (160°C, 250°C and 350°C) of the SnSe\GaSb stacked films promotes bond breaking, atom diffusion between the two layers and formation of new phases. At 160°C, GaSb films crystallise partially and no effect is observed on the crystallinity of SnSe films. After 250°C, rhombohedral SnSb emerges in addition to GaSb complete crystallisation. A major, completely new, body-centered orthorhombic unindexed quaternary Ga-Sn-Sb-Se phase formation was observed in the samples annealed at 350°C. The GaSb crystallites are fully dissolved and we have observed the formation of a minor hexagonal SnSe2 phase. The analysis of EXAFS data, measured at Se and Ga K-edges, revealed changes in the local atomic environment as a function of the annealing temperature. A tetrahedral configuration is obtained for the Ga atoms in both as-deposited and annealed samples, whereas Se is mostly bivalent in the amorphous samples and has an octahedral arrangement in crystalline SnSe. Our results show that inter-layer diffusion should always be considered and evaluated when designing memory cells composed of stacked phase change chalcogenide films.

The optical band gap and electronic structure of amorphous Al-Zr mixed oxides with Zr content ranging from 4.8 to 21.9% were determined using vacuum ultraviolet and X-ray absorption spectroscopy. The light scattering by the nano-porous structure of alumina at low wavelengths was estimated based on the Mie scattering theory. The dependence of the optical band gap of the Al-Zr mixed oxides on the Zr content deviates from linearity and decreases from 7.3 eV for pure anodized Al2O3 to 6.45 eV for Al-Zr mixed oxides with a Zr content of 21.9%. With increasing Zr content, the conduction band minimum changes non-linearly as well. Fitting of the energy band gap values resulted in a bowing parameter of ∼2 eV. The band gap bowing of the mixed oxides is assigned to the presence of the Zr d-electron states localized below the conduction band minimum of anodized Al2O3.

The structural, optical, and transport properties of sputter-deposited Al-Ti thin films have been investigated as a function of Ti alloying with a concentration ranging from 2% to 46%. The optical reflectivity of Al-Ti films at visible and near-infrared wavelengths decreases with increasing Ti content. X-ray absorption fine structure measurements reveal that the atomic ordering around Ti atoms increases with increasing Ti content up to 20% and then decreases as a result of a transition from a polycrystalline to amorphous structure. The transport properties of the Al-Ti films are influenced by electron scattering at the grain boundaries in the case of polycrystalline films and static defects, such as anti-site effects and vacancies in the case of the amorphous alloys. The combination of Ti having a real refractive index (n) comparable with the extinction coefficient (k) and Al with n much smaller than k allows us to explore the parameter space for the free-electron behavior in transition metal-Al alloys. The free electron model, applied for the polycrystalline Al-Ti films with Ti content up to 20%, leads to an optical reflectance at near infrared wavelengths that scales linearly with the square root of the electrical resistivity.

Transition metal oxides are among the most promising solar materials, whose properties rely on the generation, transport and trapping of charge carriers (electrons and holes). Identifying the latter's dynamics at room temperature requires tools that combine elemental and structural sensitivity, with the atomic scale resolution of time (femtoseconds, fs). Here, we use fs Ti K-edge X-ray absorption spectroscopy (XAS) upon 3.49 eV (355 nm) excitation of aqueous colloidal anatase titanium dioxide nanoparticles to probe the trapping dynamics of photogenerated electrons. We find that their localization at Titanium atoms occurs in < 300 fs, forming Ti3+ centres, in or near the unit cell where the electron is created. We conclude that electron localization is due to its trapping at pentacoordinated sites, mostly present in the surface shell region. The present demonstration of fs hard X-ray absorption capabilities opens the way to a detailed description of the charge carrier dynamics in transition metal oxides.

Experimental studies have evidenced the presence of some chromium oxide precipitates in chromia (Cr2O3) doped UO2 fuels, currently being used in many light water reactors. The main objective of this study was to analyze the atomic scale microstructure of these precipitates in a non-destructive way employing modern synchrotron-based X-ray radiation. To investigate UO2 microstructures and chemical compositions of the precipitates an industrial grade fresh Cr2O3-doped UO2 pellet (produced with an initial amount of 0.16wt.% Cr2O3 powder) was examined using scanning electron microscopy (SEM) and electron probe micro analysis (EPMA). Average grain diameter of the UO2 matrix was measured by SEM image analysis method. Precipitates were detected by EPMA. For all precipitates of micrometer scale analyzed by EPMA the composition was determined to be very close to Cr2O3. The structural property and the next neighbor Cr atomic environment in these precipitates were studied by a combination of more sensitive tools such as micro-focused X-ray diffraction (μ-XRD) and absorption spectroscopy (μ-XAS). According to the XRD data, the chromia precipitates contain structural disorder and have a somewhat distorted lattice structure as compared to that of standard and crystalline α-Cr2O3 hexagonal crystal unit cell. The μ-XAS results provide insight into the local atomic environment of chromium including the oxidation state assignment.

Single and double layer phase change memory structures based on GeTe and GaSb thin films were deposited by pulsed laser deposition (PLD). Their crystallization behavior was studied using in-situ synchrotron techniques. Electrical resistance vs. temperature investigations, using the four points probe method, showed transition temperatures of 138 °C and 198 °C for GeTe and GaSb single films, respectively. It was found that after GeTe crystallization in the stacked films, Ga atoms from the GaSb layer diffused in the vacancies of the GeTe crystalline structure. Therefore, the crystallization temperature of the Sb-rich GaSb layer is decreased by more than 30 °C. Furthermore, at 210 °C, the antimony excess from GaSb films crystallizes as a secondary phase. At higher annealing temperatures, the crystalline Sb phase increased on the expense of GaSb crystalline phase which was reduced. Extended X-ray absorption fine structure (EXAFS) measurements at the Ga and Ge K-edges revealed changes in their local atomic environments as a function of the annealing temperature. Simulations unveil a tetrahedral configuration in the amorphous state and octahedral configuration in the crystalline state for Ge atoms, while Ga is four-fold coordinated in both as-deposited and annealed samples.

The band structure of pure and Ti-alloyed anodic aluminum oxide has been examined as a function of Ti concentration varying from 2 to 20 at. %. The band gap energy of Ti-alloyed anodic Al oxide decreases with increasing Ti concentration. X-ray absorption spectroscopy reveals that Ti atoms are not located in a TiO2 unit in the oxide layer, but rather in a mixed Ti-Al oxide layer. The optical band gap energy of the anodic oxide layers was determined by vacuum ultraviolet spectroscopy in the energy range from 4.1 to 9.2 eV (300–135 nm). The results indicate that amorphous anodic Al2O3 has a direct band gap of 7.3 eV, which is about ∼1.4 eV lower than its crystalline counterpart (single-crystal Al2O3). Upon Ti-alloying, extra bands appear within the band gap of amorphous Al2O3, mainly caused by Ti 3d orbitals localized at the Ti site.

The structure and defect concentration of colloidal solutions of ZnO nanoparticles, synthesized by a sol gel procedure (SG-NP), as well as commercially available ZnO nanoparticles (SA-NP) are investigated by UV-vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD). The XRD patterns, in agreement with the TEM images, reveal that the SG-NPs are more ellipsoidal than the SA-NPs. XRD and XAS reveal the presence of both zinc and oxygen vacancies. The concentration of the latter is independent of the NP size. This is not the case for the zinc vacancies, whose concentration increases sharply in the SG-NPs compared to the SA-NPs, and an similar to 40% oxygen excess in comparison to the expected stoichiometric ratio is found. Importantly, an extended X-ray absorption fine structure (EXAFS) analysis shows that this large concentration of zinc vacancies does not lead to distortions of the local lattice structure. Finally, the Zn K-edge X-ray absorption near edge structure (XANES) spectra show distinct changes in the rising edge and above edge regions, which supports the presence of zinc vacancies. In all cases, two weak pre-edge features are also observed and assigned to a small concentration of oxygen vacancies.

Synchrotron-based microprobe x-ray absorption spectroscopy (XAS) has been used to study the local atomic structure of chromium in chromia-doped uranium dioxide (UO2) grains. The specimens investigated were a commercial grade chromia-doped UO2 fresh fuel pellet, and materials from a spent fuel pellet of the same batch, irradiated with an average burnup of similar to 40 MW d kg(-1). Uranium L-3-edge and chromium K-edge XAS have been measured, and the structural environments of central uranium and chromium atoms have been elucidated. The Fourier transform of uranium L-3-edge extended x-ray absorption fine structure shows two well-defined peaks of U-O and U-U bonds at average distances of 2.36 and 3.83 angstrom. Their coordination numbers are determined as 8 and 11, respectively. The chromium Fourier transform extended x-ray absorption fine structure of the pristine UO2 matrix shows similar structural features with the corresponding spectrum of the irradiated spent fuel, indicative of analogous chromium environments in the two samples studied. From the chromium XAS experimental data, detectable next neighbor atoms are oxygen and uranium of the cation-substituted UO2 lattice, and two distinct subshells of chromium and oxygen neighbors, possibly because of undissolved chromia particles present in the doped fuels. Curve-fitting analyses using theoretical amplitude and phase-shift functions of the closest Cr-O shell and calculations with ab initio computer code FEFF and atomic clusters generated from the chromium-dissolved UO2 structure have been carried out. There is a prominent reduction in the length of the adjacent Cr-O bond of about 0.3 angstrom in chromia-doped UO2 compared with the ideal U-O bond length in standard UO2 that would be expected because of the change in effective Coulomb interactions resulting from replacing U4+ with Cr3+ and their ionic size differences. The contraction of shortest Cr-U bond is similar to 0.1 angstrom relative to the U-U bond length in bulk UO2. The difference in the local chromium environment between fresh and irradiated UO2 is discussed based on the comparison of quantitative structural information obtained from the two chromia-doped fuel samples analyzed.

Microstructural changes in a set of commercial grade UO2 fuel samples have been investigated using synchrotron based micro-focused X-ray fluorescence (μ-XRF) and X-ray diffraction (μ-XRD) techniques. The results are associated with conventional UO2 materials and relatively larger grain chromia-doped UO2 fuels, irradiated in a commercial light water reactor plant (average burn-up: 40MWdkg−1). The lattice parameters of UO2 in fresh and irradiated specimens have been measured and compared with theoretical predictions. In the pristine state, the doped fuel has a somewhat smaller lattice parameter than the standard UO2 as a result of chromia doping. Increase in micro-strain and lattice parameter in irradiated materials is highlighted. All irradiated samples behave in a similar manner with UO2 lattice expansion occurring upon irradiation, where any Cr induced effect seems insignificant and accumulated lattice defects prevail. Elastic strain energy densities in the irradiated fuels are also evaluated based on the UO2 crystal lattice strain and non-uniform strain. The μ-XRD patterns further allow the evaluation of the crystalline domain size and sub-grain formation at different locations of the irradiated UO2 pellets.

Specimens of a 4.7 wt % plutonium MOX fuel, irradiated for a period of 6 years up to 60 MW d kg(-1) were investigated using synchrotron based micro X-ray diffraction technique (pXRD). The mu XRD measurements at the Swiss Light Source SLS with a beam spot size of about 2 mu m x 2 mu m were carried out on the center and periphery region on the cross section of the irradiated fuel, as well as on un-irradiated reference MOX material. The profiles of characteristic (111), (200), (220), (311) and (222) diffraction lines of the irradiated samples were analyzed in detail and compared with the data of the non-irradiated MOX material, revealing the lattice distortion and dilatation in the irradiated fuel matrix. Broadening of reflexes can be observed due to the increasing stress finally yielding strain up to fuel grain fracture. This phenomenon is quantified thanks to the analysis of the reflexes arcs fine structure. The sub-grain number per grain volume is analysed as a function of fuel location and history. (C) 2011 Elsevier Ltd. All rights reserved.

In situ Laue analysis during microcompression is carried out on Mo-alloy pillars containing defects due to focused ion beam milling or pre-strain. Independently of how the defects are introduced, if the diffraction peaks are streaked prior to deformation, slip starts in the direction matching the observed streaking, even if this corresponds to a low Schmid factor. The amount of pre-strain influences the deformation behaviour in terms of hardening and strain bursts. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

X-ray near edge absorption spectroscopy was used to probe the electronic structure of multiferroic orthorhombic LuMnO3 polycrystalline samples and strained, twin-free orthorhombic (1–10) LuMnO3 films grown by pulsed laser deposition on (1–10) YAlO3 substrates. For all o-LuMnO3 samples x-ray near edge absorption spectroscopy spectra reveal that the pre-edge structure is influenced by the increase in MnO6 distortion as a result of the smaller Re-ion or film strain. Furthermore there is clear evidence of anisotropic Mn-O bonding and Mn orbital ordering along the c- and [110] direction. The experimental film and bulk data are in agreement with ab initio simulations.

In situ Laue analysis during microcompression reveals plasticity in [001]-oriented, directionally solidified Mo alloy pillars to start with slip on the {112}〈111〉 system having the highest Schmid factor followed by slip on the (110) plane containing the same Burgers vector. The results are interpreted in terms of the microstructure analyzed by scanning transmission electron microscopy and 3-D atom probe.

Element specific investigations using X-ray magnetic circular dichroism (XMCD) were performed on FeCr alloys for Cr concentrations ranging from 6 to 16 at.% Cr. Measurements at the Fe L edge show a scattered distribution of the spin and orbital magnetic moments which is not observed for the global bulk magnetic moment. The Cr is aligned ferromagnetic up to 16 at.% Cr and in opposite direction with respect to the Fe magnetic moments.

The Cr in ferritic steels with high Cr content naturally segregates. Depending on the Cr content, the material can be in a state of short-range order (below approximately 10%Cr) or contain clusters of Cr atoms above this concentration. Using synchrotron based X-ray micro-spectroscopy, SEM imaging and fluorescence mapping, Cr-rich clusters in a high purity Fe–16%Cr alloy are identified and investigated. The Cr local structure is resolved by fitting a simple pure Cr model to extended X-ray absorption fine structure (EXAFS) spectra. The fits indicates that the Debye–Waller factor is higher inside the cluster than in the solid solution, but the nearest neighbor distances are closer to that of the pure Cr model inside the cluster than around it.