High‐resolution spectroscopy on an X‐ray absorption beamline

A bent‐crystal spectrometer based on the Rowland circle geometry has been installed and tested on the BM30b/FAME beamline at the European Synchrotron Radiation Facility to improve its performances. The energy resolution of the spectrometer allows different kinds of measurements to be performed, including X‐ray absorption spectroscopy, resonant inelastic X‐ray scattering and X‐ray Raman scattering experiments. The simplicity of the experimental device makes it easily implemented on a classical X‐ray absorption beamline. This improvement in the fluorescence detection is of particular importance when the probed element is embedded in a complex and/or heavy matrix, for example in environmental sciences.     

A large‐solid‐angle X‐ray Raman scattering spectrometer at ID20 of the European Synchrotron Radiation Facility

An end‐station for X‐ray Raman scattering spectroscopy at beamline ID20 of the European Synchrotron Radiation Facility is described. This end‐station is dedicated to the study of shallow core electronic excitations using non‐resonant inelastic X‐ray scattering. The spectrometer has 72 spherically bent analyzer crystals arranged in six modular groups of 12 analyzer crystals each for a combined maximum flexibility and large solid angle of detection. Each of the six analyzer modules houses one pixelated area detector allowing for X‐ray Raman scattering based imaging and efficient separation of the desired signal from the sample and spurious scattering from the often used complicated sample environments. This new end‐station provides an unprecedented instrument for X‐ray Raman scattering, which is a spectroscopic tool of great interest for the study of low‐energy X‐ray absorption spectra in materials under in situ conditions, such as in operando batteries and fuel cells, in situ catalytic reactions, and extreme pressure and temperature conditions.     

Sound velocities of compressed Fe3C from simultaneous synchrotron X‐ray diffraction and nuclear resonant scattering measurements

The applications of nuclear resonant scattering in laser‐heated diamond anvil cells have provided an important probe for the magnetic and vibrational properties of ⁵⁷Fe‐bearing materials under high pressure and high temperature. Synchrotron X‐ray diffraction is one of the most powerful tools for studying phase stability and equation of state over a wide range of pressure and temperature conditions. Recently an experimental capability has been developed for simultaneous nuclear resonant scattering and X‐ray diffraction measurements using synchrotron radiation. Here the application of this method to determine the sound velocities of compressed Fe₃C is shown. The X‐ray diffraction measurements allow detection of microscale impurities, phase transitions and chemical reactions upon compression or heating. They also provide information on sample pressure, grain size distribution and unit cell volume. By combining the Debye velocity extracted from the nuclear resonant inelastic X‐ray scattering measurements and the structure, density and elasticity data from the X‐ray diffraction measurements simultaneously obtained, more accurate sound velocity data can be derived. Our results on few‐crystal and powder samples indicate strong anisotropy in the sound velocities of Fe₃C under ambient conditions.     

A high‐energy‐resolution resonant inelastic X‐ray scattering spectrometer at ID20 of the European Synchrotron Radiation Facility

An end‐station for resonant inelastic X‐ray scattering and (resonant) X‐ray emission spectroscopy at beamline ID20 of ESRF – The European Synchrotron is presented. The spectrometer hosts five crystal analysers in Rowland geometry for large solid angle collection and is mounted on a rotatable arm for scattering in both the horizontal and vertical planes. The spectrometer is optimized for high‐energy‐resolution applications, including partial fluorescence yield or high‐energy‐resolution fluorescence detected X‐ray absorption spectroscopy and the study of elementary electronic excitations in solids. In addition, it can be used for non‐resonant inelastic X‐ray scattering measurements of valence electron excitations.     

A compact permanent‐magnet system for measuring magnetic circular dichroism in resonant inelastic soft X‐ray scattering

A compact and portable magnet system for measuring magnetic dichroism in resonant inelastic soft X‐ray scattering (SX‐RIXS) has been developed at the beamline BL07LSU in SPring‐8. A magnetic circuit composed of Nd–Fe–B permanent magnets, which realised ～0.25 T at the center of an 11 mm gap, was rotatable around the axis perpendicular to the X‐ray scattering plane. Using the system, a SX‐RIXS spectrum was obtained under the application of the magnetic field at an angle parallel, nearly 45° or perpendicular to the incident X‐rays. A dedicated sample stage was also designed to be as compact as possible, making it possible to perform SX‐RIXS measurements at arbitrary incident angles by rotating the sample stage in the gap between the magnetic poles. This system enables facile studies of magnetic dichroism in SX‐RIXS for various experimental geometries of the sample and the magnetic field. A brief demonstration of the application is presented.     

An extraction algorithm for core‐level excitations in non‐resonant inelastic X‐ray scattering spectra

Non‐resonant inelastic X‐ray scattering of core electrons is a prominent tool for studying site‐selective, i.e. momentum‐transfer‐dependent, shallow absorption edges of liquids and samples under extreme conditions. A bottleneck of the analysis of such spectra is the appropriate subtraction of the underlying background owing to valence and core electron excitations. This background exhibits a strong momentum‐transfer dependence ranging from plasmon and particle–hole pair excitations to Compton scattering of core and valence electrons. In this work an algorithm to extract the absorption edges of interest from the superimposed background for a wide range of momentum transfers is presented and discussed for two examples, silicon and the compound silicondioxide.     

X‐ray Raman spectroscopy of lithium‐ion battery electrolyte solutions in a flow cell

The effects of varying LiPF₆ salt concentration and the presence of lithium bis(oxalate)borate additive on the electronic structure of commonly used lithium‐ion battery electrolyte solvents (ethylene carbonate–dimethyl carbonate and propylene carbonate) have been investigated. X‐ray Raman scattering spectroscopy (a non‐resonant inelastic X‐ray scattering method) was utilized together with a closed‐circle flow cell. Carbon and oxygen K‐edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li⁺ ion concentration in the solvent manifests itself as a blue‐shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K‐edge results agree with previous soft X‐ray absorption studies on LiBF₄ salt concentration in propylene carbonate, carbon K‐edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.     

A novel method for resonant inelastic soft X‐ray scattering via photoelectron spectroscopy detection

A method for measuring resonant inelastic X‐ray scattering based on the conversion of X‐ray photons into photoelectrons is presented. The setup is compact, relies on commercially available detectors, and offers significant flexibility. This method is demonstrated at the Linac Coherent Light Source with ～0.5 eV resolution at the cobalt L₃‐edge, with signal rates comparable with traditional grating spectrometers.     

A multiplexed high‐resolution imaging spectrometer for resonant inelastic soft X‐ray scattering spectroscopy

The optical design of a two‐dimensional imaging soft X‐ray spectrometer is described. A monochromator will produce a dispersed spectrum in a narrow vertical illuminated stripe (～2 µm wide by ～2 mm tall) on a sample. The spectrometer will use inelastically scattered X‐rays to image the extended field on the sample in the incident photon energy direction (vertical), resolving the incident photon energy. At the same time it will image and disperse the scattered photons in the orthogonal (horizontal) direction, resolving the scattered photon energy. The principal challenge is to design a system that images from the flat‐field illumination of the sample to the flat field of the detector and to achieve sufficiently high spectral resolution. This spectrometer provides a completely parallel resonant inelastic X‐ray scattering measurement at high spectral resolution (～30000) over the energy bandwidth (～5 eV) of a soft X‐ray absorption resonance.     

X‐ray‐Raman‐scattering‐based EXAFS beyond the dipole limit

X‐ray Raman scattering (XRS) provides a bulk‐sensitive method of measuring the extended X‐ray absorption fine structure (EXAFS) of soft X‐ray absorption edges. Accurate measurements and data analysis procedures for the determination of XRS‐EXAFS of polycrystalline diamond are described. The contributions of various angular‐momentum components beyond the dipole limit to the atomic background and the EXAFS oscillations are incorporated using self‐consistent real‐space multiple‐scattering calculations. The properly extracted XRS‐EXAFS oscillations are in good agreement with calculations and earlier soft X‐ray EXAFS results. It is shown, however, that under certain conditions multiple‐scattering contributions to XRS‐EXAFS deviate from those in standard EXAFS, leading to noticeable changes in the real‐space signal at higher momentum transfers owing to non‐dipole contributions. These results pave the way for the accurate application of XRS‐EXAFS to previously inaccessible light‐element systems.     

Adaption of a diffractometer for time‐resolved X‐ray resonant magnetic scattering

A new set‐up is presented to measure element‐selective magnetization dynamics using the ALICE chamber [Grabis et al. (2003), Rev. Sci. Instrum. 74 , 4048–4051] at the BESSY II synchrotron at the Helmholtz‐Zentrum Berlin. A magnetic‐field pulse serves as excitation, and the magnetization precession is probed by element‐selective X‐ray resonant magnetic scattering. With the use of single‐bunch‐generated X‐rays a temporal resolution well below 100 ps is reached. The ALICE diffractometer environment enables investigations of thin films, described here, multilayers and laterally structured samples in reflection or diffuse scattering geometry. The combination of the time‐resolved set‐up with a cryostat in the ALICE chamber will allow temperature‐dependent studies of precessional magnetization dynamics and of damping constants to be conducted over a large temperature range and for a large variety of systems in reflection geometry.     

Tests and characterization of a laterally graded multilayer Montel mirror

Multilayers are becoming an increasingly important tool in X‐ray optics. The essential parameters to design a pair of laterally graded multilayer mirrors arranged in a Montel‐type configuration for use as an X‐ray collimating device are provided. The results of X‐ray reflectometry tests carried out on the optics in addition to metrology characterization are also shown. Finally, using experimental data and combined with X‐ray tracing simulations it is demonstrated that the mirror meets all stringent specifications as required for a novel ultra‐high‐resolution inelastic X‐ray scattering spectrometer at the Advanced Photon Source.     

Collimating Montel mirror as part of a multi‐crystal analyzer system for resonant inelastic X‐ray scattering

Advances in resonant inelastic X‐ray scattering (RIXS) have come in lockstep with improvements in energy resolution. Currently, the best energy resolution at the Ir L₃‐edge stands at ～25 meV, which is achieved using a diced Si(844) spherical crystal analyzer. However, spherical analyzers are limited by their intrinsic reflection width. A novel analyzer system using multiple flat crystals provides a promising way to overcome this limitation. For the present design, an energy resolution at or below 10 meV was selected. Recognizing that the angular acceptance of flat crystals is severely limited, a collimating element is essential to achieve the necessary solid‐angle acceptance. For this purpose, a laterally graded, parabolic, multilayer Montel mirror was designed for use at the Ir L₃‐absorption edge. It provides an acceptance larger than 10 mrad, collimating the reflected X‐ray beam to smaller than 100 µrad, in both vertical and horizontal directions. The performance of this mirror was studied at beamline 27‐ID at the Advanced Photon Source. X‐rays from a diamond (111) monochromator illuminated a scattering source of diameter 5 µm, generating an incident beam on the mirror with a well determined divergence of 40 mrad. A flat Si(111) crystal after the mirror served as the divergence analyzer. From X‐ray measurements, ray‐tracing simulations and optical metrology results, it was established that the Montel mirror satisfied the specifications of angular acceptance and collimation quality necessary for a high‐resolution RIXS multi‐crystal analyzer system.     

The use of X‐ray interaction data to differentiate malignant from normal breast tissue at surgical margins and biopsy analysis

X‐ray interaction data, including measuring bio‐metal levels and scattering characteristics, are being shown to be a possible discriminating variable in the classification of human tissues. However, a major concern when using X‐ray interaction data in breast cancer material is that the samples are rarely 100% tumour because of the invasive nature of the disease. The work reported here includes a methodology to help overcome this limitation as the experimental protocol includes mapping the data to histological analysis of the measured samples. This work has shown how important it is to relate the measured X‐ray parameters to the histology of the samples, particularly the clinical information that describes the percentage of tumour within each sample. Levels of K, Ca, Zn, Fe, Cu, Br and Rb were evaluated using X‐ray fluorescence and compared between tumour breast tissue and normal surrounding breast tissue. The coherent scattering properties of each sample were also examined using an angular dispersive X‐ray diffraction technique. Multivariate modelling using soft independent modelling of class analogy was used to classify samples kept out of the modelling procedure. A significant increase (p < 0.01) in the levels of Rb, Zn and K was found in the tumour samples. The levels of these elements show a correlation with the percentage of tumour reported to be present in a given sample. The results of classifying unknown tissue samples are presented using two‐class and three‐class models that help to reveal the importance of sample histology in studies involving breast cancers. Copyright © 2013 John Wiley & Sons, Ltd.     

Study on the reflectivity properties of spherically bent analyser crystals

Theoretical and experimental studies are presented on properties of spherically bent analyser crystals for high‐resolution X‐ray spectrometry. A correction to the bent‐crystal strain field owing to its finite surface area is derived. The results are used to explain the reflectivity curves and anisotropic properties of Si(660) and Si(553) analysers in near‐backscattering geometry. The results from the calculation agree very well with experimental results obtained using an inelastic X‐ray scattering synchrotron beamline.     

A miniature closed‐circle flow cell for high photon flux X‐ray scattering experiments

A closed‐circle miniature flow cell for high X‐ray photon flux experiments on radiation‐sensitive liquid samples is presented. The compact cell is made from highly inert material and the flow is induced by a rotating magnetic stir bar, which acts as a centrifugal pump inside the cell. The cell is ideal for radiation‐sensitive yet precious or hazardous liquid samples, such as concentrated acids or bases. As a demonstration of the cell's capabilities, X‐ray Raman scattering spectroscopy data on the oxygen K‐edge of liquid water under ambient conditions are presented.     

X‐ray fluorescence determination of the manganese valence state and speciation in manganese ores

This work concerns determination of the manganese valence state and speciation by wavelength‐dispersive X‐ray fluorescence analysis. The authors investigated the effect of the manganese valence state and speciation on the intensity of some К‐series lines of the X‐ray emission spectrum for the samples of manganese compounds. The intensities of MnKβ₅ line and MnKβ′ satellite are least influenced by speciation, and they may be used for evaluating the manganese valence state for the samples containing low iron. The intensities of MnKβ″ and MnKβ^x satellites may be employed for assessing the manganese speciation. The results of X‐ray fluorescence determination of the manganese valence state and speciation in the manganese ores of the South Ural deposits agree with the X‐ray diffraction data. The X‐ray fluorescence method is definitely advantageous, because it does not require a complicated process of sample preparation and allows to receive fast information on the manganese valence state and speciation with the purpose to assess the quality of manganese ores. Copyright © 2015 John Wiley & Sons, Ltd.     

A three‐crystal spectrometer for high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy and X‐ray emission spectroscopy at SSRF

A Johann‐type spectrometer for the study of high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy, X‐ray emission spectroscopy and resonant inelastic X‐ray scattering has been developed at BL14W1 X‐ray absorption fine structure spectroscopy beamline of Shanghai Synchrotron Radiation Facility. The spectrometer consists of three crystal analyzers mounted on a vertical motion stage. The instrument is scanned vertically and covers the Bragg angle range of 71.5–88°. The energy resolution of the spectrometer ranges from sub‐eV to a few eV. The spectrometer has a solid angle of about 1.87 × 0^?3 of 4π sr, and the overall photons acquired by the detector could be 10⁵ counts per second for the standard sample. The performances of the spectrometer are illustrated by the three experiments that are difficult to perform with the conventional absorption or emission spectroscopy. Copyright © 2016 John Wiley & Sons, Ltd.     

The small‐angle and wide‐angle X‐ray scattering set‐up at beamline BL9 of DELTA

The multi‐purpose experimental endstation of beamline BL9 at the Dortmund Electron Accelerator (DELTA) is dedicated to diffraction experiments in grazing‐incidence geometry, reflectivity and powder diffraction measurements. Moreover, fluorescence analysis and inelastic X‐ray scattering experiments can be performed. Recently, a new set‐up for small‐angle and wide‐angle X‐ray scattering utilizing detection by means of an image‐plate scanner was installed and is described in detail here. First small‐angle X‐ray scattering experiments on aqueous solutions of lysozyme with different cosolvents and of staphylococcal nuclease are discussed. The application of the set‐up for texture analysis is emphasized and a study of the crystallographic texture of natural bio‐nanocomposites, using lobster and crab cuticles as model materials, is presented.