Implementation of ultrafast X‐ray diffraction at the 1W2B wiggler beamline of Beijing Synchrotron Radiation Facility

The implementation of a laser pump/X‐ray probe scheme for performing picosecond‐resolution X‐ray diffraction at the 1W2B wiggler beamline at Beijing Synchrotron Radiation Facility is reported. With the hybrid fill pattern in top‐up mode, a pixel array X‐ray detector was optimized to gate out the signal from the singlet bunch with interval 85 ns from the bunch train. The singlet pulse intensity is ～2.5 × 10⁶ photons pulse^?1 at 10 keV. The laser pulse is synchronized to this singlet bunch at a 1 kHz repetition rate. A polycapillary X‐ray lens was used for secondary focusing to obtain a 72 µm (FWHM) X‐ray spot. Transient photo‐induced strain in BiFeO₃ film was observed at a ～150 ps time resolution for demonstration.     

The power of in situ pulsed laser deposition synchrotron characterization for the detection of domain formation during growth of Ba0.5Sr0.5TiO3 on MgO

A highly sophisticated pulsed laser deposition (PLD) chamber has recently been installed at the NANO beamline at the synchrotron facility ANKA (Karlsruhe, Germany), which allows for comprehensive studies on the PLD growth process of dielectric, ferroelectric and ferromagnetic thin films in epitaxial oxide heterostructures or even multilayer systems by combining in situ reflective high‐energy diffraction with the in situ synchrotron high‐resolution X‐ray diffraction and surface diffraction methods. The modularity of the in situ PLD chamber offers the opportunity to explore the microstructure of the grown thin films as a function of the substrate temperature, gas pressure, laser fluence and target–substrate separation distance. Ba_0.5Sr_0.5TiO₃ grown on MgO represents the first system that is grown in this in situ PLD chamber and studied by in situ X‐ray reflectivity, in situ two‐dimensional reciprocal space mapping of symmetric X‐ray diffraction and acquisition of time‐resolved diffraction profiles during the ablation process. In situ PLD synchrotron investigation has revealed the occurrence of structural distortion as well as domain formation and misfit dislocation which all depend strongly on the film thickness. The microstructure transformation has been accurately detected with a time resolution of 1 s. The acquisition of two‐dimensional reciprocal space maps during the PLD growth has the advantage of simultaneously monitoring the changes of the crystalline structure as well as the formation of defects. The stability of the morphology during the PLD growth is demonstrated to be remarkably affected by the film thickness. A critical thickness for the domain formation in Ba_0.5Sr_0.5TiO₃ grown on MgO could be determined from the acquisition of time‐resolved diffraction profiles during the PLD growth. A splitting of the diffraction peak into two distinguishable peaks has revealed a morphology change due to modification of the internal strain during growth.     

Polytypism in GaAs nanowires: determination of the interplanar spacing of wurtzite GaAs by X‐ray diffraction

In GaAs nanowires grown along the cubic [111]_c direction, zinc blende and wurtzite arrangements have been observed in their stacking sequence, since the energetic barriers for nucleation are typically of similar order of magnitude. It is known that the interplanar spacing of the (111)_c Ga (or As) planes in the zinc blende polytype varies slightly from the wurtzite polytype. However, different values have been reported in the literature. Here, the ratio of the interplanar spacing of these polytypes is extracted based on X‐ray diffraction measurements for thin GaAs nanowires with a mean diameter of 18–25 nm. The measurements are performed with a nano‐focused beam which facilitates the separation of the scattering of nanowires and of parasitic growth. The interplanar spacing of the (111)_c Ga (or As) planes in the wurtzite arrangement in GaAs nanowires is observed to be 0.66% ± 0.02% larger than in the zinc blende arrangement.     

A feasibility study of dynamic stress analysis inside a running internal combustion engine using synchrotron X‐ray beams

The present investigation establishes the feasibility of using synchrotron‐generated X‐ray beams for time‐resolved in situ imaging and diffraction of the interior components of an internal combustion engine during its operation. The demonstration experiment was carried out on beamline I12 (JEEP) at Diamond Light Source, UK. The external hutch of the JEEP instrument is a large‐scale engineering test bed for complex in situ processing and simulation experiments. The hutch incorporates a large capacity translation and rotation table and a selection of detectors for monochromatic and white‐beam diffraction and imaging. These capabilities were used to record X‐ray movies of a motorcycle internal combustion engine running at 1850 r.p.m. and to measure strain inside the connecting rod via stroboscopic X‐ray diffraction measurement. The high penetrating ability and high flux of the X‐ray beam at JEEP allowed the observation of inlet and outlet valve motion, as well as that of the piston, connecting rod and the timing chain within the engine. Finally, the dynamic internal strain within the moving connecting rod was evaluated with an accuracy of ～50 × 10^?6.     

In‐situ X‐ray diffraction study of an electric field induced phase transition and giant strain in Na0.5Bi0.5TiO3–x %BaTiO3 lead‐free single crystals

A giant electric field (E) induced strain of ε = 0.60% has been observed for Na_0.5Bi_0.5TiO₃–5.6%BaTiO₃ single crystals under E = 20 kV/cm at 130 °C. In‐situ X‐ray diffraction (XRD) revealed that this induced transition was between pseudocubic and tetragonal structures. Our work provides a potential alternative to lead‐based piezoelectric materials. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Utilizing broadband X‐rays in a Bragg coherent X‐ray diffraction imaging experiment

A method is presented to simplify Bragg coherent X‐ray diffraction imaging studies of complex heterogeneous crystalline materials with a two‐stage screening/imaging process that utilizes polychromatic and monochromatic coherent X‐rays and is compatible with in situ sample environments. Coherent white‐beam diffraction is used to identify an individual crystal particle or grain that displays desired properties within a larger population. A three‐dimensional reciprocal‐space map suitable for diffraction imaging is then measured for the Bragg peak of interest using a monochromatic beam energy scan that requires no sample motion, thus simplifying in situ chamber design. This approach was demonstrated with Au nanoparticles and will enable, for example, individual grains in a polycrystalline material of specific orientation to be selected, then imaged in three dimensions while under load.     

Development of variable‐magnification X‐ray Bragg optics

A novel X‐ray Bragg optics is proposed for variable‐magnification of an X‐ray beam. This X‐ray Bragg optics is composed of two magnifiers in a crossed arrangement, and the magnification factor, M, is controlled through the azimuth angle of each magnifier. The basic properties of the X‐ray optics such as the magnification factor, image transformation matrix and intrinsic acceptance angle are described based on the dynamical theory of X‐ray diffraction. The feasibility of the variable‐magnification X‐ray Bragg optics was verified at the vertical‐wiggler beamline BL‐14B of the Photon Factory. For X‐ray Bragg magnifiers, Si(220) crystals with an asymmetric angle of 14° were used. The magnification factor was calculated to be tunable between 0.1 and 10.0 at a wavelength of 0.112 nm. At various magnification factors (M≥ 1.0), X‐ray images of a nylon mesh were observed with an air‐cooled X‐ray CCD camera. Image deformation caused by the optics could be corrected by using a 2 × 2 transformation matrix and bilinear interpolation method. Not only absorption‐contrast but also edge‐contrast due to Fresnel diffraction was observed in the magnified images.     

High‐energy X‐ray diffraction using the Pixium 4700 flat‐panel detector

The Pixium 4700 detector represents a significant step forward in detector technology for high‐energy X‐ray diffraction. The detector design is based on digital flat‐panel technology, combining an amorphous Si panel with a CsI scintillator. The detector has a useful pixel array of 1910 × 2480 pixels with a pixel size of 154 µm × 154 µm, and thus it covers an effective area of 294 mm × 379 mm. Designed for medical imaging, the detector has good efficiency at high X‐ray energies. Furthermore, it is capable of acquiring sequences of images at 7.5 frames per second in full image mode, and up to 60 frames per second in binned region of interest modes. Here, the basic properties of this detector applied to high‐energy X‐ray diffraction are presented. Quantitative comparisons with a widespread high‐energy detector, the MAR345 image plate scanner, are shown. Other properties of the Pixium 4700 detector, including a narrow point‐spread function and distortion‐free image, allows for the acquisition of high‐quality diffraction data at high X‐ray energies. In addition, high frame rates and shutterless operation open new experimental possibilities. Also provided are the necessary data for the correction of images collected using the Pixium 4700 for diffraction purposes.     

X‐ray photon correlation spectroscopy in systems without long‐range order: existence of an intermediate‐field regime

Successful X‐ray photon correlation spectroscopy studies often require that signals be optimized while minimizing power density in the sample to decrease radiation damage and, at free‐electron laser sources, thermal impact. This suggests exploration of scattering outside the Fraunhofer far‐field diffraction limit d²/λR, where d is the incident beam size, λ is the photon wavelength and R is the sample‐to‐detector distance. Here it is shown that, in an intermediate regime d²/λ > Rdξ/λ, where ξ is the structural correlation length in the material, the ensemble averages of the scattered intensity and of the structure factor are equal. Similarly, in the regime d²/λ > Rdξ(τ)/λ, where ξ(τ) is a time‐dependent dynamics length scale of interest, the ensemble‐averaged correlation functions g₁(τ) and g₂(τ) of the scattered electric field are also equal to their values in the far‐field limit. This broadens the parameter space for X‐ray photon correlation spectroscopy experiments, but detectors with smaller pixel size and variable focusing are required to more fully exploit the potential for such studies.     

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.     

A new approach to synchrotron energy‐dispersive X‐ray diffraction computed tomography

A new data collection strategy for performing synchrotron energy‐dispersive X‐ray diffraction computed tomography has been devised. This method is analogous to angle‐dispersive X‐ray diffraction whose diffraction signal originates from a line formed by intersection of the incident X‐ray beam and the sample. Energy resolution is preserved by using a collimator which defines a small sampling voxel. This voxel is translated in a series of parallel straight lines covering the whole sample and the operation is repeated at different rotation angles, thus generating one diffraction pattern per translation and rotation step. The method has been tested by imaging a specially designed phantom object, devised to be a demanding validator for X‐ray diffraction imaging. The relative strengths and weaknesses of the method have been analysed with respect to the classic angle‐dispersive technique. The reconstruction accuracy of the method is good, although an absorption correction is required for lower energy diffraction because of the large path lengths involved. The spatial resolution is only limited to the width of the scanning beam owing to the novel collection strategy. The current temporal resolution is poor, with a scan taking several hours. The method is best suited to studying large objects (e.g. for engineering and materials science applications) because it does not suffer from diffraction peak broadening effects irrespective of the sample size, in contrast to the angle‐dispersive case.     

Structural evolution of self‐assisted GaAs nanowires grown on Si(111)

GaAs nanowires are grown on Si(111) by self‐assisted molecular beam epitaxy, and the ratio between wurtzite and zinc‐blende phases is determined as function of nanowire length using asymmetric X‐ray diffraction. We show that under the applied growth conditions, nanowires grow in both phases during the initial stage of growth, whereas the zinc‐blende content increases with growth time and dominates in long nanowires. Compared to the zinc‐blende units, the vertical lattice parameter of the wurtzite segments is 0.7% larger, as measured by the positions of respective diffraction peaks. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fabrication and testing of a newly designed slit system for depth‐resolved X‐ray diffraction measurements

A new system of slits called `spiderweb slits' have been developed for depth‐resolved powder or polycrystalline X‐ray diffraction measurements. The slits act on diffracted X‐rays to select a particular gauge volume of sample, while absorbing diffracted X‐rays from outside of this volume. Although the slit geometry is to some extent similar to that of previously developed conical slits or spiral slits, this new design has advantages over the previous ones in use for complex heterogeneous materials and in situ and operando diffraction measurements. For example, the slits can measure a majority of any diffraction cone for any polycrystalline material, over a continuous range of diffraction angles, and work for X‐ray energies of tens to hundreds of kiloelectronvolts. The design is generated and optimized using ray‐tracing simulations, and fabricated through laser micromachining. The first prototype was successfully tested at the X17A beamline at the National Synchrotron Light Source, and shows similar performance to simulations, demonstrating gauge volume selection for standard powders, for all diffraction peaks over angles of 2–10°. A similar, but improved, design will be implemented at the X‐ray Powder Diffraction beamline at the National Synchrotron Light Source II.     

Spectrometer for hard X‐ray free‐electron laser based on diffraction focusing

X‐ray free‐electron lasers (XFELs) generate sequences of ultra‐short spatially coherent pulses of X‐ray radiation. A diffraction focusing spectrometer (DFS), which is able to measure the whole energy spectrum of the radiation of a single XFEL pulse with an energy resolution of ΔE/E? 2 × 10^?6, is proposed. This is much better than for most modern X‐ray spectrometers. Such resolution allows one to resolve the fine spectral structure of the XFEL pulse. The effect of diffraction focusing occurs in a single‐crystal plate due to dynamical scattering, and is similar to focusing in a Pendry lens made from a metamaterial with a negative refraction index. Such a spectrometer is easier to operate than those based on bent crystals. It is shown that the DFS can be used in a wide energy range from 5 keV to 20 keV.     

I18 – the microfocus spectroscopy beamline at the Diamond Light Source

The design and performance of the microfocus spectroscopy beamline at the Diamond Light Source are described. The beamline is based on a 27 mm‐period undulator to give an operable energy range between 2 and 20.7 keV, enabling it to cover the K‐edges of the elements from P to Mo and the L₃‐edges from Sr to Pu. Micro‐X‐ray fluorescence, micro‐EXAFS and micro‐X‐ray diffraction have all been achieved on the beamline with a spot size of ～3 µm. The principal optical elements of the beamline consist of a toroid mirror, a liquid‐nitrogen‐cooled double‐crystal monochromator and a pair of bimorph Kirkpatrick–Baez mirrors. The performance of the optics is compared with theoretical values and a few of the early experimental results are summarized.     

Impact of strain induced by polymer curing in benzocyclobutene embedded semiconductor nanostructures

Polymers such as benzocyclobutene are commonly used as embedding materials for semiconductor nanostructures. During the curing process of the polymer up to 250 °C, a significant impact of strain can be induced on the embedded semiconductor material due to different thermal expansion coefficients. This strain has been revealed by X‐ray diffraction in free‐standing GaAs nanowires grown on a silicon substrate, embedded in a polymer matrix. It will be shown that this strain is released during the X‐ray irradiation if additionally an external static electric field is applied.

     

A sample cell for in situ electric‐field‐dependent structural characterization and macroscopic strain measurements

When studying electro‐mechanical materials, observing the structural changes during the actuation process is necessary for gaining a complete picture of the structure–property relationship as certain mechanisms may be meta‐stable during actuation. In situ diffraction methods offer a powerful and direct means of quantifying the structural contributions to the macroscopic strain of these materials. Here, a sample cell is demonstrated capable of measuring the structural variations of electro‐mechanical materials under applied electric potentials up to 10 kV. The cell is designed for use with X‐ray scattering techniques in reflection geometry, while simultaneously collecting macroscopic strain data using a linear displacement sensor. The results show that the macroscopic strain measured using the cell can be directly correlated with the microscopic response of the material obtained from diffraction data. The capabilities of the cell have been successfully demonstrated at the Powder Diffraction beamline of the Australian Synchrotron and the potential implementation of this cell with laboratory X‐ray diffraction instrumentation is also discussed.     

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 sagittally focusing double‐multilayer monochromator for ultrafast X‐ray imaging applications

The development of a sagittally focusing double‐multilayer monochromator is reported, which produces a spatially extended wide‐bandpass X‐ray beam from an intense synchrotron bending‐magnet source at the Advanced Photon Source, for ultrafast X‐ray radiography and tomography applications. This monochromator consists of two W/B₄C multilayers with a 25 Å period coated on Si single‐crystal substrates. The second multilayer is mounted on a sagittally focusing bender, which can dynamically change the bending radius of the multilayer in order to condense and focus the beam to various points along the beamline. With this new apparatus, it becomes possible to adjust the X‐ray beam size to best match the area detector size and the object size to facilitate more efficient data collection using ultrafast X‐ray radiography and tomography.