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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 10 2 to 10 3  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. The competition between the formation of different phases and their kinetics need to be clearly understood to make materials with on-demand and multifaceted properties. Here, the authors reveal, by a combination of complementary in situ techniques, the mechanism of a Cu-Zr-Al metallic glass’s high propensity for metastable phase formation, which is partially through a kinetic mechanism of Al partitioning.

Colloidal lead halide perovskite nanocrystals have potential for lighting applications due to their optical properties. Precise control of the nanocrystal dimensions and composition is a prerequisite for establishing practical applications. However, the rapid nature of their synthesis precludes a detailed understanding of the synthetic pathways, thereby limiting the optimisation. Here, we deduce the formation mechanisms of anisotropic lead halide perovskite nanocrystals, 1D nanorods and 2D nanoplatelets, by combining in situ X-ray scattering and photoluminescence spectroscopy. In both cases, emissive prolate nanoclusters form when the two precursor solutions are mixed. The ensuing antisolvent addition induces the divergent anisotropy: The intermediate nanoclusters are driven into a dense hexagonal mesophase, fusing to form nanorods. Contrastingly, nanoplatelets grow freely dispersed from dissolving nanoclusters, stacking subsequently in lamellar superstructures. Shape and size control of the nanocrystals are determined primarily by the antisolvent’s dipole moment and Hansen hydrogen bonding parameter. Exploiting the interplay of antisolvent and organic ligands could enable more complex nanocrystal geometries in the future. Lead halide perovskite nanocrystals show bright and colour-pure emission in the visible range, which can be tuned by nanocrystal size and composition. Here authors present the formation mechanisms of anisotropic lead halide perovskite nanocrystals, 1D nanorods and 2D nanoplatelets, by combining in situ X-ray scattering and photoluminescence spectroscopy.

Beamline P21.1 at PETRA III uses high-energy photons for the investigation of materials structure by diffraction methods. The instrumentation is particularly suited for probing ordering phenomena on a local scale in chemistry and physics. A detailed description of the instrumentation and detectors for such experiments is given. The beamline supports a number of sample environments for investigations under in situ and operando conditions, e.g. cryostats, furnaces, chemical reactors. Recent examples of measurements on amorphous, single-crystalline and thin film samples are described.

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.

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. This study introduces a catalytic profile reactor capable of simultaneously measuring spatially resolved temperature, concentration and X‐ray diffraction profiles through a catalytic fixed bed under operation. The profile reactor is a versatile and accessible research tool, allowing the usage of multiple synchrotron‐based characterization methods to understand and systematically optimize a wide range of catalytic systems.

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. High-resolution, low-dose images of biological objects were obtained in a new method using photons of 60 keV. The dose was thousands of times lower than conventional methods, overcoming the previous limitations set by radiation damage to the sample.

The discovery of unconventional superconductivity often triggers significant interest in associated electronic and structural symmetry breaking phenomena. For the infinite-layer nickelates, structural allotropes are investigated intensively. Here, using high-energy grazing-incidence x-ray diffraction, we demonstrate how in-situ temperature annealing of the infinite-layer nickelate PrNiO 2+ x ( x  ≈ 0) induces a giant superlattice structure. The annealing effect has a maximum well above room temperature. By covering a large scattering volume, we show a rare period-six in-plane (bi-axial) symmetry and a period-four symmetry in the out-of-plane direction. This giant unit-cell superstructure—likely stemming from ordering of diffusive oxygen—persists over a large temperature range and can be quenched. As such, the stability and controlled annealing process leading to the formation of this superlattice structure provides a pathway for novel nickelate chemistry. Infinite-layer nickelates are of interest for exploration of unconventional superconductivity. Here, grazing-incidence x-ray diffraction of PrNiO 2+ x reveals an unusual in-plane period-six and out-of-plane period-four symmetry upon in-situ annealing, indicating a giant unit-cell superstructure.

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.

Understanding the interaction between surfaces and their surroundings is crucial in many materials-science fields, such as catalysis, corrosion, and thin-film electronics, but existing characterization methods have not been capable of fully determining the structure of surfaces during dynamic processes, such as catalytic reactions, in a reasonable time frame. We demonstrate an x-ray-diffraction–based characterization method that uses high-energy photons (85 kiloelectron volts) to provide unexpected gains in data acquisition speed by several orders of magnitude and enables structural determinations of surfaces on time scales suitable for in situ studies. We illustrate the potential of high-energy surface x-ray diffraction by determining the structure of a palladium surface in situ during catalytic carbon monoxide oxidation and follow dynamic restructuring of the surface with subsecond time resolution.

The discovery of unconventional superconductivity often triggers significant interest in associated electronic and structural symmetry breaking phenomena. For the infinite-layer nickelates, structural allotropes are investigated intensively. Here, using high-energy grazing-incidence x-ray diffraction, we demonstrate how in-situ temperature annealing of the infinite-layer nickelate PrNiO (  ≈ 0) induces a giant superlattice structure. The annealing effect has a maximum well above room temperature. By covering a large scattering volume, we show a rare period-six in-plane (bi-axial) symmetry and a period-four symmetry in the out-of-plane direction. This giant unit-cell superstructure-likely stemming from ordering of diffusive oxygen-persists over a large temperature range and can be quenched. As such, the stability and controlled annealing process leading to the formation of this superlattice structure provides a pathway for novel nickelate chemistry.