Synchrotron Source Research Articles

Kilohertz Macromolecular Crystallography Using an EIGER Detector at Low X-ray Fluxes

Time-resolved in-house macromolecular crystallography is primarily limited by the capabilities of the in-house X-ray sources. These sources can only provide a time-averaged structure of the macromolecules. A significant effort has been made in the development of in-house laser-driven ultrafast X-ray sources, with one of the goals as realizing the visualization of the structural dynamics of macromolecules at a very short timescale within the laboratory-scale infrastructure. Most of such in-house ultrafast X-ray sources are operated at high repetition rates and usually deliver very low flux. Therefore, the necessity of a detector that can operate at the repetition rate of the laser and perform extremely well under low flux conditions is essential. Here, we present experimental results demonstrating the usability of the hybrid-pixel detectors, such as Eiger X 1M, and provide experimental proof that they can be successfully operated to collect macromolecular crystallographic data up to a detector frame rate of 3 kHz from synchrotron sources. Our results also show that the data reduction and structural analysis are successful at such high frame rates and fluxes as low as 108 photons/s, which is comparable to the values expected from a typical laser-driven X-ray source.

Seven-octave high-brightness and carrier-envelope-phase-stable light source

High-brightness sources of coherent and few-cycle-duration light waveforms with spectral coverage from the UV to the THz would offer unprecedented versatility and opportunities for a spectacular range of applications from bio-chemical sensing, to time-resolved and nonlinear spectroscopy, to attosecond light-wave electronics. Combinations of various sources with frequency conversion and supercontinuum generation can provide relatively large spectral coverage, but many applications require much broader spectral range and low-jitter synchronization for time-domain measurements. Here, we present a carrier-envelope-phase stable light source, seeded by a mid-IR frequency comb, with simultaneous spectral coverage across 7 optical octaves, from the UV (340 nm) into the THz (40,000 nm). Combining soliton self-compression and dispersive wave generation in an anti-resonant-reflection photonic crystal fibre with intra-pulse difference frequency generation in BaGa2GeSe6, the spectral brightness is 2-5 orders of magnitude above synchrotron sources. This enables high-dynamic-range spectroscopies and provides enticing prospects for attosecond physics and material sciences.

The structure of oxide glasses studied by high-energy x-ray diffraction

The use of high‑energy x‑ray diffraction techniques with the latest generation synchrotron sources has created new approaches to study quantitatively the structure of noncrystalline materials. Recently, this technique has been combined with neutron diffraction at pulsed source to provide more detailed and reliable structural information not previously available. This article reviews and summarises recent results obtained from the high energy x‑ray diffraction on several oxide glasses, SiO2, B2O3 and PbSiO3, using bending magnet beamlines at SPring‑8. In particular, it addresses the structural models of the oxide glasses obtained by the reverse Monte Carlo (RMC) modelling technique using both the high energy x‑ray and neutron diffraction data.

Three-Dimensional Coherent Bragg Imaging of Rotating Nanoparticles.

Bragg coherent diffraction imaging is a powerful strain imaging tool, often limited by beam-induced sample instability for small particles and high power densities. Here, we devise and validate an adapted diffraction volume assembly algorithm, capable of recovering three-dimensional datasets from particles undergoing uncontrolled and unknown rotations. We apply the method to gold nanoparticles which rotate under the influence of a focused coherent x-ray beam, retrieving their three-dimensional shapes and strain fields. The results show that the sample instability problem can be overcome, enabling the use of fourth generation synchrotron sources for Bragg coherent diffraction imaging to their full potential.

Synchrotron based X-ray fluorescence for trace elemental analysis of industrial sludge

This research article presents the application of the synchrotron-based X-ray fluorescence (XRF) technique for the resolution of trace elemental accumulation in industrial sludge/waste. The X-ray fluorescence using synchrotron radiation presents an expeditious exposition of a wide scale of elements (Sodium to Uranium) together with an ingenuous sample preparation procedure. The present X-ray fluorescence studies carried out for the paper and toothpaste industry sludge at synchrotron source (Beam Line -16), Indus-2, Raja Ramanna Centre for Advanced Technology, Indore, India. The XRF results show very low traces of heavy metals present in paper and toothpaste industry sludge and therefore recommend for safe and efficient reuse.

Spectroscopic imaging at compact inverse Compton X-ray sources.

While K-edge subtraction (KES) imaging is a commonly applied technique at synchrotron sources, the application of this imaging method in clinical imaging is limited although results have shown its superiority to conventional clinical subtraction imaging. Over the past decades, compact synchrotron X-ray sources, based on inverse Compton scattering, have been developed to fill the gap between conventional X-ray tubes and synchrotron facilities. These so called inverse Compton sources (ICSs) provide a tunable, quasi-monochromatic X-ray beam in a laboratory setting with reduced spatial and financial requirements. This allows for the transfer of imaging techniques that have been limited to synchrotrons until now, like KES imaging, into a laboratory environment. This review article presents the first studies that have successfully performed KES at ICSs. These have shown that KES provides improved image quality in comparison to conventional X-ray imaging. The results indicate that medical imaging could benefit from monochromatic imaging and KES techniques. Currently, the clinical application of KES is limited by the low K-edge energy of available iodine contrast agents. However, several ICSs are under development or already in commissioning which will provide monochromatic X-ray beams with higher X-ray energies and will enable KES using high-Z elements as contrast media. With these developments, KES at an ICS has the ability to become an important tool in pre-clinical research and potentially advancing existing clinical imaging techniques.

Backside-illuminated scientific CMOS detector for soft X-ray resonant scattering and ptychography.

The impressive progress in the performance of synchrotron radiation sources is nowadays driven by the so-called `ultimate storage ring' projects which promise an unprecedented improvement in brightness. Progress on the detector side has not always been at the same pace, especially as far as soft X-ray 2D detectors are concerned. While the most commonly used detectors are still based on microchannel plates or CCD technology, recent developments of CMOS (complementary metal oxide semiconductor)-type detectors will play an ever more important role as 2D detectors in the soft X-ray range. This paper describes the capabilities and performance of a camera equipped with a newly commercialized backside-illuminated scientific CMOS (sCMOS-BSI) sensor, integrated in a vacuum environment, for soft X-ray experiments at synchrotron sources. The 4 Mpixel sensor reaches a frame rate of up to 48 frames s-1 while matching the requirements for X-ray experiments in terms of high-intensity linearity (>98%), good spatial homogeneity (<1%), high charge capacity (up to 80 ke-), and low readout noise (down to 2 e- r.m.s.) and dark current (3 e- per second per pixel). Performance evaluations in the soft X-ray range have been carried out at the METROLOGIE beamline of the SOLEIL synchrotron. The quantum efficiency, spatial resolution (24 line-pairs mm-1), energy resolution (<100 eV) and radiation damage versus the X-ray dose (<600 Gy) have been measured in the energy range from 40 to 2000 eV. In order to illustrate the capabilities of this new sCMOS-BSI sensor, several experiments have been performed at the SEXTANTS and HERMES soft X-ray beamlines of the SOLEIL synchrotron: acquisition of a coherent diffraction pattern from a pinhole at 186 eV, a scattering experiment from a nanostructured Co/Cu multilayer at 767 eV and ptychographic imaging in transmission at 706 eV.

Speckle-tracking: a software suite for ptychographic X-ray speckle tracking.

In recent years, X-ray speckle-tracking techniques have emerged as viable tools for wavefront metrology and sample imaging applications. These methods are based on the measurement of near-field images. Thanks to their simple experimental setup, high angular sensitivity and compatibility with low-coherence sources, these methods have been actively developed for use with synchrotron and laboratory light sources. Not only do speckle-tracking techniques give the potential for high-resolution imaging, but they also provide rapid and robust characterization of aberrations of X-ray optical elements, focal spot profiles, and sample position and transmission properties. In order to realize these capabilities, software implementations are required that are equally rapid and robust. To address this need, a software suite has been developed for the ptychographic X-ray speckle-tracking technique, an X-ray speckle-based method suitable for highly divergent wavefields. The software suite is written in Python 3, with an OpenCL back end for GPU and multi-CPU core processing. It is accessible as a Python module, through the command line or through a graphical user interface, and is available as source code under Version 3 or later of the GNU General Public License.

Nanoscale structural analysis of Pb(Mg1/3Nb2/3)O3

The determination of local atomic structure at nanoscale for inhomogeneous systems is challenging. The local arrangement of atoms needs to be studied to understand the local or short-range order structures for disordered materials with a lack of long-range order periodicity. Pair distribution function (PDF) analysis is a technique, that is used to study the short-range order structure of materials: this technique is based on the evaluation of local atomic arrangement using synchrotron and neutron sources. An attempt was made to determine the local arrangement at 20 nm-scale for a typical relaxor ferroelectric material, Pb(Mg1/3Nb2/3)O3 (PMN). The PDF technique was employed owing to the limited structural coherence in this disordered material. It was determined that there are three types of structures depending on the distance. A glass-like network structure was observed as a short-range order structure owing to the large off-center shift of lead atoms. With an increase in distance, the structure of PMN changed from rhombohedral to cubic. Using the above-mentioned approach, we elucidated the process of local structure averaging.

Hard X-ray ptychography for optics characterization using a partially coherent synchrotron source.

Ptychography is a scanning coherent diffraction imaging technique which provides high resolution imaging and complete spatial information of the complex electric field probe and sample transmission function. Its ability to accurately determine the illumination probe has led to its use at modern synchrotrons and free-electron lasers as a wavefront-sensing technique for optics alignment, monitoring and correction. Recent developments in the ptychography reconstruction process now incorporate a modal decomposition of the illuminating probe and relax the restriction of using sources with high spatial coherence. In this article a practical implementation of hard X-ray ptychography from a partially coherent X-ray source with a large number of modes is demonstrated experimentally. A strongly diffracting Siemens star test sample is imaged using the focused beam produced by either a Fresnel zone plate or beryllium compound refractive lens. The recovered probe from each optic is back propagated in order to plot the beam caustic and determine the precise focal size and position. The power distribution of the reconstructed probe modes also allows the quantification of the beams coherence and is compared with the values predicted by a Gaussian-Schell model and the optics exit intensity.

On space charge effects in laboratory-based photoemission electron microscopy using compact gas discharge extreme ultraviolet sources

The analysis of electronic and structural properties of surfaces has been greatly advanced by photoemission electron microscopy and spectroscopy techniques. To further improve lateral and energy resolution of the instruments, it is necessary to optimize parameters of the radiation sources employed for photoemission studies (e.g. photon flux, pulse duration, spot size etc). We studied space charge effects observed in an energy-filtering photoemission electron microscope operated with a compact laboratory-scale gas-discharge extreme ultraviolet light source. In this system, we found limits of spatial- and energy-resolution controlled by the source radiation parameters. The pulse repetition rate can be varied in the kHz range and the duration of the EUV emission was measured to be several tens of nanoseconds long, and thereby very different from the standard synchrotron sources typically used for similar experiments. The spatial resolution could be improved by a factor of 5, but only on the expense of the photon density per pulse, which had to be decreased by a factor of 17 in order to reduce the image blur due to space charge effects. Furthermore, we found broadening of the x-ray photoelectron spectroscopy peaks for high photon fluxes. We have also performed a n-body Monte Carlo simulation to evaluate the difference between core-level photoelectrons and secondary electrons with respect to space charge.

Bragg coherent imaging of nanoprecipitates: role of superstructure reflections

Coherent precipitation of ordered phases is responsible for providing exceptional high-temperature mechanical properties in a wide range of compositionally complex alloys. Ordered phases are also essential to enhance the magnetic or catalytic properties of alloyed nanoparticles. The present work aims to demonstrate the relevance of Bragg coherent diffraction imaging (BCDI) for studying bulk and thin-film samples or isolated nanoparticles containing coherent nanoprecipitates/ordered phases. The structures of crystals of a few tens of nanometres in size are modelled with realistic interatomic potentials and are relaxed after introduction of coherent ordered nanoprecipitates. Diffraction patterns from fundamental and superstructure reflections are calculated in the kinematic approximation and used as input to retrieve the strain fields using algorithmic inversion. First, the case of single nanoprecipitates is tackled and it is shown that the strain field distribution from the ordered phase is retrieved very accurately. Then, the influence of the order parameter S on the strain field retrieved from the superstructure reflections is investigated. A very accurate strain distribution can be retrieved for partially ordered phases with large and inhomogeneous strains. Subsequently, the relevance of BCDI is evaluated for the study of systems containing many precipitates, and it is demonstrated that the technique is relevant for such systems. Finally, the experimental feasibility of using BCDI to image ordered phases is discussed in the light of the new possibilities offered by fourth-generation synchrotron sources.

In situ X-ray measurements over large Q-space to study the evolution of oxide thin films prepared by RF sputter deposition

Sputter deposition is a versatile and industrially important deposition technique for thin films, with increasing demand for matching the characteristics of thin film materials to specific requirements. The actual film properties are largely determined by sputtering parameters such as pressure conditions, temperature and power settings. By means of various X-ray diffraction and scattering techniques, it is shown that the characterization of film formation and growth is feasible in real time at synchrotron sources, thus adding an important dimension to the fundamental understanding of the evolution of thin film microstructure. In particular, grazing incidence small-angle X-ray scattering, grazing incidence X-ray powder diffraction and X-ray reflectometry are used in a complementary manner to study the influence of deposition temperature and substrate choice on the crystallization kinetics and growth of polycrystalline BaTiO $$_3$$ films.

Rapid Infrared Spectroscopic Nanoimaging with nano-FTIR Holography

Scattering-type scanning near-field optical microscopy (s-SNOM), and its derivate, Fourier transform infrared nanospectroscopy (nano-FTIR) are emerging techniques for infrared (IR) nanoimaging and spectroscopy with applications in diverse fields ranging from nanophotonics, chemical imaging and materials science. However, spectroscopic nanoimaging is still challenged by the limited acquisition rate of current nano-FTIR technology. Here we combine s-SNOM, nano-FTIR and synthetic optical holographic (SOH) to achieve infrared spectroscopic nanoimaging at unprecedented speed (8 spectroscopically resolved images in 20 min), which we demonstrate with a polymer composite sample. Beyond being fast, our method promises to enable nanoimaging in the long IR spectral range, which is covered by IR supercontinuum and synchrotron sources, but not by current quantum cascade laser technology.

Complete Remission of Mouse Melanoma after Temporally Fractionated Microbeam Radiotherapy.

Simple SummarySynchrotron Microbeam Radiation Therapy (MRT) provides excellent tumour control in preclinical cancer models. Most of the results obtained in the field employ average peak doses between 300 and 600 Gy. However, despite its proven efficacy, one of the biggest challenges in translating MRT to the clinic is that these high doses can be delivered only at synchrotron facilities, and there are only a few in the world. To solve this problem, we delivered three sessions of lower peak doses of 133 Gy, which approach clinical capabilities. The results showed complete tumour remission for 18 months. In fact, it ablated 50% of the primary melanomas with no metastasis. We believe that this study is of value because (i) it increased the therapeutic index of MRT, and (ii) it demonstrates that MRT can be less dependent on synchrotron sources, which opens the path for future clinical application.Background: Synchrotron Microbeam Radiotherapy (MRT) significantly improves local tumour control with minimal normal tissue toxicity. MRT delivers orthovoltage X-rays at an ultra-high “FLASH” dose rate in spatially fractionated beams, typically only few tens of micrometres wide. One of the biggest challenges in translating MRT to the clinic is its use of high peak doses, of around 300–600 Gy, which can currently only be delivered by synchrotron facilities. Therefore, in an effort to improve the translation of MRT to the clinic, this work studied whether the temporal fractionation of traditional MRT into several sessions with lower, more clinically feasible, peak doses could still maintain local tumour control. Methods: Two groups of twelve C57Bl/6J female mice harbouring B16-F10 melanomas in their ears were treated with microbeams of 50 µm in width spaced by 200 µm from their centres. The treatment modality was either (i) a single MRT session of 401.23 Gy peak dose (7.40 Gy valley dose, i.e., dose between beams), or (ii) three MRT sessions of 133.41 Gy peak dose (2.46 Gy valley dose) delivered over 3 days in different anatomical planes, which intersected at 45 degrees. The mean dose rate was 12,750 Gy/s, with exposure times between 34.2 and 11.4 ms, respectively. Results: Temporally fractionated MRT ablated 50% of B16-F10 mouse melanomas, preventing organ metastases and local tumour recurrence for 18 months. In the rest of the animals, the median survival increased by 2.5-fold in comparison to the single MRT session and by 4.1-fold with respect to untreated mice. Conclusions: Temporally fractionating MRT with lower peak doses not only maintained tumour control, but also increased the efficacy of this technique. These results demonstrate that the solution to making MRT more clinically feasible is to irradiate with several fractions of intersecting arrays with lower peak doses. This provides alternatives to synchrotron sources where future microbeam radiotherapy could be delivered with less intense radiation sources.

Sydney Leach. 11 April 1924—24 December 2019

Sydney Leach will be remembered as an outstanding and inspirational scientist, an irreplaceable friend to many—artists and musicians as well as academic colleagues. He encouraged and influenced numerous scientists as a mentor. After graduating from King's College London and carrying out war work at Farnborough, he spent all his scientific life based in Paris, working principally at Orsay and, in his later years, at the Observatoire de Paris–Meudon. Sydney was a major influence in establishing chemical physics in France after World War II, founding the highly influential Laboratoire de Photophysique Moléculaire (LPPM) at Orsay, where much of his pioneering work was performed. The ‘Sydney lab’ lives on in the newly created Institut des Sciences Moléculaires d'Orsay. Early experiments often took place at the synchrotron source (ACO, Super-ACO), just a few hundred yards from LPPM. He was a pioneering advocate of synchrotron radiation, and a driving force for its use in spectroscopy and photodynamics, along with free-electron lasers, supersonic jets, coincidence spectroscopy and matrix isolation—techniques that were applied and refined over decades and used to explore fundamental processes such as photoionization, vibronic coupling and radiationless transitions. Sydney's seminal studies of polyatomic molecular ions led him towards fresh horizons in planetary atmospheric and space science. His work opened new vistas in cometary spectroscopy, polycyclic aromatic hydrocarbons, fullerenes and their possible roles in the chemistry of the interstellar medium and, finally, biologically relevant species, helping to instigate the newly developing subject of astrobiology—a perfect example of his sustained prescience in the world of science.

Time and space resolved modelling of the heating induced by synchrotron X-ray nanobeams.

X-ray synchrotron sources, possessing high power density, nanometric spot size and short pulse duration, are extending their application frontiers up to the exploration of direct matter modification. In this field, the use of atomistic and continuum models is now becoming fundamental in the simulation of the photoinduced excitation states and eventually in the phase transition triggered by intense X-rays. In this work, the X-ray heating phenomenon is studied by coupling the Monte Carlo method (MC) with the Fourier heat equation, to first calculate the distribution of the energy absorbed by the systems and finally to predict the heating distribution and evolution. The results of the proposed model are also compared with those obtained removing the explicit definition of the energy distribution, as calculated by the MC. A good approximation of experimental thermal measurements produced irradiating a millimetric glass bead is found for both of the proposed models. A further step towards more complex systems is carried out, including in the models the different time patterns of the source, as determined by the filling modes of the synchrotron storage ring. The two models are applied in three prediction cases, in which the heating produced in Bi2Sr2CaCu2O8+δ microcrystals by means of nanopatterning experiments with intense hard X-ray nanobeams is calculated. It is demonstrated that the temperature evolution is strictly connected to the filling mode of the storage ring. By coupling the MC with the heat equation, X-ray pulses that are 48 ps long, possessing an instantaneous photon flux of ∼44 × 1013 photons s-1, were found to be able to induce a maximum temperature increase of 42 K, after a time of 350 ps. Inversely, by ignoring the energy redistribution calculated with the MC, peaks temperatures up to hundreds of degrees higher were found. These results highlight the importance of the energy redistribution operated by primary and secondary electrons in the theoretical simulation of the X-ray heating effects.

Single spectrum three-material decomposition with grating-based x-ray phase-contrast CT

Grating-based x-ray phase-contrast imaging provides three simultaneous image channels originating from a single image acquisition. While the phase signal provides direct access to the electron density in tomography, there is additional information on sub-resolutional structural information which is called dark-field signal in analogy to optical microscopy. The additional availability of the conventional attenuation image qualifies the method for implementation into existing diagnostic routines. The simultaneous access to the attenuation coefficient and the electron density allows for quantitative two-material discrimination as demonstrated lately for measurements at a quasi-monochromatic compact synchrotron source. Here, we investigate the transfer of the method to conventional polychromatic x-ray sources and the additional inclusion of the dark-field signal for three-material decomposition. We evaluate the future potential of grating-based x-ray phase-contrast CT for quantitative three-material discrimination for the specific case of early stroke diagnosis at conventional polychromatic x-ray sources. Compared to conventional CT, the method has the potential to discriminate coagulated blood directly from contrast agent extravasation within a single CT acquisition. Additionally, the dark-field information allows for the clear identification of hydroxyapatite clusters due to their micro-structure despite a similar attenuation as the applied contrast agent. This information on materials with sub-resolutional microstructures is considered to comprise advantages relevant for various pathologies.

Formation of C4H4 from photolysis of icy C2H2 with 175 nm at 60 K

ABSTRACT The absorption spectrum of solid acetylene (C2H2) at 10 K was measured in wavelength range 107–250 nm with UV light from a synchrotron source. Based on the absorption spectrum, we irradiated at 175 nm the icy acetylene at 60 K; the results yielded a new set of IR absorption lines with similar temporal profiles of production during the photolysis periods. From icy 12C2H2, these new features were recorded at 3276.8, 1598.7, 963.0, 936.3, and 671.3 cm−1, which are assigned to modes ν1, ν6, ν14, ν15, and ν11 (mixing with ν17), respectively, of vinylacetylene (C4H4) based on the results of 13C- and D-isotopic experiments and quantum-chemical calculations. These calculations using density-functional theory (B3LYP/6–311++G**) predict vibrational wavenumbers and IR intensities of vinylacetylene that agree satisfactorily with our experimental results. This work enhances our understanding of the photochemistry of icy acetylene in cold astronomical environments; for instance, the present result can be applied directly to the photochemical processes on Titan's surface.

Method for permanent magnet undulator parameter stabilizing against temperature variation

Stability of undulator parameter (Kund) is very important for operation of synchrotron radiation sources. Because Kund defines radiation harmonics energies, its variation causes drift of harmonic energies and undesirable photon flux change during data collection.Very often, the origin of Kund drift is temperature change. To stabilize Kund, the temperature of the undulator and ambient should be kept constant with ∼±0.1 °C or better precision. Although keeping the temperature constant in a large space with such precision is a challenge, it can be done with adequate resources. However, the time needed to reach operating temperature with required precision after interruption of standard operation can be quite long. Observation made at Cornell High Energy Synchrotron Source (CHESS) indicated that this time can be ∼12 h or longer. During this time period, Kund of undulator magnets is drifting, causing variation of photon flux. This compromises beam line operation. Reducing the sensitivity of Kund to temperature variation would be beneficial.In this paper, we developed the concept of stabilizing of Kund against temperature change utilizing the effect of differential thermo-expansion. According to the concept, girders should include specific parts made of materials with different coefficients of thermo-expansion (CTE). When temperature changes, it will create the desired deformation which can compensate for the change in magnetic field caused by temperature sensitivity of permanent magnet residual induction Br. Engineering FEM modeling and analysis of the magnetic field of the specific girder design reveal feasibility and practicality of the concept.In the paper we present results of the engineering modeling, magnetic field analysis, and supporting experimental data.