Direct Synthesis of CuPd Icosahedra Supercrystals Studied by In Situ X-Ray Scattering.

Nanocrystal self-assembly into supercrystals provides a versatile platform for creating novel materials and devices with tailored properties. While common self-assembly strategies imply the use of purified nanoparticles after synthesis, conversion of chemical precursors directly into nanocrystals and then supercrystals in simple procedures has been rarely reported. Here, the nucleation and growth of CuPd icosahedra and their consecutive assembly into large closed-packed face-centered cubic (fcc) supercrystals are studied. To this end, the study simultaneously and in situ measures X-ray total scattering with pair distribution function analysis (TS-PDF) and small-angle X-ray scattering (SAXS). It is found that the supercrystals' formation is preceded by an intermediate dense phase of nanocrystals displaying short-range order (SRO). It is further shown that the organization of oleic acid/oleylamine surfactants into lamellar structures likely drives the emergence of the SRO phase and later of the supercrystals by reducing the volume accessible to particle diffusion. The supercrystals' formation as well as their disassembly are triggered by temperature. The study demonstrates that ordering of solvent molecules can be crucial in the direct synthesis of supercrystals. The study also provides a general approach to investigate novel preparation routes of supercrystals in situ and across several length scales via X-ray scattering.

Chemical and Structural In-Situ Characterization of Model Electrocatalysts by Combined Infrared Spectroscopy and Surface X-ray Diffraction.

New diagnostic approaches are needed to drive progress in the field of electrocatalysis and address the challenges of developing electrocatalytic materials with superior activity, selectivity, and stability. To this end, we developed a versatile experimental setup that combines two complementary in-situ techniques for the simultaneous chemical and structural analysis of planar electrodes under electrochemical conditions: high-energy surface X-ray diffraction (HE-SXRD) and infrared reflection absorption spectroscopy (IRRAS). We tested the potential of the experimental setup by performing a model study in which we investigated the oxidation of preadsorbed CO on a Pt(111) surface as well as the oxidation of the Pt(111) electrode itself. In a single experiment, we were able to identify the adsorbates, their potential dependent adsorption geometries, the effect of the adsorbates on the surface morphology, and the structural evolution of Pt(111) during surface electro-oxidation. In a broader perspective, the combined setup has a high application potential in the field of energy conversion and storage.

Photodegradation of CuBi2 O4 Films Evidenced by Fast Formation of Metallic Bi using Operando Surface-sensitive X-ray Scattering.

CuBi2 O4 has recently emerged as a promising photocathode for photo-electrochemical (PEC) water splitting. However, its fast degradation under operation currently poses a limit to its application. Here, we report a novel method to study operando the semiconductor-electrolyte interface during PEC operation by surface-sensitive high-energy X-ray scattering. We find that a fast decrease in the generated photocurrents correlates directly with the formation of a metallic Bi phase. We further show that the slower formation of metallic Cu, as well as the dissolution of the electrode in contact with the electrolyte, further affect the CuBi2 O4 activity and morphology. Our study provides a comprehensive picture of the degradation mechanisms affecting CuBi2 O4 electrodes under operation and poses the methodological basis to investigate the photocorrosion processes affecting a wide range of PEC materials.

A reactor for time-resolved X-ray studies of nucleation and growth during solvothermal synthesis.

Understanding the nucleation and growth mechanisms of nanocrystals under hydro- and solvothermal conditions is key to tailoring functional nanomaterials. High-energy and high-flux synchrotron radiation is ideal for characterization by powder X-ray diffraction and X-ray total scattering in real time. Different versions of batch-type cell reactors have been employed in this work, exploiting the robustness of polyimide-coated fused quartz tubes with an inner diameter of 0.7 mm, as they can withstand pressures up to 250 bar and temperatures up to 723 K for several hours. Reported here are recent developments of the in situ setups available for general users on the P21.1 beamline at PETRA III and the DanMAX beamline at MAX IV to study nucleation and growth phenomena in solvothermal synthesis. It is shown that data suitable for both reciprocal-space Rietveld refinement and direct-space pair distribution function refinement can be obtained on a timescale of 4 ms.

Dose-efficient scanning Compton X-ray microscopy.

The highest resolution of images of soft matter and biological materials is ultimately limited by modification of the structure, induced by the necessarily high energy of short-wavelength radiation. Imaging the inelastically scattered X-rays at a photon energy of 60 keV (0.02 nm wavelength) offers greater signal per energy transferred to the sample than coherent-scattering techniques such as phase-contrast microscopy and projection holography. We present images of dried, unstained, and unfixed biological objects obtained by scanning Compton X-ray microscopy, at a resolution of about 70 nm. This microscope was realised using novel wedged multilayer Laue lenses that were fabricated to sub-ångström precision, a new wavefront measurement scheme for hard X rays, and efficient pixel-array detectors. The doses required to form these images were as little as 0.02% of the tolerable dose and 0.05% of that needed for phase-contrast imaging at similar resolution using 17 keV photon energy. The images obtained provide a quantitative map of the projected mass density in the sample, as confirmed by imaging a silicon wedge. Based on these results, we find that it should be possible to obtain radiation damage-free images of biological samples at a resolution below 10 nm.

Catalytic reactor for operando spatially resolved structure-activity profiling using high-energy X-ray diffraction.

In heterogeneous catalysis, operando measurements probe catalysts in their active state and are essential for revealing complex catalyst structure-activity relationships. The development of appropriate operando sample environments for spatially resolved studies has come strongly into focus in recent years, particularly when coupled to the powerful and multimodal characterization tools available at synchrotron light sources. However, most catalysis studies at synchrotron facilities only measure structural information about the catalyst in a spatially resolved manner, whereas gas analysis is restricted to the reactor outlet. Here, a fully automated and integrated catalytic profile reactor setup is shown for the combined measurement of temperature, gas composition and high-energy X-ray diffraction (XRD) profiles, using the oxidative dehydrogenation of C2H6 to C2H4 over MoO3/γ-Al2O3 as a test system. The profile reactor methodology was previously developed for X-ray absorption spectroscopy and is here extended for operando XRD. The profile reactor is a versatile and accessible research tool for combined spatially resolved structure-activity profiling, enabling the use of multiple synchrotron-based characterization methods to promote a knowledge-based optimization of a wide range of catalytic systems in a time- and resource-efficient way.

The Effect of pH on the Structure and Lateral Organization of Cardiolipin in Langmuir Monolayers.

Cardiolipin (CL) is a unique phospholipid featuring a dimeric structure. With its four alkyl chains, it has a large hydrophobic region and the charged hydrophilic head group is relatively small. Biological membranes exhibit CL exclusively in the inner bacterial and mitochondrial membranes. Alteration of CL packing can lead to structural changes and membrane instabilities. One environmental influence is the change in pH. Since the acidic properties of the phosphate head groups remain still controversial in literature, this work focusses on the influence of pH on the ionization degree of CL. For the analyses, surface pressure (π) - molecular area (A) isotherm experiments were combined with total reflection X-ray fluorescence (TRXF) and grazing incidence X-ray diffraction (GIXD). Continuous ionization with a high CL packing density was observed in the monolayer over a wide pH range. No individual pKa values can be assigned to the two phosphate groups, but mutual influence is observed.

A combined rotating disk electrode-surface x-ray diffraction setup for surface structure characterization in electrocatalysis.

Characterizing electrode surface structures under operando conditions is essential for fully understanding structure-activity relationships in electrocatalysis. Here, we combine in a single experiment high-energy surface x-ray diffraction as a characterizing technique with a rotating disk electrode to provide steady state kinetics under electrocatalytic conditions. Using Pt(111) and Pt(100) model electrodes, we show that full crystal truncation rod measurements are readily possible up to rotation rates of 1200 rpm. Furthermore, we discuss possibilities for both potentiostatic as well as potentiodynamic measurements, demonstrating the versatility of this technique. These different modes of operation, combined with the relatively simple experimental setup, make the combined rotating disk electrode-surface x-ray diffraction experiment a powerful technique for studying surface structures under operando electrocatalytic conditions.

Cycling Rate-Induced Spatially-Resolved Heterogeneities in Commercial Cylindrical Li-Ion Batteries.

Synchrotron high-energy X-ray diffraction computed tomography has been employed to investigate, for the first time, commercial cylindrical Li-ion batteries electrochemically cycled over the two cycling rates of C/2 and C/20. This technique yields maps of the crystalline components and chemical species as a cross-section of the cell with high spatiotemporal resolution (550 × 550 images with 20 × 20 × 3 µm3 voxel size in ca. 1 h). The recently developed Direct Least-Squares Reconstruction algorithm is used to overcome the well-known parallax problem and led to accurate lattice parameter maps for the device cathode. Chemical heterogeneities are revealed at both electrodes and are attributed to uneven Li and current distributions in the cells. It is shown that this technique has the potential to become an invaluable diagnostic tool for real-world commercial batteries and for their characterization under operating conditions, leading to unique insights into "real" battery degradation mechanisms as they occur.

Laser heating system at the Extreme Conditions Beamline, P02.2, PETRA III.

A laser heating system for samples confined in diamond anvil cells paired with in situ X-ray diffraction measurements at the Extreme Conditions Beamline of PETRA III is presented. The system features two independent laser configurations (on-axis and off-axis of the X-ray path) allowing for a broad range of experiments using different designs of diamond anvil cells. The power of the continuous laser source can be modulated for use in various pulsed laser heating or flash heating applications. An example of such an application is illustrated here on the melting curve of iron at megabar pressures. The optical path of the spectroradiometry measurements is simulated with ray-tracing methods in order to assess the level of present aberrations in the system and the results are compared with other systems, that are using simpler lens optics. Based on the ray-tracing the choice of the first achromatic lens and other aspects for accurate temperature measurements are evaluated.

Real-Time Observation of "Soft" Magic-Size Clusters during Hydrolysis of the Model Metallodrug Bismuth Disalicylate.

Colloidal bismuth therapeutics have been used for hundreds of years, yet remain mysterious. Here we report an X-ray pair distribution function (PDF) study of the solvolysis of bismuth disalicylate, a model for the metallodrug bismuth subsalicylate (Pepto-Bismol). This reveals catalysis by traces of water, followed by multistep cluster growth. The ratio of the two major species, {Bi9O7} and {Bi38O44}, depends on exposure to air, time, and the solvent. The solution-phase cluster structures are of significantly higher symmetry in comparison to solid-state analogues, with reduced off-center Bi3+ displacements. This explains why such "magic-size" clusters can be both stable enough to crystallize and sufficiently labile for further growth.

In situ correlation between metastable phase-transformation mechanism and kinetics in a metallic glass.

A combination of complementary high-energy X-ray diffraction, containerless solidification during electromagnetic levitation and transmission electron microscopy is used to map in situ the phase evolution in a prototype Cu-Zr-Al glass during flash-annealing imposed at a rate ranging from 102 to 103 K s-1 and during cooling from the liquid state. Such a combination of experimental techniques provides hitherto inaccessible insight into the phase-transformation mechanism and its kinetics with high temporal resolution over the entire temperature range of the existence of the supercooled liquid. On flash-annealing, most of the formed phases represent transient (metastable) states - they crystallographically conform to their equilibrium phases but the compositions, revealed by atom probe tomography, are different. It is only the B2 CuZr phase which is represented by its equilibrium composition, and its growth is facilitated by a kinetic mechanism of Al partitioning; Al-rich precipitates of less than 10 nm in a diameter are revealed. In this work, the kinetic and chemical conditions of the high propensity of the glass for the B2 phase formation are formulated, and the multi-technique approach can be applied to map phase transformations in other metallic-glass-forming systems.

Fast-current-heating devices to study in situ phase formation in metallic glasses by using high-energy synchrotron radiation.

Details of fast-resistive-heating setups, controlled heating ranging from ∼101 K s-1 to ∼103 K s-1, to study in situ phase transformations (on heating and on cooling) in metallic glasses by high-energy synchrotron x-ray diffraction are discussed. Both setups were designed and custom built at the Leibniz Institute for Solid State and Materials Research Dresden (IFW Dresden) and have been implemented at the P02.1 Powder Diffraction and Total Scattering Beamline and the P21.1 Swedish Materials Science Beamline at PETRA III storage ring, DESY, Hamburg. The devices are interchangeable at both beamlines. Joule heating is triggered automatically and is timed with the incident beam and detector. The crystallization process can be controlled via a feedback circuit by monitoring the change in the time-dependent resistivity and temperature of glasses. Different ambient atmospheres, such as vacuum and inert gases (He and Ar), can be used to control oxidation and cooling. The main focus of these devices is on understanding the crystallization mechanism and kinetics in metallic glasses, which are brittle and for which fast heating gives defined glass-crystal composites with enhanced plasticity. As an example, phase-transformation sequence(s) in a prototyped Cu-Zr-based metallic glass is described on heating, and a crystalline phase beneficial to the plasticity is identified.

Structure of strontium tellurite glass, anti-glass and crystalline phases by high-energy X-ray diffraction, reverse Monte Carlo and Rietveld analysis.

The structures of xSrO-(100 - x)TeO2 (x = 5, 7.5, 8.5 and 10 mol.%) glass, anti-glass and crystalline samples were studied by high-energy X-ray diffraction (HEXRD), reverse Monte Carlo (RMC) simulations, atomic pair distribution function analysis and Fullprof Rietveld refinement. The atomic pair distributions show the first peak at 1.90 Šdue to the Te-O equatorial bonds and the Te-O peak is asymmetrical due to the range of Te-O bond lengths in glass, anti-glass and crystalline samples. The short-range structural properties of glasses such as Te-O bond lengths, Te-O speciation, Te-Te distances and O-Te-O bond angle distributions were determined by RMC simulations. The average Te-O coordination number (NTe-O) for 5SrO-95TeO2 glass is 3.93 which decreases to 3.59 on increasing the SrO concentration to 10 mol.%. The changes in NTe-O revealed that the glass network predominantly contains TeO4 units with a small amount of TeO3 units and there is a structural transformation TeO4 → TeO3 with an increase in SrO concentration. The O-Te-O bond angle distributions have a peak at 79° and reveal that the Oequatorial-Te-Oequatorial bonds are the most abundant linkages in the tellurite network. Two glass samples containing 7.5 and 8.5 mol.% of SrO were annealed at 350°C for 1 h to produce anti-glass phases; they were further annealed at 450°C for 4 h to transform them into crystalline phases. The anti-glass samples are disordered cubic SrTe5O11 and the disordered monoclinic SrTeO3 phases, whereas the crystalline samples contain monoclinic SrTeO3 and the orthorhombic TeO2 phases. The unit-cell parameters of the anti-glass and crystalline structures were determined by Fullprof Rietveld refinement. Thermal studies found that the glass transition temperature increases with an increase in SrO mol.% and the results on the short-range structure of glasses from Raman spectroscopy are in agreement with the RMC findings.

Evolution of short-range order in chemically and physically grown thin film bilayer structures for electronic applications.

Functional thin films are commonly integrated in electronic devices as part of a multi-layer architecture. Metal/oxide/metal structures e.g. in resistive switching memory and piezoelectric microelectrochemical devices are relevant applications. The films are mostly fabricated from the vapour phase or by solution deposition. Processing conditions with a limited thermal budget typically yield nanocrystalline or amorphous layers. For these aperiodic materials, the structure is described in terms of the local atomic order on the length scale of a few chemical bonds up to several nanometres. Previous structural studies of the short-range order in thin films have addressed the simple case of single coatings on amorphous substrates. By contrast, this work demonstrates how to probe the local structure of two stacked functional layers by means of grazing incidence total X-ray scattering and pair distribution function (PDF) analysis. The key to separating the contributions of the individual thin films is the variation of the incidence angle below the critical angle of total external reflection, In this way, structural information was obtained for functional oxides on textured electrodes, i.e. PbZr0.53O0.47O3 on Pt[111] and HfO2 on TiN, as well as HfO2-TiOx bilayers. For these systems, the transformations from disordered phases into periodic structures via thermal teatment are described. These examples highlight the opportunity to develop a detailed understanding of structural evolution during the fabrication of real thin film devices using the PDF technique.

Structure of bismuth tellurite and bismuth niobium tellurite glasses and Bi2Te4O11 anti-glass by high energy X-ray diffraction.

Glass and anti-glass samples of bismuth tellurite (xBi2O3-(100 - x)TeO2) and bismuth niobium tellurite (xBi2O3-xNb2O5-(100 - 2x)TeO2) systems were prepared by melt-quenching. The bismuth tellurite system forms glasses at low Bi2O3 concentration of 3 to 7 mol%. At 20 mol% Bi2O3, the glass forming ability of the Bi2O3-TeO2 system decreases drastically and the anti-glass phase of monoclinic Bi2Te4O11 is produced. Structures of glass and the anti-glass Bi2Te4O11 samples were studied by high-energy X-ray diffraction, reverse Monte Carlo simulations and Rietveld Fullprof refinement. All glasses have short short-range disorder due to the existence of at least three types of Te-O bonds of lengths: 1.90, 2.25 and 2.59 Å, besides a variety of Bi-O and Nb-O bond-lengths. The medium-range order in glasses is also disturbed due to the distribution of Te-Te pair distances. The average Te-O co-ordination (N Te-O) in the glass network decreases with an increase in Bi2O3 and Nb2O5 mol% and is in the range: 4.17 to 3.56. The anti-glass Bi2Te4O11 has a long-range order of cations but it has vibrational disorder and it exhibits sharp X-ray reflections but broad vibrational bands similar to that in glasses. Anti-glass Bi2Te4O11 has an N Te-O of 2.96 and is significantly lower than in glass samples.

Enhanced chain packing achieved via putative headgroup ion-triplet formation in binary anionic lipid/cationic surfactant mixed monolayers.

Lipid/surfactant miscibility was investigated in monolayers composed of binary mixtures of dipalmitoylphosphatidylglycerol (DPPG) and dihexadecyldimethylammonium bromide (DHDAB). Langmuir monolayers formed from biomimetic DPPG/DHDAB mixtures based on the anionic:cationic lipid ratios observed in the bacterium Staphylococcus aureus (7:3 and 1:1) were examined alongside those of the pure amphiphiles and a surfactant rich 3:7 mixture. Using a combination of GIXD, TRXF and IRRAS, DPPG/DHDAB 1:1 monolayers were found to form a more stabilised condensed phase compared to pure DPPG, which was composed entirely of electrostatically neutral ion pairs, analogous to the so-called catanionic amphiphiles spontaneously formed by single-chain surfactants with opposing headgroup charges. Despite the lack of lateral charge repulsion the ion paired phase of DPPG/DHDAB exhibited slightly looser chain packing that was observed for DPPG indicating a significant steric effect on packing geometry caused by ion pair formation. Surprisingly, the 7:3 mixture of DPPG/DHDAB formed a completely condensed phase, with no isotherm transitions, in which the chain packing was significantly closer than was found for either DPPG or the totally ion paired monolayer. It is postulated that this mixture forms a distinct DPPG/DHDAB/DPPG ion triplet phase in which the overall negative charge is delocalised across the headgroups. Vesicles composed from the 7:3 mixture formed highly stable dispersions with an increased gel to liquid crystalline phase transition temperature with respect to its pure components. Increasing the proportion of DHDAB above 50 mol% led to demixing between the condensed ion paired phase and the more fluid surfactant, as was clearly observed in epifluorescence images taken of the surface films.

The Influence of Calcium Traces in Ultrapure Water on the Lateral Organization in Tetramyristoyl Cardiolipin Monolayers.

Cardiolipin (CL) plays an important role in administering the structural organization of biological membranes and therefore helps maintaining the integer membrane functionality. CL has a dimeric structure consisting of four acyl chains and two phosphate groups. With its unusual structure, the phospholipid is responsible for curvature formation in CL containing biological membranes. The acidic properties of the phosphate head groups are still not sufficiently investigated since there are controversial results in literature. The main aim of this work was to gain deeper insights into the influence of the pH on the ionization degree of CL. During the experiments, it became clear that the used ultrapure water contained traces of calcium. These unexpected calcium ions had a major impact on the behavior of CL monolayers. Therefore, the focus was put on the analysis of CL layers without and with EDTA in the subphase used to complex divalent calcium ions. For the analyses, traditional surface pressure (π) - molecular area (A) isotherm experiments combined with total reflection x-ray fluorescence (TRXF) and grazing incidence x-ray diffraction (GIXD) have been used.

Local atomic structure of thin and ultrathin films via rapid high-energy X-ray total scattering at grazing incidence.

Atomic pair distribution function (PDF) analysis is the most powerful technique to study the structure of condensed matter on the length scale from short- to long-range order. Today, the PDF approach is an integral part of research on amorphous, nanocrystalline and disordered materials from bulk to nanoparticle size. Thin films, however, demand specific experimental strategies for enhanced surface sensitivity and sophisticated data treatment to obtain high-quality PDF data. The approach described here is based on the surface high-energy X-ray diffraction technique applying photon energies above 60 keV at grazing incidence. In this way, reliable PDFs were extracted from films of thicknesses down to a few nanometres. Compared with recently published reports on thin-film PDF analysis from both transmission and grazing-incidence geometries, this work brought the minimum detectable film thickness down by about a factor of ten. Depending on the scattering power of the sample, the data acquisition on such ultrathin films can be completed within fractions of a second. Hence, the rapid-acquisition grazing-incidence PDF method is a major advancement in thin-film technology that opens unprecedented possibilities for in situ and operando PDF studies in complex sample environments. By uncovering how the structure of a layered material on a substrate evolves and transforms in terms of local and average ordering, this technique offers new opportunities for understanding processes such as nucleation, growth, morphology evolution, crystallization and the related kinetics on the atomic level and in real time.

Time-resolved grazing-incidence pair distribution functions during deposition by radio-frequency magnetron sputtering.

Characterization of local order in thin films is challenging with pair distribution function (PDF) analysis because of the minute mass of the scattering material. Here, it is demonstrated that reliable high-energy grazing-incidence total X-ray scattering data can be obtained in situ during thin-film deposition by radio-frequency magnetron sputtering. A benchmark system of Pt was investigated in a novel sputtering chamber mounted on beamline P07-EH2 at the PETRA III synchrotron. Robust and high-quality PDFs can be obtained from films as thin as 3 nm and atomistic modelling of the PDFs with a time resolution of 0.5 s is possible. In this way, it was found that a polycrystalline Pt thin film deposits with random orientation at 8 W and 2 × 10-2 mbar at room temperature. From the PDF it was found that the coherent-scattering domains grow with time. While the first layers are formed with a small tensile strain this relaxes towards the bulk value with increasing film thickness.