Monte Carlo simulation code for confocal 3D micro‐beam X‐ray fluorescence analysis of stratified materials

Stratified materials are of great importance for many branches of modern industry, e.g. electronics or optics and for biomedical applications. Examination of chemical composition of individual layers and determination of their thickness helps to get information on their properties and function. A confocal 3D micro X‐ray fluorescence (3D µXRF) spectroscopy is an analytical method giving the possibility to investigate 3D distribution of chemical elements in a sample with spatial resolution in the micrometer regime in a non‐destructive way. Thin foils of Ti, Cu and Au, a bulk sample of Cu and a three‐layered sandwich sample, made of two thin Fe/Ni alloy foils, separated by polypropylene, were used as test samples. A Monte Carlo (MC) simulation code for the determination of elemental concentrations and thickness of individual layers in stratified materials with the use of confocal 3D µXRF spectroscopy was developed. The X‐ray intensity profiles versus the depth below surface, obtained from 3D µXRF experiments, MC simulation and an analytical approach were compared. Correlation coefficients between experimental versus simulated, and experimental versus analytical model X‐ray profiles were calculated. The correlation coefficients were comparable for both methods and exceeded 99%. The experimental X‐ray intensity profiles were deconvoluted with iterative MC simulation and by using analytical expression. The MC method produced slightly more accurate elemental concentrations and thickness of successive layers as compared to the results of the analytical approach. This MC code is a robust tool for simulation of scanning confocal 3D µXRF experiments on stratified materials and for quantitative interpretation of experimental results. Copyright © 2011 John Wiley & Sons, Ltd.     

Full‐field X‐ray reflection microscopy of epitaxial thin‐films

Novel X‐ray imaging of structural domains in a ferroelectric epitaxial thin film using diffraction contrast is presented. The full‐field hard X‐ray microscope uses the surface scattering signal, in a reflectivity or diffraction experiment, to spatially resolve the local structure with 70 nm lateral spatial resolution and sub‐nanometer height sensitivity. Sub‐second X‐ray exposures can be used to acquire a 14 µm × 14 µm image with an effective pixel size of 20 nm on the sample. The optical configuration and various engineering considerations that are necessary to achieve optimal imaging resolution and contrast in this type of microscopy are discussed.     

Elemental depth profiling with a wire in microbeam X‐ray fluorescence analysis

This study proposes simple techniques involving the use of a thin wire set close to the sample surface to measure the elemental depth distribution in microbeam X‐ray fluorescence analysis. One is the X‐ray fluorescence detection in energy‐dispersive mode using a solid‐state detector in combination with the sample movement, and the other is in projection mode using an X‐ray charge‐coupled device camera. The minimum depth resolution (spatial resolution) obtained with a thin Mo wire is about 15 µm. Compared with a confocal depth‐profiling method, wire depth‐profile analysis is easy to implement, flexible, and has reasonable sensitivity. Copyright © 2011 John Wiley & Sons, Ltd.     

Time‐resolved X‐ray PIV technique for diagnosing opaque biofluid flow with insufficient X‐ray fluxes

X‐ray imaging is used to visualize the biofluid flow phenomena in a nondestructive manner. A technique currently used for quantitative visualization is X‐ray particle image velocimetry (PIV). Although this technique provides a high spatial resolution (less than 10 µm), significant hemodynamic parameters are difficult to obtain under actual physiological conditions because of the limited temporal resolution of the technique, which in turn is due to the relatively long exposure time (～10 ms) involved in X‐ray imaging. This study combines an image intensifier with a high‐speed camera to reduce exposure time, thereby improving temporal resolution. The image intensifier amplifies light flux by emitting secondary electrons in the micro‐channel plate. The increased incident light flux greatly reduces the exposure time (below 200 µs). The proposed X‐ray PIV system was applied to high‐speed blood flows in a tube, and the velocity field information was successfully obtained. The time‐resolved X‐ray PIV system can be employed to investigate blood flows at beamlines with insufficient X‐ray fluxes under specific physiological conditions. This method facilitates understanding of the basic hemodynamic characteristics and pathological mechanism of cardiovascular diseases.     

Large‐surface‐area diamond (111) crystal plates for applications in high‐heat‐load wavefront‐preserving X‐ray crystal optics

Fabrication and results of high‐resolution X‐ray topography characterization of diamond single‐crystal plates with large surface area (10 mm × 10 mm) and (111) crystal surface orientation for applications in high‐heat‐load X‐ray crystal optics are reported. The plates were fabricated by laser‐cutting of the (111) facets of diamond crystals grown using high‐pressure high‐temperature methods. The intrinsic crystal quality of a selected 3 mm × 7 mm crystal region of one of the studied samples was found to be suitable for applications in wavefront‐preserving high‐heat‐load crystal optics. Wavefront characterization was performed using sequential X‐ray diffraction topography in the pseudo plane wave configuration and data analysis using rocking‐curve topography. The variations of the rocking‐curve width and peak position measured with a spatial resolution of 13 µm × 13 µm over the selected region were found to be less than 1 µrad.     

Design of an ultrahigh‐energy‐resolution and wide‐energy‐range soft X‐ray beamline

A new ultrahigh‐energy‐resolution and wide‐energy‐range soft X‐ray beamline has been designed and is under construction at the Shanghai Synchrotron Radiation Facility. The beamline has two branches: one dedicated to angle‐resolved photoemission spectroscopy (ARPES) and the other to photoelectron emission microscopy (PEEM). The two branches share the same plane‐grating monochromator, which is equipped with four variable‐line‐spacing gratings and covers the 20–2000 eV energy range. Two elliptically polarized undulators are employed to provide photons with variable polarization, linear in every inclination and circular. The expected energy resolution is approximately 10 meV at 1000 eV with a flux of more than 3 × 10¹⁰ photons s^?1 at the ARPES sample positions. The refocusing of both branches is based on Kirkpatrick–Baez pairs. The expected spot sizes when using a 10 µm exit slit are 15 µm × 5 µm (horizontal × vertical FWHM) at the ARPES station and 10 µm × 5 µm (horizontal × vertical FWHM) at the PEEM station. The use of plane optical elements upstream of the exit slit, a variable‐line‐spacing grating and a pre‐mirror in the monochromator that allows the influence of the thermal deformation to be eliminated are essential for achieving the ultrahigh‐energy resolution.     

Focusing synchrotron radiation using a polycapillary half‐focusing X‐ray lens for imaging

An imaging system based on a polycapillary half‐focusing X‐ray lens (PHFXRL) and synchrotron radiation source has been designed. The focal spot size and the gain in power density of the PHFXRL were 22 µm (FWHM) and 4648, respectively, at 14.0 keV. The spatial resolution of this new imaging system was better than 5 µm when an X‐ray charge coupled device with a pixel size of 10.9 × 10.9 µm was used. A fossil of an ancient biological specimen was imaged using this system.     

Hard X‐ray nanotomography beamline 7C XNI at PLS‐II

The synchrotron‐based hard X‐ray nanotomography beamline, named 7C X‐ray Nano Imaging (XNI), was recently established at Pohang Light Source II. This beamline was constructed primarily for full‐field imaging of the inner structures of biological and material samples. The beamline normally provides 46 nm resolution for still images and 100 nm resolution for tomographic images, with a 40 µm field of view. Additionally, for large‐scale application, it is capable of a 110 µm field of view with an intermediate resolution.     

The first microbeam synchrotron X‐ray fluorescence beamline at the Siam Photon Laboratory

The first microbeam synchrotron X‐ray fluorescence (µ‐SXRF) beamline using continuous synchrotron radiation from Siam Photon Source has been constructed and commissioned as of August 2011. Utilizing an X‐ray capillary half‐lens allows synchrotron radiation from a 1.4 T bending magnet of the 1.2 GeV electron storage ring to be focused from a few millimeters‐sized beam to a micrometer‐sized beam. This beamline was originally designed for deep X‐ray lithography (DXL) and was one of the first two operational beamlines at this facility. A modification has been carried out to the beamline in order to additionally enable µ‐SXRF and synchrotron X‐ray powder diffraction (SXPD). Modifications included the installation of a new chamber housing a Si(111) crystal to extract 8 keV synchrotron radiation from the white X‐ray beam (for SXPD), a fixed aperture and three gate valves. Two end‐stations incorporating optics and detectors for µ‐SXRF and SXPD have then been installed immediately upstream of the DXL station, with the three techniques sharing available beam time. The µ‐SXRF station utilizes a polycapillary half‐lens for X‐ray focusing. This optic focuses X‐ray white beam from 5 mm × 2 mm (H × V) at the entrance of the lens down to a diameter of 100 µm FWHM measured at a sample position 22 mm (lens focal point) downstream of the lens exit. The end‐station also incorporates an XYZ motorized sample holder with 25 mm travel per axis, a 5× ZEISS microscope objective with 5 mm × 5 mm field of view coupled to a CCD camera looking to the sample, and an AMPTEK single‐element Si (PIN) solid‐state detector for fluorescence detection. A graphic user interface data acquisition program using the LabVIEW platform has also been developed in‐house to generate a series of single‐column data which are compatible with available XRF data‐processing software. Finally, to test the performance of the µ‐SXRF beamline, an elemental surface profile has been obtained for a piece of ancient pottery from the Ban Chiang archaeological site, a UNESCO heritage site. It was found that the newly constructed µ‐SXRF technique was able to clearly distinguish the distribution of different elements on the specimen.     

BioCARS: a synchrotron resource for time‐resolved X‐ray science

BioCARS, a NIH‐supported national user facility for macromolecular time‐resolved X‐ray crystallography at the Advanced Photon Source (APS), has recently completed commissioning of an upgraded undulator‐based beamline optimized for single‐shot laser‐pump X‐ray‐probe measurements with time resolution as short as 100 ps. The source consists of two in‐line undulators with periods of 23 and 27 mm that together provide high‐flux pink‐beam capability at 12 keV as well as first‐harmonic coverage from 6.8 to 19 keV. A high‐heat‐load chopper reduces the average power load on downstream components, thereby preserving the surface figure of a Kirkpatrick–Baez mirror system capable of focusing the X‐ray beam to a spot size of 90 µm horizontal by 20 µm vertical. A high‐speed chopper isolates single X‐ray pulses at 1 kHz in both hybrid and 24‐bunch modes of the APS storage ring. In hybrid mode each isolated X‐ray pulse delivers up to ～4 × 10¹⁰ photons to the sample, thereby achieving a time‐averaged flux approaching that of fourth‐generation X‐FEL sources. A new high‐power picosecond laser system delivers pulses tunable over the wavelength range 450–2000 nm. These pulses are synchronized to the storage‐ring RF clock with long‐term stability better than 10 ps RMS. Monochromatic experimental capability with Biosafety Level 3 certification has been retained.     

X‐ray position‐sensitive duo‐lateral diamond detectors at SOLEIL

The performance of a diamond X‐ray beam position monitor is reported. This detector consists of an ionization solid‐state chamber based on a thin single‐crystal chemical‐vapour‐deposition diamond with position‐sensitive resistive electrodes in a duo‐lateral configuration. The detector's linearity, homogeneity and responsivity were studied on beamlines at Synchrotron SOLEIL with various beam sizes, intensities and energies. These measurements demonstrate the large and homogeneous (absorption variation of less than 0.7% over 500 µm × 500 µm) active area of the detector, with linear responses independent of the X‐ray beam spatial distribution. Due to the excellent charge collection efficiency (approaching 100%) and intensity sensitivity (0.05%), the detector allows monitoring of the incident beam flux precisely. In addition, the in‐beam position resolution was compared with a theoretical analysis providing an estimation of the detector's beam position resolution capability depending on the experimental conditions (X‐ray flux, energy and readout acquisition time).     

Application of kinoform lens for X‐ray reflectivity analysis

In this paper the first practical application of kinoform lenses for the X‐ray reflectivity characterization of thin layered materials is demonstrated. The focused X‐ray beam generated from a kinoform lens, a line of nominal size ～50 µm × 2 µm, provides a unique possibility to measure the X‐ray reflectivities of thin layered materials in sample scanning mode. Moreover, the small footprint of the X‐ray beam, generated on the sample surface at grazing incidence angles, enables one to measure the absolute X‐ray reflectivities. This approach has been tested by analyzing a few thin multilayer structures. The advantages achieved over the conventional X‐ray reflectivity technique are discussed and demonstrated by measurements.     

Development of a two‐dimensional imaging system of X‐ray absorption fine structure

A two‐dimensional imaging system of X‐ray absorption fine structure (XAFS) has been developed at beamline BL‐4 of the Synchrotron Radiation Center of Ritsumeikan University. The system mainly consists of an ionization chamber for I₀ measurement, a sample stage, and a two‐dimensional complementary metal oxide semiconductor (CMOS) image sensor for measuring the transmitted X‐ray intensity. The X‐ray energy shift in the vertical direction, which originates from the vertical divergence of the X‐ray beam on the monochromator surface, is corrected by considering the geometrical configuration of the monochromator. This energy correction improves the energy resolution of the XAFS spectrum because each pixel in the CMOS detector has a very small vertical acceptance of ～0.5 µrad. A data analysis system has also been developed to automatically determine the energy of the absorption edge. This allows the chemical species to be mapped based on the XANES feature over a wide area of 4.8 mm (H) × 3.6 mm (V) with a resolution of 10 µm × 10 µm. The system has been applied to the chemical state mapping of the Mn species in a LiMn₂O₄ cathode. The heterogeneous distribution of the Mn oxidation state is demonstrated and is considered to relate to the slow delocalization of Li⁺‐defect sites in the spinel crystal structure. The two‐dimensional‐imaging XAFS system is expected to be a powerful tool for analyzing the spatial distributions of chemical species in many heterogeneous materials such as battery electrodes.     

Design and performance of an X‐ray scanning microscope at the Hard X‐ray Nanoprobe beamline of NSLS‐II

A hard X‐ray scanning microscope installed at the Hard X‐ray Nanoprobe beamline of the National Synchrotron Light Source II has been designed, constructed and commissioned. The microscope relies on a compact, high stiffness, low heat dissipation approach and utilizes two types of nanofocusing optics. It is capable of imaging with ～15 nm × 15 nm spatial resolution using multilayer Laue lenses and 25 nm × 26 nm resolution using zone plates. Fluorescence, diffraction, absorption, differential phase contrast, ptychography and tomography are available as experimental techniques. The microscope is also equipped with a temperature regulation system which allows the temperature of a sample to be varied in the range between 90 K and 1000 K. The constructed instrument is open for general users and offers its capabilities to the material science, battery research and bioscience communities.     

Performance of the micro‐PIC gaseous area detector in small‐angle X‐ray scattering experiments

The application of a two‐dimensional photon‐counting detector based on a micro‐pixel gas chamber (µ‐PIC) to high‐resolution small‐angle X‐ray scattering (SAXS), and its performance, are reported. The µ‐PIC is a micro‐pattern gaseous detector fabricated by printed circuit board technology. This article describes the performance of the µ‐PIC in SAXS experiments at SPring‐8. A dynamic range of >10⁵ was obtained for X‐ray scattering from a polystyrene sphere solution. A maximum counting rate of up to 5 MHz was observed with good linearity and without saturation. For a diffraction pattern of collagen, weak peaks were observed in the high‐angle region in one accumulation of photons.     

Simultaneous small‐ and wide‐angle scattering at high X‐ray energies

Combined small‐ and wide‐angle X‐ray scattering (SAXS/WAXS) is a powerful technique for the study of materials at length scales ranging from atomic/molecular sizes (a few angstroms) to the mesoscopic regime (～1 nm to ～1 µm). A set‐up to apply this technique at high X‐ray energies (E > 50 keV) has been developed. Hard X‐rays permit the execution of at least three classes of investigations that are significantly more difficult to perform at standard X‐ray energies (8–20 keV): (i) in situ strain analysis revealing anisotropic strain behaviour both at the atomic (WAXS) as well as at the mesoscopic (SAXS) length scales, (ii) acquisition of WAXS patterns to very large q (>20 Å^?1) thus allowing atomic pair distribution function analysis (SAXS/PDF) of micro‐ and nano‐structured materials, and (iii) utilization of complex sample environments involving thick X‐ray windows and/or samples that can be penetrated only by high‐energy X‐rays. Using the reported set‐up a time resolution of approximately two seconds was demonstrated. It is planned to further improve this time resolution in the near future.     

Confocal macro X‐ray fluorescence spectrometer on commercial 3D printer

Novel confocal X‐ray fluorescence (XRF) spectrometer was designed and constructed for 3D analysis of elementary composition in the surface layer of spatially extended objects having unlimited chemical composition and geometrical shape. The main elements of the XRF device were mounted on a moving frame of a commercial 3D printer. The XRF unit consists of a silicon drift detector and a low‐power transmission‐type X‐ray tube. Both the excitation and secondary X‐ray beams were formed and regulated by simple collimator systems in order to create a macro confocal measuring setup. The spatial accuracy of the mechanical stages of the 3D printer achieved was less than 5 μm at 100‐μm step‐size. The diameter of the focal spot of the confocal measuring arrangement was between 1.5 and 2.0 mm. The alignment of the excitation and secondary X‐ray beams and the selection of the measuring spot on the sample surface were ensured by two laser beams and a digital microscope for visualization of the irradiated spot. The elements of the optical system together with the XRF spectrometer were mounted on the horizontal arm of the 3D printer, which mechanical design is capable of synchronized moving the full spectroscopic device within vertical directions. Analytical capability and the 3D spatial resolution of the confocal spectrometer were determined. Copyright © 2017 John Wiley & Sons, Ltd.     

Microfocusing options for the inelastic X‐ray scattering beamline at sector 3 of the Advanced Photon Source

Synchrotron radiation from third‐generation high‐brilliance storage rings is an ideal source for X‐ray microbeams. The aim of this paper is to describe a microfocusing scheme that combines both a toroidal mirror and Kirkpatrick–Baez (KB) mirrors for upgrading the existing optical system for inelastic X‐ray scattering experiments at sector 3 of the Advanced Photon Source. SHADOW ray‐tracing simulations without considering slope errors of both the toroidal mirror and KB mirrors show that this combination can provide a beam size of 4.5 µm (H) × 0.6 µm (V) (FWHM) at the end of the existing D‐station (66 m from the source) with use of full beam transmission of up to 59%, and a beam size of 3.7 µm (H) × 0.46 µm (V) (FWHM) at the front‐end of the proposed E‐station (68 m from the source) with a transmission of up to 52%. A beam size of about 5 µm (H) × 1 µm (V) can be obtained, which is close to the ideal case, by using high‐quality mirrors (with slope errors of less than 0.5 µrad r.m.s.). Considering the slope errors of the existing toroidal and KB mirrors (5 and 2.9 µrad r.m.s., respectively), the beam size grows to about 13.5 µm (H) × 6.3 µm (V) at the end of the D‐station and to 12.0 µm (H) × 6.0 µm (V) at the front‐end of the proposed E‐station. The simulations presented here are compared with the experimental measurements that are significantly larger than the theoretical values even when slope error is included in the simulations. This is because of the experimental set‐up that could not yet be optimized.     

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.     

3D imaging of a rice pollen grain using transmission X‐ray microscopy

For the first time, the three‐dimensional (3D) ultrastructure of an intact rice pollen cell has been obtained using a full‐field transmission hard X‐ray microscope operated in Zernike phase contrast mode. After reconstruction and segmentation from a series of projection images, complete 3D structural information of a 35 µm rice pollen grain is presented at a resolution of ～100 nm. The reconstruction allows a clear differentiation of various subcellular structures within the rice pollen grain, including aperture, lipid body, mitochondrion, nucleus and vacuole. Furthermore, quantitative information was obtained about the distribution of cytoplasmic organelles and the volume percentage of each kind of organelle. These results demonstrate that transmission X‐ray microscopy can be quite powerful for non‐destructive investigation of 3D structures of whole eukaryotic cells.