Employing particle swarm optimization (PSO) combined with first-principles calculations, we systemically studied high-pressure behaviors of hard CrB4. Our predictions reveal a distinct structural evolution under pressure for CrB4 despite having the same initial structure as FeB4. CrB4 is found to adopt a new P2/m structure above 196 GPa, another Pm structure at a pressure range of 261-294 GPa and then a Pmma structure beyond 294 GPa. Instead of puckering boron sheets in the initial structure, the high-pressure phases have planar boron sheets with different motifs upon compression. Comparatively, FeB4 prefers an I4(1)/acd structure over 48 GPa with tetrahedron B-4 units and a P2(1)3 structure above 231 GPa having equilateral triangle B-3 units. Significantly, CrB4 exhibits persistent metallic behavior in contrast with the semiconducting features of FeB4 upon compression. The varied pressure response of hard tetraborides studied here is of importance for understanding boron-rich compounds and designing new materials with superlative properties.

First-principles calculations were performed to understand the structural stability, synthesis routes, mechanical and electronic properties of diverse ruthenium nitrides. RuN with a new I-4m2 symmetry stabilized by pressure is found to be energetically preferred over the experimental NaCl-type and ZnS-type ones. The Pnnm-RuN2 is found to be stable above 1.1 GPa, in agreement with the experimental results. Specifically, new stoichiometries like RuN3 and RuN4 are proposed firstly to be thermodynamically stable, and the dynamical and mechanical stabilities of the newly predicted structures have been verified by checking their phonon spectra and elastic constants. A phase transition from P4/mmm-RuN4 to C2/c-RuN4 is also uncovered at 23.0 GPa. Drawn from bonding and band structure analysis, P4/mmm-RuN4 exhibits semi-metal-like behavior and becomes a semiconductor for the high-pressure C2/c-RuN4 phase. Meanwhile the P2(1)/c-RuN3 shows metallic feature. Highly directional covalent N-N and Ru-N bonds are formed and dominating in N-enriched Ru nitrides, making them promising hard materials.

An organic-inorganic halide CH3NH3SnI3 perovskite with significantly improved structural stability is obtained via pressure-induced amorphization and recrystallization. In situ high-pressure resistance measurements reveal an increased electrical conductivity by 300% in the pressure-treated perovskite. Photocurrent measurements also reveal a substantial enhancement in visible-light responsiveness. The mechanism under lying the enhanced properties is shown to be associated with the pressure-induced structural modification.

Strong spin orbital interaction (SOI) can induce unique quantum phenomena such as topological insulators, the Rashba effect, or p-wave superconductivity. Combining these three quantum phenomena into a single compound has important scientific implications. Here we report experimental observations of consecutive quantum phase transitions from a Rashba type topological trivial phase to topological insulator state then further proceeding to superconductivity in a SOI compound BiTeI tuned via pressures. The electrical resistivity measurement with V shape change signals the transition from a Rashba type topological trivial to a topological insulator phase at 2 GPa, which is caused by an energy gap close then reopen with band inverse. Superconducting transition appears at 8 GPa with a critical temperature T-C of 5.3 K. Structure refinements indicate that the consecutive phase transitions are correlated to the changes in the Bi-Te bond and bond angle as function of pressures. The Hall Effect measurements reveal an intimate relationship between superconductivity and the unusual change in carrier density that points to possible unconventional superconductivity.

We utilized the pair distribution function method to characterize the pressure-induced polyamorphic transition in Ce60Al20Cu20 and Ce55Al45 metallic glass at room temperature. Using synchrotron high-energy x-ray diffraction we collected scattering information from a large Q-space coverage, which in turn gave a high resolution g(r) that provided accurate local structure information. We observed a sudden change in compressibility and the nearest neighbor distance at 3.50-6.32 GPa for Ce60Al20Cu20 and 2.20-6.89 GPa for Ce55Al45. The origin of the volume collapse seemed to be pressure-induced qualitative changes in bond shortening that corresponded to different coordination spheres. The polyamorphic transitions in these two systems from low-density glass (LDG) to high-density glass (HDG) are associated with local atomic rearrangements. (C) 2016 Elsevier B.V. All rights reserved.

Boron carbide (B4C) is one of the hardest materials known to date. The extreme hardness of B4C arises from architecturally efficient B-12 or B11C icosahedrons and strong inter-icosahedral B-C bonding. As an excellent material for use in ballistic armor, the mechanic limit of B4C and possible phase transitions under extreme stress conditions are of great interest. Here we systematically explored the post-icosahedral solid structures of B4C under high pressure, using an unbiased structure search method. A new structure composed of extended framework of B and zigzag chains of C is predicted to be stable above 96 GPa. The new structure was predicted to have a high Vickers hardness of 55 GPa and simultaneously to retain a metallic ground state. The exceptional mechanical properties found in this structure are attributed to strong sp(3) covalent network formed under extreme pressure conditions. The predicted structure represents a new type of superhard boron carbides that form under high pressure without the presence of boron icosahedrons, which encourages experimental exploration in this direction.

Controlled nanotwinning is an effective way to enhance the mechanical properties of materials. Recent discovery of nanotwinned diamond converted from carbon nano-onions with high-density defects reveals that the presence of nanotwinned structures can increase the hardness of the product to exceed that of natural diamond by a surprisingly large margin. To understand the mechanism of nanotwinning, the microscopic transformation pathway from carbon nano-onions to nanotwinned diamond was investigated in the present study. We carried out a direct high-pressure high-temperature synthesis of nanotwinned diamond from onion carbon without high-density defects. The obtained nanotwinned diamond possesses an exceptionally high Vickers hardness of 215 GPa at 4.9 N. The transformation path was analyzed using aberration-corrected transmission electron microscopy (TEM) which suggests a martensitic process strongly influenced by the pressure-temperature conditions. Specifically, the appearance of {111} nanotwinned structure and stacking faults was determined by the characteristics of the onion shells, while the accumulation of the stress due to the sliding of the shells cause the crystal to re-align along the shear direction. These findings not only clarify the direct transformation mechanism from onion-like precursors to nanotwinned diamond, but also have broad implications for further exploration of new materials with exceptional properties. (C) 2017 Elsevier Ltd. All rights reserved.

While the layered 122 iron arsenide superconductors are highly anisotropic, unconventional, and exhibit several forms of electronic orders that coexist or compete with superconductivity in different regions of their phase diagrams, we find in the absence of iron in the structure that the superconducting characteristics of the end member BaPd2As2 are surprisingly conventional. Here we report on complementary measurements of specific heat, magnetic susceptibility, resistivity measurements, Andreev spectroscopy, and synchrotron high pressure x-ray diffraction measurements supplemented with theoretical calculations for BaPd2As2. Its superconducting properties are completely isotropic as demonstrated by the critical fields, which do not depend on the direction of the applied field. Under the application of high pressure, T-c is linearly suppressed, which is the typical behavior of classical phonon-mediated superconductors with some additional effect of a pressure-induced decrease in the electronic density of states and the electron-phonon coupling parameters. Structural changes in the layered BaPd2As2 have been studied by means of angle-dispersive diffraction in a diamond-anvil cell. At 12 GPa and 24.2 GPa we observed pressure induced lattice distortions manifesting as the discontinuity and, hence discontinuity in the Birch-Murnaghan equation of state. The bulk modulus is B-0 = 40(6) GPa below 12 GPa and B-0 = 142(3) GPa below 27.2 GPa.

Amorphous sulfur was prepared by rapid compression of liquid sulfur at temperatures above the lambda-transition for to preserve the high-temperature liquid structure. We conducted synchrotron high-energy X-ray diffraction and Raman spectroscopyto diagnose the structural evolution of amorphous sulfur from room temperature to post-lambda-transition temperature. Discontinuous changes of the first and second peaks in atomic pair-distribution-function, g(r), were observed during the transition from amorphous to liquid sulfur. The average first-neighbor coordination numbers showed an abrupt drop from 1.92 to 1.81. The evolution of the chain length clearly shows that the transition was accompanied by polymeric chains breaking. Furthermore, a re-entry of the lambda-transition structure was involved in the heating process. The amorphous sulfur, which inherits the post-lambda-transition structure from its parent melts, transformed to the pre-lambda-transition liquid structure at around 391 K. Upon further heating, the pre-lambda-transition liquid transformed to a post-lambda-transition s tructure through the well-known lambda-transition process. This discovery offers a new perspective on amorphous sulfur's structural inheritance from its parent liquid and has implications for understanding the structure, evolution and properties of amorphous sulfur and its liquids.

Considerable excitement was generated by the observation of large and linear positive magnetoresistance in nonmagnetic silver chalcogenides. Renewed interest in these materials was kindled by the discovery that Ag-2 Te in particular is a topological insulator with gapless linear Dirac-type surface states. High-pressure x-ray-diffraction studies, combined with first-principles electronic structure calculations, have identified three phase transitions as the pressure is increased: an isostructural transition identified with an electronic topological transition followed by two structural phase transitions. These recent studies were carried out on nominally stoichiometric Ag2Te. For the present work we have prepared single-phase self-doped Ag2-delta Te samples with a well-characterized silver deficit (delta = 2.0 x10(-4)) for structural and electrical transport measurements over extended ranges of pressure (0-43 GPa), temperature (2-300 K), and magnetic field (0-9 T). The temperature dependence of the resistivity exhibits anomalous behavior at 2.3 GPa, slightly above the isostructural transition, which we postulate is due to Fermi surface reconstruction associated with a charge density wave (CDW) phase. The anomaly is enhanced by the application of a 9-T magnetic field and shifted to higher temperature, implying that the electronic Zeeman energy is sufficient to alter the gapping of the Fermi surface. A peak in the pressure dependence of the resistivity and a sudden drop in the pressure dependence of the mobility, occurring at 2.3 GPa, provide additional evidence for a CDW phase at pressures slightly above the isostructural transition.