X-ray focusing to 62 keV by compound refractive lenses for high-pressure x-ray diffraction.

This study describes high-energy x-ray focusing optics using compound refractive lenses (CRLs) for high-pressure x-ray diffraction (XRD) with a monochromatic x-ray beam. A CRL-based x-ray transfocator was upgraded and installed in the optics hutch at the BL10XU beamline of SPring-8. The instrument can be equipped with two types of CRLs in parallel: a newly designed aluminum (Al) CRL for x-ray energies of 40-62 keV and an existing glassy carbon CRL for those up to 40 keV. In only the Al-CRL-based x-ray transfocator, a 62 keV monochromatic x-ray beam with horizontal (H) and vertical (V) focused spots, whose sizes were 189 and 10.5 µm, respectively, and a flux of 1.32 × 1011 phs/s were generated. A polymer SU-8 CRL fabricated via deep x-ray lithography was installed to further reduce the x-ray beam size. The Al-CRL and the SU-8 CRL were combined to generate a smaller spot size of 12.5 (H) × 11.0 (V) µm2 with a flux of 3 × 1010 phs/s at 62 keV. A two-step optical configuration combining an x-ray transfocator and SU-8 CRL provides a valuable method for high-pressure XRD using a high-energy x-ray focused beam. The optical design and performance of the Al-CRL-based x-ray transfocator, its combination with the SU-8 CRL, and the first results of the focusing optics commissioning are presented here.

Suppression of Pressure-Induced Phase Transitions in a Monoclinically Distorted LiNbO3-Type CuNbO3 by Preference for a CuO3 Triangular Coordination Environment.

Pressure-induced phase transitions in a monoclinically distorted LiNbO3-type CuNbO3 with triangularly coordinated Cu and octahedrally coordinated Nb were experimentally and computationally investigated. Phase transitions into GdFeO3-type or NaIO3-type structures generally observed in LiNbO3-type compounds below 30 GPa were not detected in CuNbO3 even at the maximum experimental pressure, 32.4 GPa. Our density functional theory calculations revealed that the phase transition is suppressed by the preference for the CuO3 triangular coordination environment, which reduces the total internal energy. This study clarifies that the change in the coordination environment of given ions can affect the pressure-induced phase transition.

Pressure-induced transitions inRCo5(R=Y, La) studied by x-ray emission spectroscopy, x-ray diffraction and density functional theory.

The hydrostatic pressure dependent evolution of the electronic and magnetic structure of LaCo5and YCo5was investigated by means of x-ray emission spectroscopy, x-ray diffraction, and spin-polarized density functional theory (DFT) calculations. Using experimental lattice parameters the DFT correctly predicts the pressure of the magnetic transition in both compounds to be 26 GPa (La) and 22-23 GPa (Y). The transition was experimentally resolved in the changes of the electronic structure via the integrated absolute difference of the CoKßemission spectra. Comparison of theory and experiment confirm for the first time a common feature in both LaCo5and YCo5to be the source of the transition; the Fermi-level crossing of an up-spin polarized flat band driving the systems into a low spin configuration via a Lifshitz type transition of the Fermi surface. Another phase transition observed around 12 GPa in LaCo5was clarified to be caused by the change in the down-spin density of states at the Fermi level.

Equation of states for dense ice up to 80 GPa at low-temperature conditions.

We have measured the lattice volume of ice VIII in different pressure-temperature pathways and found that the volume depends on the pathway, implying that deviatoric stress makes the volume larger. Dense ice is in the ice VIII phase with the molar volume of 6.56 cm3 and in a high-pressure phase with the molar volume of 6.45 cm3 at 10 K where the pressure can be estimated as 57.0 ± 3.4 and 60.4 ± 3.6 GPa, respectively, based on the third-order Birch-Murnaghan equation with parameters determined in this study (K0 = 30.8 ± 1.3 GPa and K'0 = 3.7 ± 0.1 with V0 fixed to 12.030 cm3).

Incorporation mechanism of Fe and Al into bridgmanite in a subducting mid-ocean ridge basalt and its crystal chemistry.

The compositional difference between subducting slabs and their surrounding lower-mantle can yield the difference in incorporation mechanism of Fe and Al into bridgmanite between both regions, which should cause heterogeneity in physical properties and rheology of the lower mantle. However, the precise cation-distribution has not been examined in bridgmanites with Fe- and Al-contents expected in a mid-ocean ridge basalt component of subducting slabs. Here we report on Mg0.662Fe0.338Si0.662Al0.338O3 bridgmanite single-crystal characterized by a combination of single-crystal X-ray diffraction, synchrotron 57Fe-Mössbauer spectroscopy and electron probe microanalysis. We find that the charge-coupled substitution AMg2+ + BSi4+ ↔ AFe3+(high-spin) + BAl3+ is predominant in the incorporation of Fe and Al into the practically eightfold-coordinated A-site and the sixfold-coordinated B-site in bridgmanite structure. The incorporation of both cations via this substitution enhances the structural distortion due to the tilting of BO6 octahedra, yielding the unusual expansion of mean bond-length due to flexibility of A-O bonds for the structural distortion, in contrast to mean bond-length depending reasonably on the ionic radius effect. Moreover, we imply the phase-transition behavior and the elasticity of bridgmanite in slabs subducting into deeper parts of the lower mantle, in terms of the relative compressibility of AO12 (practically AO8) and BO6 polyhedra.

Low-spin ferric iron in primordial bridgmanite crystallized from a deep magma ocean.

The crystallization of the magma ocean resulted in the present layered structure of the Earth's mantle. An open question is the electronic spin state of iron in bridgmanite (the most abundant mineral on Earth) crystallized from a deep magma ocean, which has been neglected in the crystallization history of the entire magma ocean. Here, we performed energy-domain synchrotron Mössbauer spectroscopy measurements on two bridgmanite samples synthesized at different pressures using the same starting material (Mg0.78Fe0.13Al0.11Si0.94O3). The obtained Mössbauer spectra showed no evidence of low-spin ferric iron (Fe3+) from the bridgmanite sample synthesized at relatively low pressure of 25 gigapascals, while that directly synthesized at a higher pressure of 80 gigapascals contained a relatively large amount. This difference ought to derive from the large kinetic barrier of Fe3+ rearranging from pseudo-dodecahedral to octahedral sites with the high-spin to low-spin transition in experiments. Our results indicate a certain amount of low-spin Fe3+ in the lower mantle bridgmanite crystallized from an ancient magma ocean. We therefore conclude that primordial bridgmanite with low-spin Fe3+ dominated the deeper part of an ancient lower mantle, which would contribute to lower mantle heterogeneity preservation and call for modification of the terrestrial mantle thermal evolution scenarios.

Diamond formation from methane hydrate under the internal conditions of giant icy planets.

Hydrocarbon chemistry in the C-O-H system at high pressure and high temperature is important for modelling the internal structure and evolution of giant icy planets, such as Uranus and Neptune, as their interiors are thought to be mainly composed of water and methane. In particular, the formation of diamond from the simplest hydrocarbon, i.e., methane, under the internal conditions of these planets has been discussed for nearly 40 years. Here, we demonstrate the formation of diamond from methane hydrate up to 3800 K and 45 GPa using a CO2 laser-heated diamond anvil cell combined with synchrotron X-ray diffraction, Raman spectroscopy, and scanning electron microscopy observations. The results show that the process of dissociation and polymerisation of methane molecules to produce heavier hydrocarbons while releasing hydrogen to ultimately form diamond proceeds at milder temperatures (~ 1600 K) and pressures (13-45 GPa) in the C-O-H system than in the C-H system due to the influence of water. Our findings suggest that diamond formation can also occur in the upper parts of the icy mantles of giant icy planets.

Equation of State of Liquid Iron under Extreme Conditions.

The density of liquid iron has been determined up to 116 GPa and 4350 K via static compression experiments following an innovative analysis of diffuse scattering from liquid. The longitudinal sound velocity was also obtained to 45 GPa and 2700 K based on inelastic x-ray scattering measurements. Combining these results with previous shock-wave data, we determine a thermal equation of state for liquid iron. It indicates that Earth's outer core exhibits 7.5%-7.6% density deficit, 3.7%-4.4% velocity excess, and an almost identical adiabatic bulk modulus, with respect to liquid iron.

Electronic structure of dense solid oxygen from insulator to metal investigated with X-ray Raman scattering.

Electronic structures of dense solid oxygen have been investigated up to 140 GPa with oxygen K-edge X-ray Raman scattering spectroscopy with the help of ab initio calculations based on density functional theory with semilocal metageneralized gradient approximation and nonlocal van der Waals density functionals. The present study demonstrates that the transition energies (Pi*, Sigma*, and the continuum) increase with compression, and the slopes of the pressure dependences then change at 94 GPa. The change in the slopes indicates that the electronic structure changes at the metallic transition. The change in the Pi* and Sigma* bands implies metallic characteristics of dense solid oxygen not only in the crystal a-b plane but also parallel to the c axis. The pressure evolution of the spectra also changes at ∼40 GPa. The experimental results are qualitatively reproduced in the calculations, indicating that dense solid oxygen transforms from insulator to metal via the semimetallic transition.

A simple variant selection in stress-driven martensitic transformation.

The study of orientation variant selection helps to reveal the mechanism and dynamic process of martensitic transformations driven by temperature or pressure/stress. This is challenging due to the multiple variants which may coexist. While effects of temperature and microstructure in many martensitic transformations have been studied in detail, effects of stress and pressure are much less understood. Here, an in situ variant selection study of Mn2O3 across the cubic-to-orthorhombic martensitic transformation explores orientation variants at pressures up to 51.5 GPa and stresses up to 5.5 GPa, using diamond anvil cells in radial geometry with synchrotron X-ray diffraction. The diamonds not only exert pressure but also impose stress and cause plastic deformation and texture development. The crystal orientation changes were followed in situ and a {110} c 〈001〉 c // (100) o 〈010〉 o relationship was observed. Only the {110} c plane perpendicular to the stress direction was selected to become (100) o , resulting in a very strong texture of the orthorhombic phase. Contrary to most other martensitic transformations, this study reveals a clear and simple variant selection that is attributed to structural distortions under pressure and stress.

Pressure-induced fluorescence enhancement of FAαPbBr2+α composite perovskites.

FAαPbBr2+α composite perovskites consisting of 0D FA4PbBr6 and 3D FAPbBr3 have been synthesized by a solid state reaction. Due to the endotaxy passivation of FAPbBr3 by FA4PbBr6, FAPbBr3 crystals were stably deformed without agglomeration from the cubic to the orthorhombic structure by compression, which led to a significant PL enhancement.

Pancakes under Pressure: A Case Study on Isostructural Dithia- and Diselenadiazolyl Radical Dimers.

The isostructural dimers of the 1,4-phenylene-bridged bis-1,2,3,5-dithia- and bis-1,2,3,5-diselenadiazolyl diradicals 1,4-S/Se are small band gap semiconductors. The response of their molecular and solid state electronic structures to pressure has been explored over the range 0-10 GPa. The crystal structures, which consist of cofacially aligned (pancake) π-dimers packed into herringbone arrays, experience a continuous, near-isotropic compression. While the intramolecular covalent E-E (E = S/Se) bonds remain relatively unchanged with pressurization, the intradimer E···E separations are significantly shortened. Molecular and band electronic structure calculations using density functional theory methods indicate that compression of the π-dimers leads to a widening of the gap Δ E between the highest occupied and lowest unoccupied molecular orbitals of the dimer, an effect that offsets the expected decrease in the valence-to-conduction band gap Eg occasioned by pressure-induced spreading of the valence and conduction bands. Consistent with the predicted consequences of this competition between intra- and interdimer interactions, variable temperature high pressure conductivity measurements reveal at best an order-of-magnitude increase in conductivity with pressure for the two compounds over the pressure range 0-10 GPa. While a small reduction in the thermal activation energy Eact with increasing pressure is observed, extrapolation of the rate of decrease suggests a projected onset of metallization ( Eact ≈ 0) in excess of 20 GPa.

Unexpected Semimetallic BiS2 at High Pressure and High Temperature.

In the past decade, the group V-VI compounds have been widely investigated due to their excellent properties and applications. It is now accepted that diverse stoichiometry can yield new compounds with unanticipated properties, uncovering potentially new physicochemical mechanisms. However, in this group, aside from the conventional A2B3-type, no other energetically stable stoichiometry has been reported yet. Here, we report that Bi2S3 is unstable and decomposes into stoichiometric BiS2 and BiS with different Bi valence states upon compression. Encouragingly, we successfully synthesized the predicted BiS2 phase and thus, confirmed its existence. Our current calculations reveal that the found BiS2 phase is a semimetal, associated with the increased concentration of nonmetallic S. The present results represent the first counterintuitive stable stoichiometry of group V-VI and provide a good example in designing and synthesizing new compounds under compression.

Discovery of moganite in a lunar meteorite as a trace of H2O ice in the Moon's regolith.

Moganite, a monoclinic SiO2 phase, has been discovered in a lunar meteorite. Silica micrograins occur as nanocrystalline aggregates of mostly moganite and occasionally coesite and stishovite in the KREEP (high potassium, rare-earth element, and phosphorus)-like gabbroic-basaltic breccia NWA 2727, although these grains are seemingly absent in other lunar meteorites. We interpret the origin of these grains as follows: alkaline water delivery to the Moon via carbonaceous chondrite collisions, fluid capture during impact-induced brecciation, moganite precipitation from the captured H2O at pH 9.5 to 10.5 and 363 to 399 K on the sunlit surface, and meteorite launch from the Moon caused by an impact at 8 to 22 GPa and >673 K. On the subsurface, this captured H2O may still remain as ice at estimated bulk content of >0.6 weight %. This indicates the possibility of the presence of abundant available water resources underneath local sites of the host bodies within the Procellarum KREEP and South Pole Aitken terranes.

At-wavelength optics characterisation via X-ray speckle- and grating-based unified modulated pattern analysis.

The current advances in new generation X-ray sources are calling for the development and improvement of high-performance optics. Techniques for high-sensitivity phase sensing and wavefront characterisation, preferably performed at-wavelength, are increasingly required for quality control, optimisation and development of such devices. We here show that the recently proposed unified modulated pattern analysis (UMPA) can be used for these purposes. We characterised two polymer X-ray refractive lenses and quantified the effect of beam damage and shape errors on their refractive properties. Measurements were performed with two different setups for UMPA and validated with conventional X-ray grating interferometry. Due to its adaptability to different setups, the ease of implementation and cost-effectiveness, we expect UMPA to find applications for high-throughput quantitative optics characterisation and wavefront sensing.

Emergence of a new valence-ordered structure and collapse of the magnetic order under high pressure in EuPtP.

The layered hexagonal EuPtP is a rare substance that exhibits two successive valence transitions occurring simultaneously with valence ordering transitions and an antiferromagnetic order. Anticipating that the application of pressure to this sample would induce a new valence-ordered structure and/or a new phenomenon associated with valence fluctuation, we examined the electrical resistivity ρ, the Eu L3-edge x-ray absorption spectroscopy, and the powder x-ray diffraction under high pressure. We found a new valence transition at around P = 2.5 GPa. After the transition, a new valence-ordered structure is realized at the lowest temperature. The valence-ordered structure is inferred to be stacking of [Formula: see text] (2+: Eu2+ layer, 3+: Eu3+ layer) along the c-axis. Upon further increases in pressure, the valence-ordered structure is suppressed and another valance-ordered phase is realized up to P = 6 GPa. The antiferromagnetic order collapses in the pressure range between 6 GPa and 8 GPa.

Significant improvement in Mn2O3 transition metal oxide electrical conductivity via high pressure.

Highly efficient energy storage is in high demand for next-generation clean energy applications. As a promising energy storage material, the application of Mn2O3 is limited due to its poor electrical conductivity. Here, high-pressure techniques enhanced the electrical conductivity of Mn2O3 significantly. In situ synchrotron micro X-Ray diffraction, Raman spectroscopy and resistivity measurement revealed that resistivity decreased with pressure and dramatically dropped near the phase transition. At the highest pressure, resistivity reduced by five orders of magnitude and the sample showed metal-like behavior. More importantly, resistivity remained much lower than its original value, even when the pressure was fully released. This work provides a new method to enhance the electronic properties of Mn2O3 using high-pressure treatment, benefiting its applications in energy-related fields.

Diamond formation in the deep lower mantle: a high-pressure reaction of MgCO3 and SiO2.

Diamond is an evidence for carbon existing in the deep Earth. Some diamonds are considered to have originated at various depth ranges from the mantle transition zone to the lower mantle. These diamonds are expected to carry significant information about the deep Earth. Here, we determined the phase relations in the MgCO3-SiO2 system up to 152 GPa and 3,100 K using a double sided laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction. MgCO3 transforms from magnesite to the high-pressure polymorph of MgCO3, phase II, above 80 GPa. A reaction between MgCO3 phase II and SiO2 (CaCl2-type SiO2 or seifertite) to form diamond and MgSiO3 (bridgmanite or post-perovsktite) was identified in the deep lower mantle conditions. These observations suggested that the reaction of the MgCO3 phase II with SiO2 causes formation of super-deep diamond in cold slabs descending into the deep lower mantle.

The Room-Temperature Superionic Conductivity of Silver Iodide Nanoparticles under Pressure.

We performed variable-temperature synchrotron powder X-ray diffraction measurements and impedance spectroscopy under pressure for silver iodide (AgI) nanoparticles with a diameter of 11 nm. The superionic conducting α-phase of AgI nanoparticles was successfully stabilized down to at least 20 °C by applying a pressure of 0.18 GPa, whereas the transition temperature was 147 °C in bulk AgI at ambient pressure. To our knowledge, this is the first example of the α-phase of AgI existing stably at room temperature.

Pushing TC to 27.5 K in a heavy atom radical ferromagnet.

In the solid state the iodo-substituted bisdiselenazolyl radical 1c orders as a ferromagnet with TC = 10.5 K. With the application of pressure TC rises rapidly, reaching a value of 27.5 K at 2.4 GPa. The accompanying structural and magnetic changes have been examined by high resolution powder X-ray diffraction and by DFT calculations of magnetic exchange interactions.