X‐ray‐excited optical luminescence and X‐ray absorption fine‐structures studies of CdWO4 scintillator

X‐ray‐excited optical luminescence (XEOL) emission and excitation spectra as well as the EXAFS signal of CdWO₄ were measured in the energy region of the Cd and W absorption edges. From EXAFS refinement, structural parameters such as number of atoms, distance from the absorbing atom and width of coordination shells in the W neighborhood were determined. The role of W–O interactions on the intrinsic luminescence of CdWO₄ is discussed. The efficiencies of conversion, transfer and emission processes involved in the scintillation mechanism showed to be high when self‐trapped excitons are formed locally by direct excitation of W ions. Annihilation of these excitons provides the characteristic scintillation of CdWO₄, a broad band emission with maximum at 500 nm. The presence of two energetically different O positions in the lattice gives rise to the composite structure of the luminescence band, and no influence of extrinsic defects was noticed. A mismatch between the X‐ray absorption coefficient and the zero‐order luminescence curves corroborates that the direct excitation of Cd ions induces secondary electronic excitations not very effective in transferring energy to the luminescent group, WO₆.     

SUT‐NANOTEC‐SLRI beamline for X‐ray absorption spectroscopy

The SUT‐NANOTEC‐SLRI beamline was constructed in 2012 as the flagship of the SUT‐NANOTEC‐SLRI Joint Research Facility for Synchrotron Utilization, co‐established by Suranaree University of Technology (SUT), National Nanotechnology Center (NANOTEC) and Synchrotron Light Research Institute (SLRI). It is an intermediate‐energy X‐ray absorption spectroscopy (XAS) beamline at SLRI. The beamline delivers an unfocused monochromatic X‐ray beam of tunable photon energy (1.25–10 keV). The maximum normal incident beam size is 13 mm (width) × 1 mm (height) with a photon flux of 3 × 10⁸ to 2 × 10¹⁰ photons s^?1 (100 mA)^?1 varying across photon energies. Details of the beamline and XAS instrumentation are described. To demonstrate the beamline performance, K‐edge XANES spectra of MgO, Al₂O₃, S₈, FeS, FeSO₄, Cu, Cu₂O and CuO, and EXAFS spectra of Cu and CuO are presented.     

A setup for synchrotron‐radiation‐induced total reflection X‐ray fluorescence and X‐ray absorption near‐edge structure recently commissioned at BESSY II BAMline

An automatic sample changer chamber for total reflection X‐ray fluorescence (TXRF) and X‐ray absorption near‐edge structure (XANES) analysis in TXRF geometry was successfully set up at the BAMline at BESSY II. TXRF and TXRF‐XANES are valuable tools for elemental determination and speciation, especially where sample amounts are limited (<1 mg) and concentrations are low (ng ml^?1 to µg ml^?1). TXRF requires a well defined geometry regarding the reflecting surface of a sample carrier and the synchrotron beam. The newly installed chamber allows for reliable sample positioning, remote sample changing and evacuation of the fluorescence beam path. The chamber was successfully used showing accurate determination of elemental amounts in the certified reference material NIST water 1640. Low limits of detection of less than 100 fg absolute (10 pg ml^?1) for Ni were found. TXRF‐XANES on different Re species was applied. An unknown species of Re was found to be Re in the +7 oxidation state.     

Pressure study of monoclinic ReO2 up to 1.2 GPa using X‐ray absorption spectroscopy and X‐ray diffraction

The crystal and local atomic structure of monoclinic ReO₂ (α‐ReO₂) under hydrostatic pressure up to 1.2 GPa was investigated for the first time using both X‐ray absorption spectroscopy and high‐resolution synchrotron X‐ray powder diffraction and a home‐built B₄C anvil pressure cell developed for this purpose. Extended X‐ray absorption fine‐structure (EXAFS) data analysis at pressures from ambient up to 1.2 GPa indicates that there are two distinct Re—Re distances and a distorted ReO₆ octahedron in the α‐ReO₂ structure. X‐ray diffraction analysis at ambient pressure revealed an unambiguous solution for the crystal structure of the α‐phase, demonstrating a modulation of the Re—Re distances. The relatively small portion of the diffraction pattern accessed in the pressure‐dependent measurements does not allow for a detailed study of the crystal structure of α‐ReO₂ under pressure. Nonetheless, a shift and reduction in the (011) Bragg peak intensity between 0.4 and 1.2 GPa is observed, with correlation to a decrease in Re—Re distance modulation, as confirmed by EXAFS analysis in the same pressure range. This behavior reveals that α‐ReO₂ is a possible inner pressure gauge for future experiments up to 1.2 GPa.     

The multi‐purpose hard X‐ray beamline BL10 at the DELTA storage ring

The layout and the characteristics of the hard X‐ray beamline BL10 at the superconducting asymmetric wiggler at the 1.5 GeV Dortmund Electron Accelerator DELTA are described. This beamline is equipped with a Si(111) channel‐cut monochromator and is dedicated to X‐ray studies in the spectral range from ～4 keV to ～16 keV photon energy. There are two different endstations available. While X‐ray absorption studies in different detection modes (transmission, fluorescence, reflectivity) can be performed on a designated table, a six‐axis kappa diffractometer is installed for X‐ray scattering and reflectivity experiments. Different detector set‐ups are integrated into the beamline control software, i.e. gas‐filled ionization chambers, different photodiodes, as well as a Pilatus 2D‐detector are permanently available. The performance of the beamline is illustrated by high‐quality X‐ray absorption spectra from several reference compounds. First applications include temperature‐dependent EXAFS experiments from liquid‐nitrogen temperature in a bath cryostat up to ～660 K by using a dedicated furnace. Besides transmission measurements, fluorescence detection for dilute sample systems as well as surface‐sensitive reflection‐mode experiments are presented.     

The materials science X‐ray beamline BL8 at the DELTA storage ring

The hard X‐ray beamline BL8 at the superconducting asymmetric wiggler at the 1.5 GeV Dortmund Electron Accelerator DELTA is described. This beamline is dedicated to X‐ray studies in the spectral range from ～1 keV to ～25 keV photon energy. The monochromator as well as the other optical components of the beamline are optimized accordingly. The endstation comprises a six‐axis diffractometer that is capable of carrying heavy loads related to non‐ambient sample environments such as, for example, ultrahigh‐vacuum systems, high‐pressure cells or liquid‐helium cryostats. X‐ray absorption spectra from several reference compounds illustrate the performance. Besides transmission measurements, fluorescence detection for dilute sample systems as well as surface‐sensitive reflection‐mode experiments have been performed. The results show that high‐quality EXAFS data can be obtained in the quick‐scanning EXAFS mode within a few seconds of acquisition time, enabling time‐resolved in situ experiments using standard beamline equipment that is permanently available. The performance of the new beamline, especially in terms of the photon flux and energy resolution, is competitive with other insertion‐device beamlines worldwide, and several sophisticated experiments including surface‐sensitive EXAFS experiments are feasible.     

X‐ray absorption study of the local structure at the NiO/oxide interfaces

This work reports an X‐ray absorption near‐edge structure (XANES) spectroscopy study at the Ni K‐edge in the early stages of growth of NiO on non‐ordered SiO₂, Al₂O₃ and MgO thin films substrates. Two different coverages of NiO on the substrates have been studied. The analysis of the XANES region shows that for high coverages (80 Eq‐ML) the spectra are similar to that of bulk NiO, being identical for all substrates. In contrast, for low coverages (1 Eq‐ML) the spectra differ from that of large coverages indicating that the local order around Ni is limited to the first two coordination shells. In addition, the results also suggest the formation of cross‐linking bonds Ni—O—M (M = Si, Al, Mg) at the interface.     

A high‐temperature furnace for in situ synchrotron X‐ray spectroscopy under controlled atmospheric conditions

A high‐temperature furnace with an induction heater coil has been designed and constructed for in situ X‐ray spectroscopic experiments under controlled atmospheric conditions and temperatures up to 3275 K. The multi‐purpose chamber design allows working in backscattering and normal fluorescence mode for synchrotron X‐ray absorption and emission spectroscopy. The use of the furnace is demonstrated in a study of the in situ formation of Cr oxide between 1823 K and 2023 K at logPO₂ values between ?10.0 and ?11.3 using X‐ray absorption near‐edge spectroscopy. The set‐up is of particular interest for studying liquid metals, alloys and other electrically conductive materials under extreme conditions.     

Effects of organic ligands on Pb absorption and speciation changes in Arabidopsis as determined by micro X‐ray fluorescence and X‐ray absorption near‐edge structure analysis

Pb can pass through the food chain via plants and threaten human health, which has attracted widespread attention. Changes in Pb speciation affect its bioavailability in soils and water. However, whether organic ligands can change the uptake and mobility of Pb in plants and increase or decrease Pb bioavailability remains uncertain. To reveal the roles of organic and inorganic Pb in Pb metabolism in plants, the localization and speciation changes of Pb in Arabidopsis thaliana plants grown in organic and inorganic Pb were characterized by synchrotron radiation micro X‐ray fluorescence and X‐ray absorption near‐edge structure, respectively. These results demonstrated that Arabidopsis absorbed more Pb from Pb(NO₃)₂ than Pb(CH₃COO)₂ at the same exposure concentration. A higher percentage of Pb‐citrate was found in Arabidopsis exposed to inorganic Pb solution, which suggested that Pb‐citrate was the main complex for root‐to‐shoot transportation in Arabidopsis exposed to inorganic Pb solutions. Pb complexed with the organic ligand CH₃COO^? significantly inhibited primary root growth and lateral root development, while, at the same time, Pb was blocked by root hairs, which represented another way to reduce Pb absorption and protect the plant from biotoxicity.     

X‐ray absorption near‐edge structure anomalous behaviour in structures with buried layers containing silicon nanocrystals

Substructure and phase composition of silicon suboxide films containing silicon nanocrystals and implanted with carbon have been investigated by means of the X‐ray absorption near‐edge structure technique with the use of synchrotron radiation. It is shown that formation of silicon nanocrystals in the films' depth (more than 60 nm) and their following transformation into silicon carbide nanocrystals leads to abnormal behaviour of the X‐ray absorption spectra in the elementary silicon absorption‐edge energy region (100–104 eV) or in the silicon oxide absorption‐edge energy region (104–110 eV). This abnormal behaviour is connected to X‐ray elastic backscattering on silicon or silicon carbide nanocrystals located in the silicon oxide films depth.     

Performance of a fuel cell optimized for in situ X‐ray absorption experiments

A commercial fuel cell has been successfully modified to carry out X‐ray absorption spectroscopy (XAS) measurements under optimized in operando conditions. The design is conceived for the performance of XAS experiments in transmission mode over a wide range of X‐ray energies above 6 keV, owing to the reduced absorption of the cell. The wide angular aperture allows the collection of XAS in fluorescence mode and of X‐ray diffraction patterns when needed. Details of the design of the cell and its performances are given. The quality of the extended X‐ray absorption fine‐structure spectra under working conditions has been verified at the ESRF and ELETTRA synchrotron radiation facilities, showing that relatively fast and low‐noise transmission measurements on electrodes over a wide range of catalyst concentrations and energies are feasible.     

Early commissioning results for spectroscopic X‐ray Nano‐Imaging Beamline BL 7C sXNI at PLS‐II

For spectral imaging of chemical distributions using X‐ray absorption near‐edge structure (XANES) spectra, a modified double‐crystal monochromator, a focusing plane mirrors system and a newly developed fluorescence‐type X‐ray beam‐position monitoring and feedback system have been implemented. This major hardware upgrade provides a sufficiently stable X‐ray source during energy scanning of more than hundreds of eV for acquisition of reliable XANES spectra in two‐dimensional and three‐dimensional images. In recent pilot studies discussed in this paper, heavy‐metal uptake by plant roots in vivo and iron's phase distribution in the lithium–iron–phosphate cathode of a lithium‐ion battery have been imaged. Also, the spatial resolution of computed tomography has been improved from 70 nm to 55 nm by means of run‐out correction and application of a reconstruction algorithm.     

An attempt to analyze the bark disease in Havea brasiliensis using X‐ray absorption near‐edge spectroscopy

The X‐ray absorption near‐edge spectroscopy (XANES) technique has been used to determine the chemical change of elements induced by bark diseases in Havea brasiliensis (rubber latex tree). The results show the good sensitivity of in situ XANES for characterizing the chemical structure of phosphorus, sulfur, potassium and calcium in healthy and diseased Havea brasiliensis. Important information for understanding the bark disease involved in the sulfur metabolism of plants was also obtained from XANES.     

In situ diffuse reflectance IR spectroscopy and X‐ray absorption spectroscopy for fast catalytic processes

A new instrument for synchronous in situ investigations of catalytic materials by IR and X‐ray absorption spectroscopies was designed and built at the X18A beamline of the National Synchrotron Light Source of Brookhaven National Laboratory. It provides analytical tools for solving structural, electronic and kinetic problems in catalysis science by two complementary methods. Among the features attractive for catalysis research are the broad range of catalytically active elements that can be investigated (starting with Ni and beyond), the wide range of reaction conditions (temperatures up to 873 K, various reactive gases) and time scales (starting from tens of seconds). The results of several representative experiments that illustrate the attractive capabilities of the new set‐up are discussed.     

Data analysis method to achieve sub‐10 pm spatial resolution using extended X‐ray absorption fine‐structure spectroscopy

Obtaining sub‐10 pm spatial resolution by extended X‐ray absorption fine structure (EXAFS) spectroscopy is required in many important fields of research, such as lattice distortion studies in colossal magnetic resistance materials, high‐temperature superconductivity materials etc. However, based on the existing EXAFS data analysis methods, EXAFS has a spatial resolution limit of π/2Δk which is larger than 0.1 Å. In this paper a new data analysis method which can easily achieve sub‐10 pm resolution is introduced. Theoretically, the resolution limit of the method is three times better than that normally available. The method is examined by numerical simulation and experimental data. As a demonstration, the LaFe_1–xCr_xO₃ system (x = 0, 1/3, 2/3) is studied and the structural information of FeO₆ octahedral distortion as a function of Cr doping is resolved directly from EXAFS, where a resolution better than 0.074 Å is achieved.     

Local structure of NiAl compounds investigated by extended X‐ray absorption fine‐structure spectroscopy

The local structures of pure NiAl and Ti‐, Co‐doped NiAl compounds have been obtained utilizing extended X‐ray absorption fine‐structure (EXAFS) spectroscopy. The results provide experimental evidence that Ni antisite defects exist in the Ni‐rich NiAl compounds. The site preference of Ti and Co has been confirmed. Ti occupies the Al sublattice, while Co occupies the Ni sublattice. The structure parameters obtained by EXAFS were consistent with the X‐ray diffraction results. Owing to the precipitation of α‐Cr, the local structure of NiAl‐Cr has not been obtained, making the site preference of Cr unclear.     

Investigation of nanoparticulate silicon as printed layers using scanning electron microscopy,transmission electron microscopy,X‐ray absorption spectroscopy and X‐ray photoelectron spectroscopy

The presence of native oxide on the surface of silicon nanoparticles is known to inhibit charge transport on the surfaces. Scanning electron microscopy (SEM) studies reveal that the particles in the printed silicon network have a wide range of sizes and shapes. High‐resolution transmission electron microscopy reveals that the particle surfaces have mainly the (111)‐ and (100)‐oriented planes which stabilizes against further oxidation of the particles. X‐ray absorption spectroscopy (XANES) and X‐ray photoelectron spectroscopy (XPS) measurements at the O 1s‐edge have been utilized to study the oxidation and local atomic structure of printed layers of silicon nanoparticles which were milled for different times. XANES results reveal the presence of the +4 (SiO₂) oxidation state which tends towards the +2 (SiO) state for higher milling times. Si 2p XPS results indicate that the surfaces of the silicon nanoparticles in the printed layers are only partially oxidized and that all three sub‐oxide, +1 (Si₂O), +2 (SiO) and +3 (Si₂O₃), states are present. The analysis of the change in the sub‐oxide peaks of the silicon nanoparticles shows the dominance of the +4 state only for lower milling times.     

Versatile vacuum chamber for in situ surface X‐ray scattering studies

A compact portable vacuum‐compatible chamber designed for surface X‐ray scattering measurements on beamline ID01 of the European Synchrotron Radiation Facility, Grenoble, is described. The chamber is versatile and can be used for in situ investigation of various systems, such as surfaces, nanostructures, thin films etc., using a variety of X‐ray‐based techniques such as reflectivity, grazing‐incidence small‐angle scattering and diffraction. It has been conceived for the study of morphology and structure of semiconductor surfaces during ion beam erosion, but it is also used for the study of surface oxidation or thin film growth under ultra‐high‐vacuum conditions. Coherent X‐ray beam experiments are also possible. The chamber is described in detail, and examples of its use are given.     

Correction method for the self‐absorption effects in fluorescence extended X‐ray absorption fine structure on multilayer samples

A novel correction method for self‐absorption effects is proposed for extended X‐ray absorption fine structure (EXAFS) detected in the fluorescence mode on multilayer samples. The effects of refraction and multiple reflection at the interfaces are fully considered in this correction method. The correction is performed in k‐space before any further data analysis, and it can be applied to single‐layer or multilayer samples with flat surfaces and without thickness limit when the model parameters for the samples are known. The validity of this method is verified by the fluorescence EXAFS data collected for a Cr/C multilayer sample measured at different experimental geometries.     

X‐ray spectromicroscopy in soil and environmental sciences

X‐ray microscopy is capable of imaging particles in the nanometer size range directly with sub‐micrometer spatial resolution and can be combined with high spectral resolution for spectromicroscopy studies. Two types of microscopes are common in X‐ray microscopy: the transmission X‐ray microscope and the scanning transmission X‐ray microscope; their set‐ups are explained in this paper. While the former takes high‐resolution images from an object with exposure times of seconds or faster, the latter is very well suited as an analytical instrument for spectromicroscopy. The morphology of clusters or particles from soil and sediment samples has been visualized using a transmission X‐ray microscope. Images are shown from a cryo‐tomography experiment based on X‐ray microscopy images to obtain information about the three‐dimensional structure of clusters of humic substances. The analysis of a stack of images taken with a scanning transmission X‐ray microscope to combine morphology and chemistry within a soil sample is shown. X‐ray fluorescence is a method ideally applicable to the study of elemental distributions and binding states of elements even on a trace level using X‐ray energies above 1 keV.