Modern Synchrotron Research Articles

AGES: Automated Gas Environment System for in situ neutron powder diffraction.

High fluxes available at modern neutron and synchrotron sources have opened up a wide variety of in situ and operando studies of real processes using scattering techniques. This has allowed the user community to follow chemistry in the beam, which often requires high temperatures, gas flow, etc. In this paper, we describe an integrated gas handling system for the general-purpose powder diffraction beamline Powgen at the Spallation Neutron Source. The Automated Gas Environment System (AGES) allows control of both gas flow and temperature (room temperature to 850 °C), while measuring the partial pressure of oxygen and following the effluent gas by mass spectrometry, concurrent with neutron powder diffraction, in order to follow the structural evolution of materials under these conditions. The versatility of AGES is illustrated by two examples of experiments conducted with the system. In solid oxide fuel cell electrode materials, oxygen transport pathways in double perovskites PrBaCo2O5+δ and NdBaCo2O5+δ were elucidated by neutron diffraction measurements under atmosphere with oxygen partial pressures (pO2) of 10-1 to 10-4 (achieved using mixtures of nitrogen and oxygen) and temperatures from 575 to 850 °C. In another example, the potential oxygen storage material La1-xSrxFeO3 was measured under alternating flows of 15% CH4 in N2 and air (20% O2 in N2) at temperatures from 135 to 835 °C. From the oxygen stoichiometry, the optimal composition for oxygen storage was determined.

Turning Nano Porous Aluminium Black: An in Situ High-Energy X-Ray Diffraction and X-Ray Fluorescence Study

Anodized aluminum, commonly used everyday applications, is effectively coloured by electro chemical deposition of materials into the nano-porous anodized aluminum oxide (NP-AAO). The colouring process is sensitive to the details of the nano-porous structure, and increased knowledge is essential to increase the effectiveness of the process to prevent cost, time and environmental losses. To study the electro deposition of material into nano-scale objects and coloring as it happens in a harsh electrolyte is notoriously difficult. As a consequence, knowledge about the coloring process has been obtained from time consuming ex-situ studies, in which the composition of the sample may change upon exposure to ambient environments. We have recently performed in situ studies of the formation of ordered NP-AAO using Grazing Transmission Small Angle X-ray Scattering (GTSAXS) [1]. The small x-ray beams produced by modern synchrotron radiation facilities provides the means for non-intrusive X-Ray Diffraction (XRD) and X-Ray Fluorescence (XRF) on a micron and sub-micron scale, allowing for high temporal and spatial resolution as the coloring process is occurring. In the present study, we have used micro XRD and XRF to study the electro deposition of Sn into the NP-AAO. An X-ray beam of 5 microns and an energy of 70 keV was used to penetrate the electrolyte and focused on the 20 micron thick layer of NP-AAO. Prior to deposition, the anodized alumina was pre-treated electrochemically in situ using a selected number of chemical procedures. The Sn deposition, which colours the aluminum black, was followed by XRF and initiates at the pore bottom and crystalizes as Sn metal nanowires along the pore height according to XRD.

Smaller capillaries improve the small-angle X-ray scattering signal and sample consumption for biomacromolecular solutions.

Radiation damage by intense X-ray beams at modern synchrotron facilities is one of the major complications for biological small-angle X-ray scattering (SAXS) investigations of macromolecules in solution. To limit the damage, samples are typically measured under a laminar flow through a cell (typically a capillary) such that fresh solution is continuously exposed to the beam during measurement. The diameter of the capillary that optimizes the scattering-to-absorption ratio at a given X-ray wavelength can be calculated a priori based on fundamental physical properties. However, these well established scattering and absorption principles do not take into account the radiation susceptibility of the sample or the often very limited amounts of precious biological material available for an experiment. Here it is shown that, for biological solution SAXS, capillaries with smaller diameters than those calculated from simple scattering/absorption criteria allow for a better utilization of the available volumes of radiation-sensitive samples. This is demonstrated by comparing two capillary diameters di (di = 1.7 mm, close to optimal for 10 keV; and di = 0.9 mm, which is nominally sub-optimal) applied to study different protein solutions at various flow rates. The use of the smaller capillaries ultimately allows one to collect higher-quality SAXS data from the limited amounts of purified biological macromolecules.

Recent developments in small-angle X-ray scattering and hybrid method approaches for biomacromolecular solutions.

Small-angle X-ray scattering (SAXS) has become a streamline method to characterize biological macromolecules, from small peptides to supramolecular complexes, in near-native solutions. Modern SAXS requires limited amounts of purified material, without the need for labelling, crystallization, or freezing. Dedicated beamlines at modern synchrotron sources yield high-quality data within or below several milliseconds of exposure time and are highly automated, allowing for rapid structural screening under different solutions and ambient conditions but also for time-resolved studies of biological processes. The advanced data analysis methods allow one to meaningfully interpret the scattering data from monodisperse systems, from transient complexes as well as flexible and heterogeneous systems in terms of structural models. Especially powerful are hybrid approaches utilizing SAXS with high-resolution structural techniques, but also with biochemical, biophysical, and computational methods. Here, we review the recent developments in the experimental SAXS practice and in analysis methods with a specific focus on the joint use of SAXS with complementary methods.

Observation of Pore Growth and Self-Organization in Anodic Alumina by Time-Resolved X-ray Scattering

The anodic oxidation of metals such as aluminum and titanium can lead to the development of self-ordering pores. These pores make excellent templates for a range of nanoscale objects with many applications in nanoscience. Theoretical studies on pore formation have proposed several models for the establishment, growth, and ordering of these pores; however, experimental verification has mostly been limited to ex situ measurements. Here we show that the lateral and vertical pore structure can be probed in situ with high precision, using grazing transmission X-ray scattering. By making use of the high flux available at modern synchrotrons and fitting only the difference between scattering patterns we show the nearly real-time evolution of the pore’s arrangement. We observe no dependence on the substrate crystallographic orientation for domain size or pore separation. We do however observe an anisotropy in the oxide growth rate for the different substrate surfaces. This experimental approach can be applied to ...

Robust X-ray angular correlations for the study of meso-structures

As self-assembling nanomaterials become more sophisticated, it is becoming increasingly important to measure the structural order of finite-sized assemblies of nano-objects. These mesoscale clusters represent an acute challenge to conventional structural probes, owing to the range of implicated size scales (10 nm to several micrometres), the weak scattering signal and the dynamic nature of meso-clusters in native solution environments. The high X-ray flux and coherence of modern synchrotrons present an opportunity to extract structural information from these challenging systems, but conventional ensemble X-ray scattering averages out crucial information about local particle configurations. Conversely, a single meso-cluster scatters too weakly to recover the full diffraction pattern. Using X-ray angular cross-correlation analysis, it is possible to combine multiple noisy measurements to obtain robust structural information. This paper explores the key theoretical limits and experimental challenges that constrain the application of these methods to probing structural order in real nanomaterials. A metric is presented to quantify the signal-to-noise ratio of angular correlations, and it is used to identify several experimental artifacts that arise. In particular, it is found that background scattering, data masking and inter-cluster interference profoundly affect the quality of correlation analyses. A robust workflow is demonstrated for mitigating these effects and extracting reliable angular correlations from realistic experimental data.

Time Resolved Operando X-ray Techniques in Catalysis, a Case Study: CO Oxidation by O2 over Pt Surfaces and Alumina Supported Pt Catalysts

The catalytic oxidation of CO by O2 to form CO2 over Pt surfaces and supported catalysts is one of the most studied catalytic reactions from both fundamental and applied points of view. This review aims to show how the application of a range of time resolved, X-ray based techniques, such as X-ray diffraction (XRD), Surface X-ray diffraction (SXRD), total X-ray scattering/pair distribution function (PDF), X-ray absorption (XAFS), X-ray emission (XES), and X-ray photoelectron spectroscopies (XPS), applied under operando conditions and often coupled to adjunct techniques (for instance mass spectrometry (MS) and infrared spectroscopy (IR)) have shed new light on the structures and mechanisms at work in this most studied of systems. The aim of this review is therefore to demonstrate how a fusion of the operando philosophy with the ever augmenting capacities of modern synchrotron sources can lead to new insight and catalytic possibilities, even in the case of a process that has been intensely studied for almost 100 years.

Advances in threshold photoelectron spectroscopy (TPES) and threshold photoelectron photoion coincidence (TPEPICO).

The history and evolution of molecular threshold photoelectron spectroscopy and threshold photoelectron photoion coincidence spectroscopy (TPEPICO) over the last fifty years are reviewed. Emphasis is placed on instrumentation and the extraction of dynamical information about energy selected ion dissociation, not on the detailed spectroscopy of certain molecules. Three important advances have expanded greatly the power of the technique, and permitted its implementation on modern synchrotron radiation beamlines. The use of velocity focusing of threshold electrons onto an imaging detector in the 1990s simultaneously improved the sensitivity and electron energy resolution, and also facilitated the subtraction of hot electron background in both threshold electron spectroscopy and TPEPICO studies. The development of multi-start multi-stop collection detectors for both electrons and ions in the 2000s permitted the use of the full intensity of modern synchrotron radiation thereby greatly improving the signal-to-noise ratio. Finally, recent developments involving imaging electrons in a range of energies as well as ions onto separate position-sensitive detectors has further improved the collection sensitivity so that low density samples found in a variety of studies can be investigated. As a result, photoelectron photoion coincidence spectroscopy is now well positioned to address a range of challenging problems that include the quantitative determination of compositions of isomer mixtures, and the detection and spectroscopy of free radicals produced in pyrolysis or discharge sources as well as in combustion studies.

High-resolution interference-monochromator for hard X-rays.

An X-ray interference-monochromator combining a Fabry-Perot resonator (FPR) and a double-crystal monochromator (DCM) is proposed and realized for obtaining single-mode X-rays with 3.45 meV energy resolution. The monochromator is based on the generation of cavity interference fringes from a FPR and single-mode selection of the transmission spectrum by a DCM of a nearly backward symmetric reflection geometry. The energy of the monochromator can be tuned within 2500 meV(= ΔE) by temperature control of the FPR and the DCM crystals in the range of ΔT = 70 K at room temperature. The diffraction geometry and small size of the optical components used make the interference-monochromator very easy to be adapted in modern synchrotron beamlines and X-ray optics applications.

Investigating Polymer-Metal Interfaces by Grazing Incidence Small-Angle X-Ray Scattering from Gradients to Real-Time Studies.

Tailoring the polymer–metal interface is crucial for advanced material design. Vacuum deposition methods for metal layer coating are widely used in industry and research. They allow for installing a variety of nanostructures, often making use of the selective interaction of the metal atoms with the underlying polymer thin film. The polymer thin film may eventually be nanostructured, too, in order to create a hierarchy in length scales. Grazing incidence X-ray scattering is an advanced method to characterize and investigate polymer–metal interfaces. Being non-destructive and yielding statistically relevant results, it allows for deducing the detailed polymer–metal interaction. We review the use of grazing incidence X-ray scattering to elucidate the polymer–metal interface, making use of the modern synchrotron radiation facilities, allowing for very local studies via in situ (so-called “stop-sputter”) experiments as well as studies observing the nanostructured metal nanoparticle layer growth in real time.

Real-time control of the beam attenuation with XPAD hybrid pixel detector

In order to fully benefit from a beam produced by modern synchrotron light sources, characterised by a wide and continuous energy spectrum, high brightness and a very high intensity, advancement in detector technology has been made over the last decades. However, one of the main limitations of the state-of-the-art counting hybrid pixel detectors is the maximum count-rate that is very often few orders of magnitudes lower than of the incident, reflected or diffracted beam flux. Therefore, direct beam attenuation is mandatory in order to perform the measurements according to the detector's characteristics. In this work we present a major upgrade of a fast attenuation system developed at Synchrotron SOLEIL, which allows for a dynamical change of the beam attenuation as a function of the photon flux received by XPAD S140 photon counting detector. The system performs a cyclic real-time estimation of the flux received by every pixel during acquisition of an image and searches for clusters of at least two pixels that exceed user defined levels of counts/s. The beam attenuation is immediately and automatically changed in order to guarantee that the detector will always operate in its linear range even during a long continuous scan, by acting on the direct attenuators.

Design and construction of a multi-sensor position monitoring system applied to key components of synchrotron sources

High-accuracy position monitoring of key components is required for modern synchrotron sources, such as free-electron lasers and diffraction-limited storage rings. Although various position monitoring sensors have been adopted to monitor the displacement of key components in each direction in real time, these monitoring systems are usually based on their own coordinate system. Data from such systems are meaningful when evaluating and examining the data from each positioning monitoring system in a unified coordinate system. This paper presents the design and construction of a multi-sensor position monitoring system (MPMS). A hydrostatic levelling system, a wire position sensor (WPS) and a tiltmeter are fixed to a stainless steel plate that has been calibrated by a coordinate-measurement machine. Several plates form the MPMS. The system must compensate for the sag of the stretched wires so that the WPSs create a straight line. The method of the coordinate transformation from the sensor coordinate system to the MPMS coordinate system was thoroughly studied. An experimental MPMS that includes five plates was setup in a 20-m tunnel, and a validation study to verify fully the feasibility of the MPMS was performed.

Speckle-based at-wavelength metrology of X-ray mirrors with super accuracy

X-ray active mirrors, such as bimorph and mechanically bendable mirrors, are increasingly being used on beamlines at modern synchrotron source facilities to generate either focused or "tophat" beams. As well as optical tests in the metrology lab, it is becoming increasingly important to optimise and characterise active optics under actual beamline operating conditions. Recently developed X-ray speckle-based at-wavelength metrology technique has shown great potential. The technique has been established and further developed at the Diamond Light Source and is increasingly being used to optimise active mirrors. Details of the X-ray speckle-based at-wavelength metrology technique and an example of its applicability in characterising and optimising a micro-focusing bimorph X-ray mirror are presented. Importantly, an unprecedented angular sensitivity in the range of two nanoradians for measuring the slope error of an optical surface has been demonstrated. Such a super precision metrology technique will be beneficial to the manufacturers of polished mirrors and also in optimization of beam shaping during experiments.

Rock porosity quantification by dual-energy X-ray computed microtomography

Porous media investigation by X-ray microtomography allows obtaining valuable quantitative and qualitative information, while preserving sample integrity. Modern X-ray nanotomography or Synchrotron radiation systems may distinguish structures sized only hundreds of nanometers. However, pores sized less than a few microns (microporosity) may be undetectable due to the system’s spatial resolution and noise in microfocus sources, compromising the quality of the measurement. In this study a dual-energy methodology was developed to generate density-based images from two scans made at two different voltages (80kV and 130KV) with a microfocus bench-top microtomography system. The images obtained were quantized in 256 gray levels, where the lowest value (zero) corresponded to voids and the highest value (255) corresponded to the densest regions mapped. From density images and single energy images, porosity was evaluated and compared. Results indicate that density images present better results than single energy images when both are compared with porosity obtained by the helium injection method. In addition, images acquired in dual-energy show good agreement with the sample’s real density values.

Distinguishing Protein Nanocrystals from Amorphous Precipitate by Depolarized Dynamic Light Scattering

Growth and preparation of high quality micro-sized protein crystals, optimal for data collection experiments at modern micro-focus synchrotron (SR) beamlines and growth of nanocrystals required for data collection at Free-Electron-Laser (FEL) radiation sources is a new and challenging task. We will present advanced methods to precisely monitor and optimize the preparation of crystalline particles, too small to be observed by light microscopy. The identification of the presence of a spatial repetitive orientation of macromolecules (crystal nuclei) in the early stages of the crystallization process is essential to detect nanocrystals. The optical properties of a crystal lattice offer the potential to detect the transition from disordered to higher ordered particles. A unique experimental setup was designed and constructed to detect nanocrystal formation by analyzing depolarized scattered laser light. The ability of a lattice to depolarize laser light depends on the different refractive indices along different crystal axes. The results obtained so far demonstrate the successful detection of nano-sized protein crystals at early stages of crystal growth, by analyzing the signal intensity of the depolarized component of the scattered light. The method and approach allows an effective differentiation between protein-dense liquid cluster formation and ordered nanocrystals[1].Further, this particular advanced laser light scattering technique can be combined with a state of the art protein crystallization robotic setup (Xtal-Controller[2]), allowing the controlled nanoliter increments addition of protein, precipitant and additive solution towards a crystallization solution sitting on a microbalance. Examples on how these methods can be used for the characterization of crystallization phenomena and the efficient production of nanocrystals are demonstrated and details are presented.[1] Schubert et al., Journal of Applied Crystallography, Issue 48, 1476-1484, (2015)[2] Meyer et al. Acta Crystallographica Section F68, 994-998, (2012)

Detective quantum efficiency for photon-counting hybrid pixel detectors in the tender X-ray domain: application to Medipix3RX.

Synchrotron-radiation-based X-ray imaging techniques using tender X-rays are facing a growing demand, in particular to probe the K absorption edges of low-Z elements. Here, a mathematical model has been developed for estimating the detective quantum efficiency (DQE) at zero spatial frequency in the tender X-ray energy range for photon-counting detectors by taking into account the influence of electronic noise. The experiments were carried out with a Medipix3RX ASIC bump-bonded to a 300 µm silicon sensor at the Soft X-ray Spectroscopy beamline (D04A-SXS) of the Brazilian Synchrotron Light Laboratory (LNLS, Campinas, Brazil). The results show that Medipix3RX can be used to develop new imaging modalities in the tender X-ray range for energies down to 2 keV. The efficiency and optimal DQE depend on the energy and flux of the photons. The optimal DQE values were found in the 7.9-8.6 keV photon energy range. The DQE deterioration for higher energies due to the lower absorption efficiency of the sensor and for lower energies due to the electronic noise has been quantified. The DQE for 3 keV photons and 1 × 10(4) photons pixel(-1) s(-1) is similar to that obtained with 19 keV photons. Based on our model, the use of Medipix3RX could be extended down to 2 keV which is crucial for coming applications in imaging techniques at modern synchrotron sources.

Design and performance of the APPLE-Knot undulator.

Along with the development of accelerator technology, synchrotron emittance has continuously decreased. This results in increased brightness, but also causes a heavy heat load on beamline optics. Recently, optical surfaces with 0.1 nm micro-roughness and 0.05 µrad slope error (r.m.s.) have become commercially available and surface distortions due to heat load have become a key factor in determining beamline performance, and heat load has become a serious problem at modern synchrotron radiation facilities. Here, APPLE-Knot undulators which can generate photons with arbitrary polarization, with low on-axis heat load, are reported.

Rayleigh x-ray scattering from many-electron atoms and ions

A theoretical analysis is presented for the elastic Rayleigh scattering of x-rays by many-electron atoms and ions. Special emphasis is placed on the angular distribution and linear polarization of the scattered photons for the case when the incident light is completely (linearly) polarized. Based on second-order perturbation theory and the independent particle approximation, we found that the Rayleigh angular distribution is strongly affected by the charge state and shell structure of the target ions or atoms. This effect can be observed experimentally at modern synchrotron facilities and might provide further insight into the structure of heavy atomic systems.

Upgrade of MacCHESS facility for X-ray scattering of biological macromolecules in solution.

X-ray scattering of biological macromolecules in solution is an increasingly popular tool for structural biology and benefits greatly from modern high-brightness synchrotron sources. The upgraded MacCHESS BioSAXS station is now located at the 49-pole wiggler beamline G1. The 20-fold improved flux over the previous beamline F2 provides higher sample throughput and autonomous X-ray scattering data collection using a unique SAXS/WAXS dual detectors configuration. This setup achieves a combined q-range from 0.007 to 0.7 Å(-1), enabling better characterization of smaller molecules, while opening opportunities for emerging wide-angle scattering methods. In addition, a facility upgrade of the positron storage ring to continuous top-up mode has improved beam stability and eliminated beam drift over the course of typical BioSAXS experiments. Single exposure times have been reduced to 2 s for 3.560 mg ml(-1) lysozyme with an average quality factor I/σ of 20 in the Guinier region. A novel disposable plastic sample cell design that incorporates lower background X-ray window material provides users with a more pristine sample environment than previously available. Systematic comparisons of common X-ray window materials bonded to the cell have also been extended to the wide-angle regime, offering new insight into best choices for various q-space ranges. In addition, a quantitative assessment of signal-to-noise levels has been performed on the station to allow users to estimate necessary exposure times for obtaining usable signals in the Guinier regime. Users also have access to a new BioSAXS sample preparation laboratory which houses essential wet-chemistry equipment and biophysical instrumentation. User experiments at the upgraded BioSAXS station have been on-going since commissioning of the beamline in Summer 2013. A planned upgrade of the G1 insertion device to an undulator for the Winter 2014 cycle is expected to further improve flux by an order of magnitude.

Nanoscale structure of Si/SiO2/organics interfaces.

X-ray reflectivity measurements of increasingly more complex interfaces involving silicon (001) substrates reveal the existence of a thin low-density layer intruding between the single-crystalline silicon and the amorphous native SiO2 terminating it. The importance of accounting for this layer in modeling silicon/liquid interfaces and silicon-supported monolayers is demonstrated by comparing fits of the measured reflectivity curves by models including and excluding this layer. The inclusion of this layer, with 6-8 missing electrons per silicon unit cell area, consistent with one missing oxygen atom whose bonds remain hydrogen passivated, is found to be particularly important for an accurate and high-resolution determination of the surface normal density profile from reflectivities spanning extended momentum transfer ranges, now measurable at modern third-generation synchrotron sources.