X‐ray speckle visibility spectroscopy in the single‐photon limit

The technique of speckle visibility spectroscopy has been employed for the measurement of dynamics using coherent X‐ray scattering. It is shown that the X‐ray contrast within a single exposure can be related to the relaxation time of the intermediate scattering function, and this methodology is applied to the diffusion of 72 nm‐radius latex spheres in glycerol. Data were collected with exposure times as short as 2 ms by employing a resonant shutter. The weak scattering present for short exposures necessitated an analysis formalism based on the spatial correlation function of individual photon charge droplets on an area detector, rather than the usual methods employed for intensity correlations. It is demonstrated that this method gives good agreement between theory and experiment and thus holds promise for extending area‐detector‐based coherent scattering methods to the study of faster dynamics than previously obtainable.     

Coherent X‐ray scattering beamline at port 9C of Pohang Light Source II

The coherent X‐ray scattering beamline at the 9C port of the upgraded Pohang Light Source (PLS‐II) at Pohang Accelerator Laboratory in Korea is introduced. This beamline provides X‐rays of 5–20 keV, and targets coherent X‐ray experiments such as coherent diffraction imaging and X‐ray photon correlation spectroscopy. The main parameters of the beamline are summarized, and some preliminary experimental results are described.     

Application of an ePix100 detector for coherent scattering using a hard X‐ray free‐electron laser

A prototype ePix100 detector was used in small‐angle scattering geometry to capture speckle patterns from a static sample using the Linac Coherent Light Source (LCLS) hard X‐ray free‐electron laser at 8.34 keV. The average number of detected photons per pixel per pulse was varied over three orders of magnitude from about 23 down to 0.01 to test the detector performance. At high average photon count rates, the speckle contrast was evaluated by analyzing the probability distribution of the pixel counts at a constant scattering vector for single frames. For very low average photon counts of less than 0.2 per pixel, the `droplet algorithm' was first applied to the patterns for correcting the effect of charge sharing, and then the pixel count statistics of multiple frames were analyzed collectively to extract the speckle contrast. Results obtained using both methods agree within the uncertainty intervals, providing strong experimental evidence for the validity of the statistical analysis. More importantly it confirms the suitability of the ePix100 detector for X‐ray coherent scattering experiments, especially at very low count rates with performances surpassing those of previously available LCLS detectors.     

Combined measurement of X‐ray photon correlation spectroscopy and diffracted X‐ray tracking using pink beam X‐rays

Combined X‐ray photon correlation spectroscopy (XPCS) and diffracted X‐ray tracking (DXT) measurements of carbon‐black nanocrystals embedded in styrene–butadiene rubber were performed. From the intensity fluctuation of speckle patterns in a small‐angle scattering region (XPCS), dynamical information relating to the translational motion can be obtained, and the rotational motion is observed through the changes in the positions of DXT diffraction spots. Graphitized carbon‐black nanocrystals in unvulcanized styrene–butadiene rubber showed an apparent discrepancy between their translational and rotational motions; this result seems to support a stress‐relaxation model for the origin of super‐diffusive particle motion that is widely observed in nanocolloidal systems. Combined measurements using these two techniques will give new insights into nanoscopic dynamics, and will be useful as a microrheology technique.     

X‐ray photon correlation spectroscopy under flow

X‐ray photon correlation spectroscopy was used to probe the diffusive dynamics of colloidal particles in a shear flow. Combining X‐ray techniques with microfluidics is an experimental strategy that reduces the risk of X‐ray‐induced beam damage and also allows time‐resolved studies of processes taking place in flow cells. The experimental results and theoretical predictions presented here show that in the low shear limit for a `transverse flow' scattering geometry (scattering wavevector q perpendicular to the direction of flow) the measured relaxation times are independent of the flow rate and determined only by the diffusive motion of the particles. This is not generally valid and, in particular, for a `longitudinal flow' ( q ∥ flow) scattering geometry the relaxation times are strongly affected by the flow‐induced motion of the particles. The results here show that the Brownian diffusion of colloidal particles can be measured in a flowing sample and that, up to flux limitations, the experimental conditions under which this is possible are easier to achieve at higher values of q.     

Brownian and advective dynamics in microflow studied by coherent X‐ray scattering experiments

Combining microfluidics with coherent X‐ray illumination offers the possibility to not only measure the structure but also the dynamics of flowing samples in a single‐scattering experiment. Here, the power of this combination is demonstrated by studying the advective and Brownian dynamics of colloidal suspensions in microflow of different geometries. Using an experimental setup with a fast two‐dimensional detector and performing X‐ray correlation spectroscopy by calculating two‐dimensional maps of the intensity auto‐correlation functions, it was possible to evaluate the sample structure and furthermore to characterize the detailed flow behavior, including flow geometry, main flow directions, advective flow velocities and diffusive dynamics. By scanning a microfocused X‐ray beam over a microfluidic device, the anisotropic auto‐correlation functions of driven colloidal suspensions in straight, curved and constricted microchannels were mapped with the spatial resolution of the X‐ray beam. This method has not only a huge potential for studying flow patterns in complex fluids but also to generally characterize anisotropic dynamics in materials.     

The dedicated high‐resolution grazing‐incidence X‐ray scattering beamline 8‐ID‐E at the Advanced Photon Source

As an increasingly important structural‐characterization technique, grazing‐incidence X‐ray scattering (GIXS) has found wide applications for in situ and real‐time studies of nanostructures and nanocomposites at surfaces and interfaces. A dedicated beamline has been designed, constructed and optimized at beamline 8‐ID‐E at the Advanced Photon Source for high‐resolution and coherent GIXS experiments. The effectiveness and applicability of the beamline and the scattering techniques have been demonstrated by a host of experiments including reflectivity, grazing‐incidence static and kinetic scattering, and coherent surface X‐ray photon correlation spectroscopy. The applicable systems that can be studied at 8‐ID‐E include liquid surfaces and nanostructured thin films.     

Kinoform optics applied to X‐ray photon correlation spectroscopy

Moderate‐demagnification higher‐order silicon kinoform focusing lenses have been fabricated to facilitate small‐angle X‐ray photon correlation spectroscopy (XPCS) experiments. The geometric properties of such lenses, their focusing performance and their applicability for XPCS measurements are described. It is concluded that one‐dimensional vertical X‐ray focusing via silicon kinoform lenses significantly increases the usable coherent flux from third‐generation storage‐ring light sources for small‐angle XPCS experiments.     

High‐efficiency coherence‐preserving harmonic rejection with crystal optics

This work reports a harmonic‐rejection scheme based on the combination of Si(111) monochromator and Si(220) harmonic‐rejection crystal optics. This approach is of importance to a wide range of X‐ray applications in all three major branches of modern X‐ray science (scattering, spectroscopy, imaging) based at major facilities, and especially relevant to the capabilities offered by the new diffraction‐limited storage rings. It was demonstrated both theoretically and experimentally that, when used with a synchrotron undulator source over a broad range of X‐ray energies of interest, the harmonic‐rejection crystals transmit the incident harmonic X‐rays on the order of 10^?6. Considering the flux ratio of fundamental and harmonic X‐rays in the incident beam, this scheme achieves a total flux ratio of harmonic radiation to fundamental radiation on the order of 10^?10. The spatial coherence of the undulator beam is preserved in the transmitted fundamental radiation while the harmonic radiation is suppressed, making this scheme suitable not only for current third‐generation synchrotron sources but also for the new diffraction‐limited storage rings where coherence preservation is an even higher priority. Compared with conventional harmonic‐rejection mirrors, where coherence is poorly preserved and harmonic rejection is less effective, this scheme has the added advantage of lower cost and footprint. This approach has been successfully utilized at the ultra‐small‐angle X‐ray scattering instrument at the Advanced Photon Source for scattering, imaging and coherent X‐ray photon correlation spectroscopy experiments. With minor modification, the harmonic rejection can be improved by a further five orders of magnitude, enabling even more performance capabilities.     

Fast two‐dimensional detection for X‐ray photon correlation spectroscopy using the PILATUS detector

The first X‐ray photon correlation spectroscopy experiments using the fast single‐photon‐counting detector PILATUS (Paul Scherrer Institut, Switzerland) have been performed. The short readout time of this detector permits access to intensity autocorrelation functions describing dynamics in the millisecond range that are difficult to access with charge‐coupled device detectors with typical readout times of several seconds. Showing no readout noise the PILATUS detector enables measurements of samples that either display fast dynamics or possess only low scattering power with an unprecedented signal‐to‐noise ratio.     

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.     

XDS: a flexible beamline for X‐ray diffraction and spectroscopy at the Brazilian synchrotron

The majority of the beamlines at the Brazilian Synchrotron Light Source Laboratory (LNLS) use radiation produced in the storage‐ring bending magnets and are therefore currently limited in the flux that can be used in the harder part of the X‐ray spectrum (above ～10 keV). A 4 T superconducting multipolar wiggler (SCW) was recently installed at LNLS in order to improve the photon flux above 10 keV and fulfill the demands set by the materials science community. A new multi‐purpose beamline was then installed at the LNLS using the SCW as a photon source. The XDS is a flexible beamline operating in the energy range between 5 and 30 keV, designed to perform experiments using absorption, diffraction and scattering techniques. Most of the work performed at the XDS beamline concentrates on X‐ray absorption spectroscopy at energies above 18 keV and high‐resolution diffraction experiments. More recently, new setups and photon‐hungry experiments such as total X‐ray scattering, X‐ray diffraction under high pressures, resonant X‐ray emission spectroscopy, among others, have started to become routine at XDS. Here, the XDS beamline characteristics, performance and a few new experimental possibilities are described.     

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.     

Anisotropy enhanced X‐ray scattering from solvated transition metal complexes

Time‐resolved X‐ray scattering patterns from photoexcited molecules in solution are in many cases anisotropic at the ultrafast time scales accessible at X‐ray free‐electron lasers (XFELs). This anisotropy arises from the interaction of a linearly polarized UV–Vis pump laser pulse with the sample, which induces anisotropic structural changes that can be captured by femtosecond X‐ray pulses. In this work, a method for quantitative analysis of the anisotropic scattering signal arising from an ensemble of molecules is described, and it is demonstrated how its use can enhance the structural sensitivity of the time‐resolved X‐ray scattering experiment. This method is applied on time‐resolved X‐ray scattering patterns measured upon photoexcitation of a solvated di‐platinum complex at an XFEL, and the key parameters involved are explored. It is shown that a combined analysis of the anisotropic and isotropic difference scattering signals in this experiment allows a more precise determination of the main photoinduced structural change in the solute, i.e. the change in Pt—Pt bond length, and yields more information on the excitation channels than the analysis of the isotropic scattering only. Finally, it is discussed how the anisotropic transient response of the solvent can enable the determination of key experimental parameters such as the instrument response function.     

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.     

Structure determination of Pt‐coated Au dumbbells via fluctuation X‐ray scattering

A fluctuation X‐ray scattering experiment has been carried out on platinum‐coated gold nanoparticles randomly oriented on a substrate. A complete algorithm for determining the electron density of an individual particle from diffraction patterns of many particles randomly oriented about a single axis is demonstrated. This algorithm operates on angular correlations among the measured intensity distributions and recovers the angular correlation functions of a single particle from measured diffraction patterns. Taking advantage of the cylindrical symmetry of the nanoparticles, a cylindrical slice model is proposed to reconstruct the structure of the nanoparticles by fitting the experimental ring angular auto‐correlation and small‐angle scattering data obtained from many scattering patterns. The physical meaning of the refined structure is discussed in terms of their statistical distributions of the shape and electron density profile.     

Si PIN X‐ray photon counter

A Si PIN detector for visible light detection, instead of a Geiger‐Müller tube, is applied to X‐ray photon counting. We counted radiation from a checking source of a Geiger‐Müller counter with a Si PIN counter and with a Geiger‐Müller counter. White X‐ray of energy up to 20 keV emitted from a pyroelectric X‐ray emitter was also counted, and the Si PIN X‐ray counter showed a similar curve of count rate versus source distance in both measurements. Pulse counting was performed by spectroscopy circuits. An audio digitizer with computer software for signal processing was also used to simplify the photon counter. A plot of count rate versus time was obtained with this setup. With simple pulse counting circuits, Si PIN X‐ray counters have advantages such as compact structure, low cost and easy application. Copyright © 2011 John Wiley & Sons, Ltd.     

A Geiger‐mode avalanche photodiode array for X‐ray photon correlation spectroscopy

X‐ray photon correlation spectroscopy (XPCS) provides an opportunity to study the dynamics of systems by measuring the temporal fluctuations in a far‐field diffraction pattern. A two‐dimensional detector system has been developed to investigate fluctuations in the frequency range of several Hz to kHz. The X‐ray detector system consists of a thin 100 µm scintillation crystal coupled to a Geiger‐mode avalanche photodiode array. In this article the elements of the system are detailed and the detector for XPCS measurements is demonstrated.     

Vanadium K‐edge XANES in vanadium‐bearing model compounds: a full multiple scattering study

A systematic study is presented on a set of vanadium‐bearing model compounds, representative of the most common V coordination geometries and oxidation states, analysed by means of vanadium K‐edge X‐ray absorption near‐edge spectroscopy calculations in the full multiple scattering (FMS) framework. Analysis and calibration of the free parameters of the theory under the muffin‐tin approximation (muffin‐tin overlap and interstitial potential) have been carried out by fitting the experimental spectra using the MXAN program. The analysis shows a correlation of the fit parameters with the V coordination geometry and oxidation state. By making use of this correlation it is possible to approach the study of unknown V‐bearing compounds with useful preliminary information.