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The exploration of superconductors in metastable phases by manipulating crystal structures through high-pressure techniques has attracted significant interest in materials science to achieve a high critical temperature ($T_c$). In this study, we report an emergence of novel superconductivity in a metastable phase of Th$_3$P$_4$-type cubic In$_{3-x}$S$_4$ with remarkably high $T_c$ at 20 K under 45 GPa by using an originally designed diamond anvil cell equipped with boron-doped diamond electrodes, which can perform a high-pressure synthesis and an in-situ electrical transport measurement simultaneously. In-situ structural analysis indicates that the In$_{3-x}$S$_4$ appears partially above 40 GPa without heating. The high-pressure annealing treatment induces complete transformation to the Th$_3$P$_4$-type structure, and the defected concentration of x in In$_{3-x}$S$_4$ decreases with increasing annealing temperature. The $T_c$ in In$_{3-x}$S$_4$ is maximized at x = 0 and approaches 20 K. Electronic band calculations show that the high density of states composed of sulfur and indium bands are located at the conduction band bottom near Fermi energy. The record high $T_c$ in In$_{3-x}$S$_4$ among superconducting sulfides accelerates the further exploration of high $T_c$ materials within the Th$_3$P$_4$-type cubic family by using flexibility in crystal structure.

High-pressure techniques open exploration of functional materials in broad research fields. An established diamond anvil cell with a boron-doped diamond heater and transport measurement terminals has performed the high-pressure synthesis of a cubic Sn$_{3}$S$_{4}$ superconductor. X-ray diffraction and Raman spectroscopy reveal that the Sn$_{3}$S$_{4}$ phase is stable in the pressure range of P>5 GPa in a decompression process. Transport measurement terminals in the diamond anvil cell detect a metallic nature and superconductivity in the synthesized Sn$_{3}$S$_{4}$ with a maximum onset transition temperature of 13.3 K at 5.6 GPa. The observed pressure-T$_{c}$ relationship is consistent with that from the first-principles calculation. The observation of superconductivity in Sn$_{3}$S$_{4}$ opens further materials exploration under high temperature and pressure conditions.

Temperature and pressure are essential parameters in the synthesis, evaluation, and application of functional materials. This study proposes the addition of a heating function to a high-pressure diamond anvil cell (DAC) with in-situ measurement probes. The proposed DAC allows for simultaneous control of temperature and pressure within the sample space and can be used to synthesize functional materials under extreme conditions. The various components, namely the heater, thermometer, and measurement probes, were fabricated with a boron-doped diamond epitaxial film and could be used repeatedly. The developed DAC was used to successfully conduct the high-pressure annealing of La(O,F)BiS$_{2}$ single crystal and the high-pressure synthesis of EuFBiS$_{2}$ superconductors. The proposed technique shows promise for further exploration of superconductors to broaden the research field.

The martensitic transformation is a fundamental physical phenomenon at the origin of important industrial applications. However, the underlying microscopic mechanism, which is of critical importance to explain the outstanding mechanical properties of martensitic materials, is still not fully understood. This is because for most martensitic materials the transformation is a fast process that makes in situ studies extremely challenging. Noble solids krypton and xenon undergo a progressive pressure induced fcc to hcp martensitic transition with a very wide coexistence domain. Here, we took advantage of this unique feature to study the detailed mechanism of the transformation by employing in situ X-ray diffraction and absorption. We evidenced a four stages mechanism where the lattice mismatch between the fcc and hcp forms plays a key role in the generation of strain. We also determined precisely the effect of the transformation on the compression behavior of these materials., Comment: Main file: 31 pages, 9 figure

Layered ternary transition-metal chalcogenides have been focused as a vein of exploration for superconductors. In this study, TiGeTe$_{6}$ single crystals were synthesized and characterized by structural and valence state analyses and electrical transport measurements. The transport properties were measured under various pressures up to 71 GPa. The activation energy gets smaller as the applied pressure increases, and a signature of a pressure-induced metallization was observed under around 8.4 GPa. Under 13 GPa, pressure-induced superconductivity was discovered in this compound for the first time, with successive drops at 3 K and 6 K in the resistance, indicating the presence of multiple superconducting transitions. The superconducting transition temperature kept increasing as we further applied the pressure to the TiGeTe$_{6}$ single crystal in the performed pressure range, reaching as high as 8.1 K under 71 GPa.

Layered transition-metal chalcogenides (Zr,Hf)GeTe$_{4}$ were screened out from database of Atomwork as a candidate for pressure-induced superconductivity due to their narrow band gap and high density of state near the Fermi level. The (Zr,Hf)GeTe$_{4}$ samples were synthesized in single crystal and then the compositional ratio, crystal structures, and valence states were investigated via energy dispersive spectrometry, single crystal X-ray diffraction, and X-ray photoelectron spectroscopy, respectively. The pressure-induced superconductivity in both crystals were first time reported by using a diamond anvil cell with a boron-doped diamond electrode and an undoped diamond insulating layer. The maximum superconducting transition temperatures of ZrGeTe$_{4}$ and HfGeTe$_{4}$ were 6.5 K under 57 GPa and 6.6 K under 60 GPa, respectively.

A diamond anvil cell (DAC) which can generate extremely high pressure of multi-megabar is promising tool to develop a further physics such a high-transition temperature superconductivity. However, electrical transport measurements, which is one of the most important properties of such functional materials, using the DAC is quite difficult because the sample space is very small and a deformation of electrodes under extreme condition. In this study, we fabricated a boron-doped diamond micro-electrode and an undoped diamond insulation on a beveled culet surface of the diamond anvil. By using the developed DAC, we demonstrated the electrical transport measurements for sulfur hydride H$_2$S which known as a pressure-induced high-transition temperature superconducting H$_3$S at high pressure. The measurements were successfully conducted under high pressure up to 192 GPa, and then a multi-step superconducting transition composed from pure sulfur and some kinds of surfer hydrides, which is possible HS$_2$, was observed with zero resistance.

We have studied the amorphization process of SnI4 up to 26.8GPa with unprecedented experimental details by combining Sn and I K edge X-ray absorption spectroscopy and powder X-ray diffraction. Standards and reverse Monte Carlo extended X-ray absorption fine structure (EXAFS) refinements confirm that the SnI4 tetrahedron is a fundamental structural unit that is preserved through the crystalline phase-I to crystalline phase-II transition about 7 to 10GPa and then in the amorphous phase that appears above 20GPa. Up to now unexploited Iodine EXAFS reveals to be extremely informative and confirms the formation of iodine iodine short bonds close to 2.85{\AA} in the amorphous phase at 26.8 GPa. A coordination number increase of Sn in the crystalline phase-II appears to be excluded, while the deformation of the tetrahedral units proceeds through a flattening that keeps the average I-Sn-I angle close to 109.5{\deg}. Moreover, we put in evidence the impact of pressure on the Sn near edge structure under competing geometrical and electronic effects.

Metallization and dissociation are key transformations in diatomic molecules at high densities particularly significant for modeling giant planets. Using X-ray absorption spectroscopy and atomistic modeling, we demonstrate that in halogens, the formation of a \textit{connected} molecular structure takes place at pressures well below metallization. Here we show that the iodine diatomic molecule first elongates of $\sim$0.007 \AA~up to a critical pressure of $P_c$ $\backsim$7~GPa developing bonds between molecules. Then its length continuously decreases with pressure up to 15-20~GPa. Universal trends in halogens are shown and allow to predict for chlorine a pressure of 42$\pm$8~GPa for molecular bond-length reversal. Our findings tackle the molecule invariability paradigm in diatomic molecular phases at high pressures and may be generalized to other abundant diatomic molecules in the universe, including hydrogen., Comment: 6 pages, 4 figures

Polycrystalline samples of layered pnictogen diselenide NdO0.8F0.2Sb1-xBixSe2 (x = 0 to 0.8) were successfully synthesized by solid-state reactions. Electrical resistivity in the synthesized samples was systematically decreased with an increase in Bi content x. Crystal structure analysis using synchrotron X-ray diffraction suggests that insulator to metal transition upon Bi doping correlates with anomalous change in c-axis length and/or corrugation in conducting layer. The emergence of superconductivity under high pressure is demonstrated using diamond anvil cell (DAC) with boron-doped diamond electrodes, for x = 0.3 and 0.7 as the representative samples. For Sb-rich one (x = 0.3), we observed a superconducting transition with Tconset = 5.3 K at 50 GPa, which is the first-ever report of the superconductivity in layered SbCh2-based (Ch: chalcogen) compounds. The Tconset of x = 0.3 increased with increasing pressure and reached 7.9 K at 70.8 GPa, followed by the gradual decrease in Tc up to 90 GPa. For Bi-rich one (x = 0.7), a superconducting transition with Tconset = 5.9 K was observed at 43.5 GPa, which is the almost comparable to that of x = 0.3; besides, upper critical field (Hc2) is evaluated to be ~10 T for x = 0.7, which is higher than that of x = 0.3 (Hc2 = 6.7 T at 50 GPa).

Candidates compounds for new thermoelectric and superconducting materials, which have narrow band gap and flat bands near band edges, were exhaustively searched by a high-throughput first-principles calculation from an inorganic materials database named AtomWork. We focused on AgIn$_{5}$Se$_{8}$ which has high density of state near the Fermi level. AgIn$_{5}$Se$_{8}$ was successfully synthesized as single crystals using a melt and slow cooling method. The single-crystal X-ray diffraction analysis revealed the obtained crystal is high quality without deficiencies. The valence states in AgIn$_{5}$Se$_{8}$ were determined to be Ag1+, In3+ and Se2- in accordance with a formal charge by the core level X-ray photoelectron spectroscopy analysis. The electrical resistance was evaluated under high pressure using a diamond anvil cell with boron-doped diamond electrodes. Although the sample was insulator with a resistance of above 40 M{\Omega} at ambient pressure, the resistance markedly decreased with increase of the pressure, and a pressure-induced superconducting transition was discovered at 3.4 K under 52.5 GPa. The transition temperature increased up to 3.7 K under further pressure of 74.0 GPa.

Tin sulfide (SnS) was successfully synthesized in single crystals by a melt and slow-cooling method. The obtained sample was characterized by an X-ray diffraction, an energy dispersive spectrometry, and an X-ray photoelectron spectroscopy. Electrical transport properties in SnS were investigated under high pressure using a diamond anvil cell with boron-doped metallic diamond electrodes and undoped diamond insulating layer. We successfully observed an insulator to metal transition from 12.5 GPa and pressure-induced superconductivity at 5.8 K under 47.8 GPa as predicted by a theoretical calculation.

Transport properties of Ce$_{0.85}$F0.15SbS$_{2}$ and undoped CeOSbS$_{2}$ under high pressure were investigated experimentally and theoretically. Electrical resistivity measurements of the Ce$_{0.85}$F0.15SbS$_{2}$ single crystals were performed under various high pressures using a diamond anvil cell with boron-doped diamond electrodes. The samples showed the insulator to metal transition by applying high pressure up to 30-40 GPa. On the other hand, the undoped CeOSbS$_{2}$ showed almost same transport property with the F-doped sample under high pressure. The valence state analysis using X-ray photoelectron spectroscopy revealed a simple valence state of Ce3+ in Ce$_{0.85}$F0.15SbS$_{2}$ and mixed valence state between Ce3+ and Ce4+ in undoped CeOSbS$_{2}$. The valence fluctuation in Ce carried out the comparable transport nature in the both samples. A band calculation suggests that the undoped CeOSbS$_{2}$ could be metallic under high pressure of 30 GPa in accordance with the experimental results. A superior thermoelectric property of power factor in CeOSbS$_{2}$ was estimated under high pressure around 20 GPa in comparison with that of ambient pressure.

Candidates compounds for new thermoelectric and superconducting materials, which have narrow band gap and flat bands near band edges, were exhaustively searched by the high-throughput first-principles calculation from an inorganic materials database named AtomWork. We focused on PbBi$_2$Te$_4$ which has the similar electronic band structure and the same crystal structure with those of a pressure-induced superconductor SnBi2Se4 explored by the same data-driven approach. The PbBi$_2$Te$_4$ was successfully synthesized as single crystals using a melt and slow cooling method. The core level X-ray photoelectron spectroscopy analysis revealed Pb2+, Bi3+ and Te2- valence states in PbBi$_2$Te$_4$. The thermoelectric properties of the PbBi$_2$Te$_4$ sample were measured at ambient pressure and the electrical resistivity was also evaluated under high pressure using a diamond anvil cell with boron-doped diamond electrodes. The resistivity decreased with increase of the pressure, and two pressure-induced superconducting transitions were discovered at 3.4 K under 13.3 GPa and at 8.4 K under 21.7 GPa. The data-driven approach shows promising power to accelerate the discovery of new thermoelectric and superconducting materials.

Sulfur-doped SnSe single crystal was successfully synthesized using a melt and slow-cooling method. The chemical composition and valence state of the obtained sample were analyzed by X-ray photoelectron spectroscopy. The pressure range of a diamond anvil cell with boron-doped diamond electrodes was upgraded to 104 GPa using nano-polycrystalline diamond anvil to investigate a pressure effect for the sample. Electrical resistivity measurements of sulfur-doped SnSe single crystal showed the insulator-metal-superconductor transition by applying high pressure up to 75.9 GPa.

Diamond anvil cell using boron-doped metallic diamond electrodes covered with undoped diamond insulating layer have been developed for electrical transport measurements under high pressure. These designed diamonds were grown on a bottom diamond anvil via a nanofabrication process combining microwave plasma-assisted chemical vapor deposition and electron beam lithography. The resistance measurements of high quality FeSe superconducting single crystal under high pressure were successfully demonstrated by just putting the sample and gasket on the bottom diamond anvil directly. The superconducting transition temperature of FeSe single crystal was enhanced up to 43 K by applying uniaxial-like pressure.

Pressure induced structural modifications in vitreous Ge$_{x}$Se$_{100-x}$ (where 10 $\leq$ x $\leq$ 25)are investigated using X-ray absorption spectroscopy (XAS) along with supplementary X-ray diffraction (XRD) experiments and ab initio molecular dynamics (AIMD) simulations. Universal changes in distances and angle distributions are observed when scaled to reduced densities. All compositions are observed to remain amorphous under pressure values up to 42 GPa. The Ge-Se interatomic distances extracted from XAS data show a two-step response to the applied pressure; a gradual decrease followed by an increase at around 15-20 GPa, depending on the composition. This increase is attributed to the metallization event that can be traced with the red shift in Ge K edge energy which is also identified by the principal peak position of the structure factor. The densification mechanisms are studied in details by means of AIMD simulations and compared to the experimental results. The evolution of bond angle distributions, interatomic distances and coordination numbers are examined and lead to similar pressure-induced structural changes for any composition.

The pressure evolution of the local structure of Fe2O3 hematite has been determined for the first time by extended x-ray absorption fine structure up to 79 GPa. The comparison to the different high-pressure forms proposed in the literature suggests that the orthorhombic structure with space group Aba2 is the most probable. The crossover from Fe high-spin to low-spin states with pressure increase has been monitored from the pre-edge region of the Fe K-edge absorption spectra. The "simultaneous" comparison with the local structural changes allows us to definitively conclude that it is the electronic transition that drives the structural transition and not viceversa.

The Vickers hardness of polycrystalline {\gamma}-B was measured using a diamond indentation method. The elastic properties of polycrystalline {\gamma}-B (B=213.9 GPa, G=227.2 GPa, and E=503.3 GPa) were determined using ultrasonic measurement at ambient condition. Under the loading force up to 20 N, our test gave an average Vickers hardness in the asymptotic-hardness region of 30.3 GPa. The average fracture toughness was measured as 4.1MPa m1/2. Additionally, We also measured the hardness and elastic properties of polycrystalline {\beta}-B and PcBN for comparison. The hardness and elastic properties for polycrystalline {\gamma}-B was found to be very close to that of PcBN. Our results suggest that the polycrystalline {\gamma}-B could be a superhard polycrystalline material for industrial applications., Comment: 16 pages

The phase relations in boron have been investigated at high pressure and high temperature using a multianvil apparatus, and the quenched sample has been analyzed by x-ray diffraction, Raman spectra and transmission electron microscopy. We demonstrate that {\gamma}-B28 can be synthesized over a wide P-T range, and T-B50 is obtained at higher temperatures and similar pressures. The phase boundary of the {\beta}-B106, {\gamma}-B28 and T-B50 is determined at pressures between 7 and 18 GPa and the temperatures of 500-2200 {\deg}C. The results suggest that T-B50 might be an intermediate phase-metastable, formed for kinetic reasons (Ostwald rule) on the way from {\beta}-B106 to T-192 and {\gamma}-B28 to T-192., Comment: 14 pages, 4 figures