Search

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., Funding Agencies: Federal Ministry of Education and Research, Germany (BMBF) [05K19WC1]; Deutsche Forschungsgemeinschaft (DFG) [DU 954-11/1, DU 393-9/2, DU 393-13/1]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Alexander von Humboldt Foundation

Extreme pressures and temperatures are known to drastically affect the chemistry of iron oxides, resulting in numerous compounds forming homologous series nFeOmFe2O3 and the appearance of FeO2. Here, based on the results of in situ single-crystal x-ray diffraction, Mössbauer spectroscopy, x-ray absorption spectroscopy, and density-functional theory+dynamical mean-field theory calculations, we demonstrate that iron in high-pressure cubic FeO2 and isostructural FeO2H0.5 is ferric (Fe3+), and oxygen has a formal valence less than 2. Reduction of oxygen valence from 2, common for oxides, down to 1.5 can be explained by a formation of a localized hole at oxygen sites. © 2021 American Physical Society.

The high-precision X-ray diffraction setup for work with diamond anvil cells (DACs) in interaction chamber 2 (IC2) of the High Energy Density instrument of the European X-ray Free-Electron Laser is described. This includes beamline optics, sample positioning and detector systems located in the multipurpose vacuum chamber. Concepts for pump–probe X-ray diffraction experiments in the DAC are described and their implementation demonstrated during the First User Community Assisted Commissioning experiment. X-ray heating and diffraction of Bi under pressure, obtained using 20 fs X-ray pulses at 17.8 keV and 2.2 MHz repetition, is illustrated through splitting of diffraction peaks, and interpreted employing finite element modeling of the sample chamber in the DAC.

The European XFEL delivers up to 27000 intense (>1012 photons) pulses per second, of ultrashort (≤50 fs) and transversely coherent X-ray radiation, at a maximum repetition rate of 4.5 MHz. Its unique X-ray beam parameters enable groundbreaking experiments in matter at extreme conditions at the High Energy Density (HED) scientific instrument. The performance of the HED instrument during its first two years of operation, its scientific remit, as well as ongoing installations towards full operation are presented. Scientific goals of HED include the investigation of extreme states of matter created by intense laser pulses, diamond anvil cells, or pulsed magnets, and ultrafast X-ray methods that allow their diagnosis using self-amplified spontaneous emission between 5 and 25 keV, coupled with X-ray monochromators and optional seeded beam operation. The HED instrument provides two target chambers, X-ray spectrometers for emission and scattering, X-ray detectors, and a timing tool to correct for residual timing jitter between laser and X-ray pulses.

The high-precision X-ray diffraction setup for work with diamond anvil cells (DACs) in interaction chamber 2 (IC2) of the High Energy Density instrument of the European X-ray Free-Electron Laser is described. This includes beamline optics, sample positioning and detector systems located in the multipurpose vacuum chamber. Concepts for pump-probe X-ray diffraction experiments in the DAC are described and their implementation demonstrated during the First User Community Assisted Commissioning experiment. X-ray heating and diffraction of Bi under pressure, obtained using 20 fs X-ray pulses at 17.8 keV and 2.2 MHz repetition, is illustrated through splitting of diffraction peaks, and interpreted employing finite element modeling of the sample chamber in the DAC.

Extreme pressures and temperatures are known to drastically affect the chemistry of iron oxides, resulting in numerous compounds forming homologous series nFeOmFe2O3 and the appearance of FeO2. Here, based on the results of in situ single-crystal x-ray diffraction, Mössbauer spectroscopy, x-ray absorption spectroscopy, and density-functional theory+dynamical mean-field theory calculations, we demonstrate that iron in high-pressure cubic FeO2 and isostructural FeO2H0.5 is ferric (Fe3+), and oxygen has a formal valence less than 2. Reduction of oxygen valence from 2, common for oxides, down to 1.5 can be explained by a formation of a localized hole at oxygen sites.

In the laboratory study of extreme conditions of temperature and density, the exposure of matter to high intensity radiation sources has been of central importance. Here, we interrogate the performance of multi-layered targets in experiments involving high intensity, hard x-ray irradiation, motivated by the advent of extremely high brightness hard x-ray sources, such as free electron lasers and 4th-generation synchrotron facilities. Intense hard x-ray beams can deliver significant energy in targets having thick x-ray transparent layers (tampers) around samples of interest for the study of novel states of matter and materials’ dynamics. Heated-state lifetimes in such targets can approach the microsecond level, regardless of radiation pulse duration, enabling the exploration of conditions of local thermal and thermodynamic equilibrium at extreme temperature in solid density matter. The thermal and mechanical responses of such thick layered targets following x-ray heating, including hydrodynamic relaxation and heat flow on picosecond to millisecond timescales, are modeled using radiation hydrocode simulation, finite element analysis, and thermodynamic calculations. Assessing the potential for target survival over one or more exposures and resistance to damage arising from heating and resulting mechanical stresses, this study doubles as an investigation into the performance of diamond anvil high pressure cells under high x-ray fluences. Long used in conjunction with synchrotron x-ray radiation and high power optical lasers, the strong confinement afforded by such cells suggests novel applications at emerging high intensity x-ray facilities and new routes to studying thermodynamic equilibrium states of warm, very dense matter.

Silicon, being one of the most abundant elements in nature, attracts wide-ranging scientific and technological interest. Specifically, in its elemental form, crystals of remarkable purity can be produced. One may assume that this would lead to silicon being well understood, and indeed, this is the case for many ambient properties, as well as for higher-pressure behaviour under quasi-static loading. However, despite many decades of study, a detailed understanding of the response of silicon to rapid compression—such as that experienced under shock impact—remains elusive. Here, we combine a novel free-electron laser-based X-ray diffraction geometry with laser-driven compression to elucidate the importance of shear generated during shock compression on the occurrence of phase transitions. We observe lowering of the hydrostatic phase boundary in elemental silicon, an ideal model system for investigating high-strength materials, analogous to planetary constituents. Moreover, we unambiguously determine the onset of melting above 14 GPa, previously ascribed to a solid–solid phase transition, undetectable in the now conventional shocked diffraction geometry; transitions to the liquid state are expected to be ubiquitous in all systems at sufficiently high pressures and temperatures.

The structural evolution of a liquid GaIn eutectic alloy under high temperature and high pressure is investigated by combining in situ X-ray diffraction (XRD) and ab initio molecular dynamics simulations. Both experimental and theoretical results confirm that no pressure-induced sudden structural changes are detected in the liquid state along different isotherms below 700 K. The XRD patterns indicate that the liquids at 400 and 673 K both crystallize into a tetragonal crystalline phase under high pressure, whose structure is locally face centered cubic (fcc)-like. The theoretical simulations successfully describe the atomic-scale structural evolution from disordered liquid to ordered solid phases during the isothermal compression at different temperatures, revealing a strong competition between the body-centered cubic (bcc)-like and fcc-like local atomic packings at the early stage of nucleation. The liquid can directly solidify into the bcc-like atomic packing at temperatures above 650 K, whereas this bcc-like structure becomes transient and metastable below 600 K and finally transforms into a stable fcc-like atomic packing with increasing pressure. Furthermore, a high-pressure and high-temperature “phase diagram” of the GaIn eutectic alloy is roughly constructed, providing new insight into atomic-scale disorder-to-order transition of the liquid GaIn eutectic alloy in extreme conditions.

Poly-nitrogen compounds have been considered as potential high energy density materials for a long time due to the large number of energetic N-N or N=N bonds. In most cases high nitrogen content and stability at ambient conditions are mutually exclusive, thereby making the synthesis of such materials challenging. One way to stabilize such compounds is the application of high pressure. Here, through a direct reaction between Fe and N-2 in a laser-heated diamond anvil cell, we synthesize three ironnitrogen compounds Fe3N2, FeN2 and FeN4. Their crystal structures are revealed by single-crystal synchrotron X-ray diffraction. Fe3N2, synthesized at 50 GPa, is isostructural to chromium carbide Cr3C2. FeN2 has a marcasite structure type and features covalently bonded dinitrogen units in its crystal structure. FeN4, synthesized at 106 GPa, features polymeric nitrogen chains of [N-4(2-)](n) units. Based on results of structural studies and theoretical analysis, [N-4(2-)](n) units in this compound reveal catena-poly[tetraz-1-ene-1,4-diyl] anions., Funding Agencies|National Science Foundation-Earth Sciences [EAR-1634415]; Department of Energy-GeoSciences [DE-FG02-94ER14466]; DOE Office of Science [DE-AC02-06CH11357]; Deutsche Forschungsgemeinschaft (DFG) [DU 954-11/1, DU 393-10/1]; Federal Ministry of Education and Research, Germany (BMBF) [5K16WC1]; Swedish Research Council [2015-04391]; VINN Excellence Center Functional Nanoscale Materials (FunMat-2) [2016-05156]; Swedish Government Strategic Research Areas in Materials Science on Functional Materials at Linkoping University [2009-00971]; Swedish e-Science Research Centre (SeRC); Ministry of Education and Science of the Russian Federation [14.Y26.31.0005, K2-2017-080]; RFBR [16-02-00797]

Synchrotrons can provide very intense and focused X-ray beams, which can be used to study the structure of matter down to the atomic scale. In many experiments, the quality of the results depends strongly on detector performance; in particular, experiments studying dynamics of samples require fast, sensitive X-ray detectors. "LAMBDA" is a photon-counting hybrid pixel detector system for experiments at synchrotrons, based on the Medipix3 readout chip. Its main features are a combination of comparatively small pixel size (55 μm), high readout speed at up to 2000 frames per second with no time gap between images, a large tileable module design, and compatibility with high-Z sensors for efficient detection of higher X-ray energies. A large LAMBDA system for hard X-ray detection has been built using Cr-compensated GaAs as a sensor material. The system is composed of 6 GaAs tiles, each of 768 by 512 pixels, giving a system with approximately 2 megapixels and an area of 8.5 by 8.5 cm2. While the sensor uniformity of GaAs is not as high as that of silicon, its behaviour is stable over time, and it is possible to correct nonuniformities effectively by postprocessing of images. By using multiple 10 Gigabit Ethernet data links, the system can be read out at the full speed of 2000 frames per second. The system has been used in hard X-ray diffraction experiments studying the structure of samples under extreme pressure in diamond anvil cells. These experiments can provide insight into geological processes. Thanks to the combination of high speed readout, large area and high sensitivity to hard X-rays, it is possible to obtain previously unattainable information in these experiments about atomic-scale structure on a millisecond timescale during rapid changes of pressure or temperature.

The stability of high-entropy alloys (HEAs) is a key issue before their selection for industrial applications. In this study, in-situ high-pressure and high-temperature synchrotron radiation X-ray diffraction experiments have been performed on three typical HEAs Ni20Co20Fe20Mn20Cr20, Hf25Nb25Zr25Ti25, and Re25Ru25Co25Fe25 (at. %), having face-centered cubic (fcc), body-centered cubic (bcc), and hexagonal close-packed (hcp) crystal structures, respectively, up to the pressure of ∼80 GPa and temperature of ∼1262 K. Under the extreme conditions of the pressure and temperature, all three studied HEAs remain stable up to the maximum pressure and temperatures achieved. For these three types of studied HEAs, the pressure-dependence of the volume can be well described with the third order Birch-Murnaghan equation of state. The bulk modulus and its pressure derivative are found to be 88.3 GPa and 4 for bcc-Hf25Nb25Zr25Ti25, 193.9 GPa and 5.9 for fcc-Ni20Co20Fe20Mn20Cr20, and 304.6 GPa and 3.8 for hcp-Re25Ru25Co25Fe25 HEAs, respectively. The thermal expansion coefficient for the three studied HEAs is found to be in the order as follows: fcc-Ni20Co20Fe20Mn20Cr20 > bcc-Hf25Nb25Zr25Ti25 ≈ hcp-Re25Ru25Co25Fe25.

Synchrotron x-ray diffraction reveals a pressure induced crystallization at about 3.4 GPa and a polymorphic transition near 10.3 GPa when compressed a liquid GaIn eutectic alloy up to ~13 GPa at room temperature in a diamond anvil cell. Upon decompression, the high pressure crystalline phase remains almost unchanged until it transforms to the liquid state at around 2.3 GPa. The ab initio molecular dynamics calculations can reproduce the low pressure crystallization and give some hints on the understanding of the transition between the liquid and the crystalline phase on the atomic level. The calculated pair correlation function g(r) shows a non-uniform contraction reflected by the different compressibility between the short (1st shell) and the intermediate (2nd to 4th shells). It is concluded that the pressure-induced liquid-crystalline phase transformation likely arises from the changes in local atomic packing of the nearest neighbors as well as electronic structures at the transition pressure.