Sub-micrometer focusing setup for high-pressure crystallography at the Extreme Conditions beamline at PETRA†III.

Scientific tasks aimed at decoding and characterizing complex systems and processes at high pressures set new challenges for modern X-ray diffraction instrumentation in terms of X-ray flux, focal spot size and sample positioning. Presented here are new developments at the Extreme Conditions beamline (P02.2, PETRA III, DESY, Germany) that enable considerable improvements in data collection at very high pressures and small scattering volumes. In particular, the focusing of the X-ray beam to the sub-micrometer level is described, and control of the aberrations of the focusing compound refractive lenses is made possible with the implementation of a correcting phase plate. This device provides a significant enhancement of the signal-to-noise ratio by conditioning the beam shape profile at the focal spot. A new sample alignment system with a small sphere of confusion enables single-crystal data collection from grains of micrometer to sub-micrometer dimensions subjected to pressures as high as 200 GPa. The combination of the technical development of the optical path and the sample alignment system contributes to research and gives benefits on various levels, including rapid and accurate diffraction mapping of samples with sub-micrometer resolution at multimegabar pressures.

High-pressure reactions between the pnictogens: the rediscovery of BiN.

We explore chemical reactions within pnictogens with an example of bismuth and nitrogen under extreme conditions. Understanding chemical reactions between Bi and N, elements representing the first and the last stable elements of the nitrogen group, and the physical properties of their compounds under ambient and high pressure is far from being complete. Here, we report the high-pressure high-temperature synthesis of orthorhombic Pbcn BiN (S.G. #60) from Bi and N2 precursors at pressures above 40 GPa. Using synchrotron single-crystal X-ray diffraction on the polycrystalline sample, we solved and refined the compound's structure and studied its behavior and compressibility on decompression to ambient pressure. We confirm the stability of Pbcn BiN to pressures as low as 12.5(4) GPa. Below that pressure value, a group-subgroup phase transformation occurs, resulting in the formation of a non-centrosymmetric BiN solid with a space group Pca21 (S.G. #29). We use ab initio calculations to characterize the polymorphs of BiN. They also provide support and explanation for our experimental observations, in particular those corresponding to peculiar Bi-N bond evolution under pressure, resulting in a change in the coordination numbers of Bi and N as a function of pressure within the explored stability field of Pbcn BiN.

Isothermal equation of state of crystalline and glassy materials from optical measurements in diamond anvil cells.

Here, we present a method to study the equation of state of opaque amorphous and crystalline materials in diamond anvil cells. The approach is based on measurements of sample dimensions using high-resolution optical microscopy. Data on the volumetric strain as a function of pressure allow deriving the isothermal equation of state of the studied material. The analysis of optical images is fully automatized and allows measuring the sample dimensions with the precision of about 60 nm. The methodology was validated by studying isothermal compression of ω-Ti up to 30 GPa in a Ne pressure transmitting medium. Within the accuracy of the measurements, the bulk modulus of ω-Ti determined using optical microscopy was similar to that obtained from x-ray diffraction. For glassy carbon compressed to ∼30 GPa, the previously unknown bulk modulus was found to be equal to K0 = 28 (2) GPa [K' = 5.5(5)].