Small‐angle solution scattering using the mixed‐mode pixel array detector

Solution small‐angle X‐ray scattering (SAXS) measurements were obtained using a 128 × 128 pixel X‐ray mixed‐mode pixel array detector (MMPAD) with an 860 µs readout time. The MMPAD offers advantages for SAXS experiments: a pixel full‐well of >2 × 10⁷ 10 keV X‐rays, a maximum flux rate of 10⁸ X‐rays pixel^?1 s^?1, and a sub‐pixel point‐spread function. Data from the MMPAD were quantitatively compared with data from a charge‐coupled device (CCD) fiber‐optically coupled to a phosphor screen. MMPAD solution SAXS data from lysozyme solutions were of equal or better quality than data captured by the CCD. The read‐noise (normalized by pixel area) of the MMPAD was less than that of the CCD by an average factor of 3.0. Short sample‐to‐detector distances were required owing to the small MMPAD area (19.2 mm × 19.2 mm), and were revealed to be advantageous with respect to detector read‐noise. As predicted by the Shannon sampling theory and confirmed by the acquisition of lysozyme solution SAXS curves, the MMPAD at short distances is capable of sufficiently sampling a solution SAXS curve for protein shape analysis. The readout speed of the MMPAD was demonstrated by continuously monitoring lysozyme sample evolution as radiation damage accumulated. These experiments prove that a small suitably configured MMPAD is appropriate for time‐resolved solution scattering measurements.     

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.     

A new small‐angle X‐ray scattering set‐up on the crystallography beamline I711 at MAX‐lab

A small‐angle X‐ray scattering (SAXS) set‐up has recently been developed at beamline I711 at the MAX II storage ring in Lund (Sweden). An overview of the required modifications is presented here together with a number of application examples. The accessible q range in a SAXS experiment is 0.009–0.3 Å^?1 for the standard set‐up but depends on the sample‐to‐detector distance, detector offset, beamstop size and wavelength. The SAXS camera has been designed to have a low background and has three collinear slit sets for collimating the incident beam. The standard beam size is about 0.37 mm × 0.37 mm (full width at half‐maximum) at the sample position, with a flux of 4 × 10¹⁰ photons s^?1 and λ = 1.1 Å. The vacuum is of the order of 0.05 mbar in the unbroken beam path from the first slits until the exit window in front of the detector. A large sample chamber with a number of lead‐throughs allows different sample environments to be mounted. This station is used for measurements on weakly scattering proteins in solutions and also for colloids, polymers and other nanoscale structures. A special application supported by the beamline is the effort to establish a micro‐fluidic sample environment for structural analysis of samples that are only available in limited quantities. Overall, this work demonstrates how a cost‐effective SAXS station can be constructed on a multipurpose beamline.     

Characterization of an in‐vacuum PILATUS 1M detector

A dedicated in‐vacuum X‐ray detector based on the hybrid pixel PILATUS 1M detector has been installed at the four‐crystal monochromator beamline of the PTB at the electron storage ring BESSY II in Berlin, Germany. Owing to its windowless operation, the detector can be used in the entire photon energy range of the beamline from 10 keV down to 1.75 keV for small‐angle X‐ray scattering (SAXS) experiments and anomalous SAXS at absorption edges of light elements. The radiometric and geometric properties of the detector such as quantum efficiency, pixel pitch and module alignment have been determined with low uncertainties. The first grazing‐incidence SAXS results demonstrate the superior resolution in momentum transfer achievable at low photon energies.     

Performance of a four‐element Si drift detector for X‐ray absorption fine‐structure spectroscopy: resolution, maximum count rate,and dead‐time correction with incorporation into the ATHENA data analysis software

The performance of a four‐element Si drift detector for energy‐dispersive fluorescence‐yield X‐ray absorption fine‐structure measurements is reported, operating at the National Institute of Standards and Technology beamline X23A2 at the National Synchrotron Light Source. The detector can acquire X‐ray absorption fine‐structure spectra with a throughput exceeding 4 × 10⁵ counts per second per detector element (>1.6 × 10⁶ total counts per second summed over all four channels). At this count rate the resolution at 6 keV is approximately 220 eV, which adequately resolves the Mn Kα and Kβ fluorescence lines. Accurate dead‐time correction is demonstrated, and it has been incorporated into the ATHENA data analysis program. To maintain counting efficiency and high signal to background, it is suggested that the incoming count rate should not exceed ～70% of the maximum throughput.     

The application of hybrid pixel detectors for in‐house SAXS instrumentation with a view to combined chromatographic operation

This study analyses the potential for laboratory‐based size‐exclusion chromatography (SEC) integrated small‐angle X‐ray scattering (SAXS) instrumentation to characterize protein complexes. Using a high‐brilliance home source in conjunction with a hybrid pixel X‐ray detector, the efficacy of SAXS data collection at pertinent protein concentrations and exposure times has been assessed. Scattering data from SOD1 and from the complex of SOD1 with its copper chaperone, using 10 min exposures, provided data quality in the range 0.03 < q < 0.25 Å^?1 that was sufficient to accurately assign radius of gyration, maximum dimension and molecular mass. These data demonstrate that a home source with integrated SEC–SAXS technology is feasible and would enable structural biologists studying systems containing transient protein complexes, or proteins prone to aggregation, to make advanced preparations in‐house for more effective use of limited synchrotron beam time.     

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.     

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.     

Application of a pnCCD in X‐ray diffraction: a three‐dimensional X‐ray detector

The first application of a pnCCD detector for X‐ray scattering experiments using white synchrotron radiation at BESSY II is presented. A Cd arachidate multilayer was investigated in reflection geometry within the energy range 7 keV < E < 35 keV. At fixed angle of incidence the two‐dimensional diffraction pattern containing several multilayer Bragg peaks and respective diffuse‐resonant Bragg sheets were observed. Since every pixel of the detector is able to determine the energy of every incoming photon with a resolution ΔE/E? 10^?2, a three‐dimensional dataset is finally obtained. In order to achieve this energy resolution the detector was operated in the so‐called single‐photon‐counting mode. A full dataset was evaluated taking into account all photons recorded within 10⁵ detector frames at a readout rate of 200 Hz. By representing the data in reciprocal‐space coordinates, it becomes obvious that this experiment with the pnCCD detector provides the same information as that obtained by combining a large number of monochromatic scattering experiments using conventional area detectors.     

A dedicated small‐angle X‐ray scattering beamline with a superconducting wiggler source at the NSRRC

At the National Synchrotron Radiation Research Center (NSRRC), which operates a 1.5 GeV storage ring, a dedicated small‐angle X‐ray scattering (SAXS) beamline has been installed with an in‐achromat superconducting wiggler insertion device of peak magnetic field 3.1 T. The vertical beam divergence from the X‐ray source is reduced significantly by a collimating mirror. Subsequently the beam is selectively monochromated by a double Si(111) crystal monochromator with high energy resolution (ΔE/E? 2 × 10^?4) in the energy range 5–23 keV, or by a double Mo/B₄C multilayer monochromator for 10–30 times higher flux (～10¹¹ photons s^?1) in the 6–15 keV range. These two monochromators are incorporated into one rotating cradle for fast exchange. The monochromated beam is focused by a toroidal mirror with 1:1 focusing for a small beam divergence and a beam size of ～0.9 mm × 0.3 mm (horizontal × vertical) at the focus point located 26.5 m from the radiation source. A plane mirror installed after the toroidal mirror is selectively used to deflect the beam downwards for grazing‐incidence SAXS (GISAXS) from liquid surfaces. Two online beam‐position monitors separated by 8 m provide an efficient feedback control for an overall beam‐position stability in the 10 µm range. The beam features measured, including the flux density, energy resolution, size and divergence, are consistent with those calculated using the ray‐tracing program SHADOW. With the deflectable beam of relatively high energy resolution and high flux, the new beamline meets the requirements for a wide range of SAXS applications, including anomalous SAXS for multiphase nanoparticles (e.g. semiconductor core‐shell quantum dots) and GISAXS from liquid surfaces.     

Sub‐microsecond‐resolved multi‐speckle X‐ray photon correlation spectroscopy with a pixel array detector

Small‐angle X‐ray photon correlation spectroscopy (XPCS) measurements spanning delay times from 826 ns to 52.8 s were performed using a photon‐counting pixel array detector with a dynamic range of 0–3 (2 bits). Fine resolution and a wide dynamic range of time scales was achieved by combining two modes of operation of the detector: (i) continuous mode, where data acquisition and data readout are performed in parallel with a frame acquisition time of 19.36 µs, and (ii) burst mode, where 12 frames are acquired with frame integration times of either 2.56 µs frame^?1 or 826 ns frame^?1 followed by 3.49 ms or 1.16 ms, respectively, for readout. The applicability of the detector for performing multi‐speckle XPCS was demonstrated by measuring the Brownian dynamics of 10 nm‐radius gold and 57 nm‐radius silica colloids in water at room temperature. In addition, the capability of the detector to faithfully record one‐ and two‐photon counts was examined by comparing the statistical distribution of photon counts with expected probabilities from the negative binomial distribution. It was found that in burst mode the ratio of 2 s to 1 s is markedly smaller than predicted and that this is attributable to pixel‐response dead‐time.     

Quality evaluation of quick‐frozen biological specimens by simultaneous microbeam SAXS/WAXS recordings

The quality of small‐angle X‐ray scattering (SAXS) patterns from quick‐frozen hydrated biological specimens was correlated with the extent of ice crystal formation by simultaneously recording wide‐angle X‐ray scattering (WAXS) of ice, at a micrometer‐order spatial resolution by using X‐ray microbeams. Flight muscle fibers from a giant waterbug, Lethocerus, known to generate well defined small‐angle reflection spots originating from the hexagonal lattices of myofilaments, were quick‐frozen in the presence or absence of various cryoprotectants. Freezing without a cryoprotectant resulted in massive ice‐crystal formation at almost all depths of the specimen, and the occurrence of reflection spots was limited to the region close to the specimen surface. Inclusion of 20% dimethyl sulfoxide or methylpentanediol ensured ideal vitreous ice formation and good diffraction qualities for up to 100 µm from the specimen surface. Glycerol and sucrose were found to be inferior at a 20% concentration, but left the reflection spots observable at depths of up to 100 µm. Thus, the microbeam SAXS/WAXS recording offers a high‐spatial‐resolution means of evaluating the extent of structure preservation of quick‐frozen biological specimens. The technique presented here may also provide useful information in cryoelectron microscopy.     

Thorough small‐angle X‐ray scattering analysis of the instability of liquid micro‐jets in air

Liquid jets are of interest, both for their industrial relevance and for scientific applications (more important, in particular for X‐rays, after the advent of free‐electron lasers that require liquid jets as sample carrier). Instability mechanisms have been described theoretically and by numerical simulation, but confirmed by few experimental techniques. In fact, these are mainly based on cameras, which is limited by the imaging resolution, and on light scattering, which is hindered by absorption, reflection, Mie scattering and multiple scattering due to complex air/liquid interfaces during jet break‐up. In this communication it is demonstrated that synchrotron small‐angle X‐ray scattering (SAXS) can give quantitative information on liquid jet dynamics at the nanoscale, by detecting time‐dependent morphology and break‐up length. Jets ejected from circular tubes of different diameters (100–450 µm) and speeds (0.7–21 m s^?1) have been explored to cover the Rayleigh and first wind‐induced regimes. Various solvents (water, ethanol, 2‐propanol) and their mixtures have been examined. The determination of the liquid jet behaviour becomes essential, as it provides background data in subsequent studies of chemical and biological reactions using SAXS or X‐ray diffraction based on synchrotron radiation and free‐electron lasers.     

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.     

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.     

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).     

One‐dimensional small‐angle X‐ray scattering tomography of dip‐coated polyamide 6 monofilaments

A synchrotron study is presented in which the concept of one‐dimensional tomographic reconstruction of small‐angle X‐ray scattering patterns is applied to investigate polyamide 6 monofilaments, dip‐coated with alumina particles. The filaments are scanned with a focused synchrotron beam and the resulting scattering patterns are recorded with a PILATUS 2M detector. The reconstructed sequence of SAXS images reflects the local nanostructure variation along the filament radius. In particular, the influence of coating process parameters on the polyamide 6 is investigated.     

A high‐spatial‐resolution three‐dimensional detector array for 30–200 keV X‐rays based on structured scintillators

A three‐dimensional X‐ray detector for imaging 30–200 keV photons is described. It comprises a set of semi‐transparent structured scintillators, where each scintillator is a regular array of waveguides in silicon, and with pores filled with CsI. The performance of the detector is described theoretically and explored in detail through simulations. Based on available hardware, a spatial resolution of 1 µm is obtainable. The resolution of a single screen is shown to be determined only by the pitch, at least up to 100 keV. In comparison with conventional homogeneous screens, an improvement in efficiency by a factor of 5–15 is obtainable. The cross‐talk between screens in the three‐dimensional detector is shown to be negligible. The three‐dimensional concept enables ray‐tracing and super‐resolution algorithms to be applied.     

Pixelated transmission‐mode diamond X‐ray detector

Fabrication and testing of a prototype transmission‐mode pixelated diamond X‐ray detector (pitch size 60–100 µm), designed to simultaneously measure the flux, position and morphology of an X‐ray beam in real time, are described. The pixel density is achieved by lithographically patterning vertical stripes on the front and horizontal stripes on the back of an electronic‐grade chemical vapor deposition single‐crystal diamond. The bias is rotated through the back horizontal stripes and the current is read out on the front vertical stripes at a rate of ～1 kHz, which leads to an image sampling rate of ～30 Hz. This novel signal readout scheme was tested at beamline X28C at the National Synchrotron Light Source (white beam, 5–15 keV) and at beamline G3 at the Cornell High Energy Synchrotron Source (monochromatic beam, 11.3 keV) with incident beam flux ranges from 1.8 × 10^?2 to 90 W mm^?2. Test results show that the novel detector provides precise beam position (positional noise within 1%) and morphology information (error within 2%), with an additional software‐controlled single channel mode providing accurate flux measurement (fluctuation within 1%).     

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.