Pressure-Induced Collapse Transition in BaTi2Pn2O (Pn = As, Sb) with an Unusual Pn-Pn Bond Elongation.

Making and breaking bonds in a solid-state compound greatly influences physical properties. A well-known playground for such bonding manipulation is the ThCr2Si2-type structure AT2X2, allowing a collapse transition where a X-X dimer forms by a chemical substitution or external stimuli. Here, we report a pressure-induced collapse transition in the structurally related BaTi2Pn2O (Pn = As, Sb) at a transition pressure Pc of ∼15 GPa. The Pn-Pn bond formation is related with Pn-p band filling, which is controlled by charge transfer from the Ti-3d band. At Pc, the Sb-Sb distance in BaTi2Sb2O shrinks due to bond formation, but interestingly, the Sb-Sb expands with increasing pressure above Pc. This expansion, which was not reported in ThCr2Si2-type compounds, may arise from heteroleptic coordination geometry around titanium, where a compression of the Ti-O bond plays a role. Electrical resistivity measurements of BaTi2Sb2O up to 55 GPa revealed an increasing trend of the superconducting transition temperature with pressure. This study presents structure motifs that allow flexible bonding manipulation and property control with heteroleptic coordination geometry.

Impact of Lanthanoid Substitution on the Structural and Physical Properties of an Infinite-Layer Iron Oxide.

The effect of lanthanoid (Ln = Nd, Sm, Ho) substitution on the structural and physical properties of the infinite-layer iron oxide SrFeO2 was investigated by X-ray diffraction (XRD) at ambient and high pressure, neutron diffraction, and 57Fe Mössbauer spectroscopy. Ln for Sr substituted samples up to ∼30% were synthesized by topochemical reduction using CaH2. While the introduction of the smaller Ln3+ ion reduces the a axis as expected, we found an unusual expansion of the c axis as well as the volume. Rietveld refinements along with pair distribution function analysis revealed the incorporation of oxygen atoms between FeO2 layers with a charge-compensated composition of (Sr1-xLnx)FeO2+x/2, which accounts for the failed electron doping to the FeO2 layer. The incorporated partial apical oxygen or the pyramidal coordination induces incoherent buckling of the FeO2 sheet, leading to a significant reduction of the Néel temperature. High-pressure XRD experiments for (Sr0.75Ho0.25)FeO2.125 suggest a possible stabilization of an intermediate spin state in comparison with SrFeO2, revealing a certain contribution of the in-plane Fe-O distance to the pressure-induced transition.

Phase changes of filled ice Ih methane hydrate under low temperature and high pressure.

Low-temperature and high-pressure experiments were performed with filled ice Ih structure of methane hydrate under 2.0-77.0 GPa and 30-300 K using diamond anvil cells and a helium-refrigeration cryostat. In situ X-ray diffractometry revealed distinct changes in the compressibility of the axial ratios of the host framework with pressure. Raman spectroscopy showed a split in the C-H vibration modes of the guest methane molecules, which was previously explained by the orientational ordering of the guest molecules. The pressure and temperature conditions at the split of the vibration modes agreed well with those of the compressibility change. The results indicate the following: (i) the orientational ordering of the guest methane molecules from an orientationally disordered state occurred at high pressures and low temperatures; and (ii) this guest ordering led to anisotropic contraction in the host framework. Such guest orientational ordering and subsequent anisotropic contraction of the host framework were similar to that reported previously for filled ice Ic hydrogen hydrate. Since phases with different guest-ordering manners were regarded as different phases, existing regions of the guest disordered-phase and the guest ordered-phase were roughly estimated by the X-ray study. In addition, above the pressure of the guest-ordered phase, another high-pressure phase developed in the low-temperature region. The deuterated-water host samples were also examined, and the influence of isotopic effects on guest ordering and phase transformation was observed.

Structural changes of filled ice Ic hydrogen hydrate under low temperatures and high pressures from 5 to 50 GPa.

Low-temperature and high-pressure experiments were performed on the filled ice Ic structure of hydrogen hydrate at previously unexplored conditions of 5-50 GPa and 30-300 K using diamond anvil cells and a helium-refrigeration cryostat. In situ x-ray diffractometry revealed that the cubic filled ice Ic structure transformed to tetragonal at low temperatures and high pressures; the axis ratio of the tetragonal phase changed depending on the pressure and temperature. These results were consistent with theoretical predictions performed via first principle calculations. The tetragonal phase was determined to be stable above 20 GPa at 300 K, above 15 GPa at 200 K, and above 10 GPa at 100 K. Further changes in the lattice parameters were observed from about 45-50 GPa throughout the temperature region examined, which suggests the transformation to another high-pressure phase above 50 GPa. In our previous x-ray study that was performed up to 80 GPa at room temperature, a similar transformation was observed above 50 GPa. In this study, the observed change in the lattice parameters corresponds to the beginning of that transformation. The reasons for the transformation to the tetragonal structure are briefly discussed: the tetragonal structure might be induced due to changes in the vibrational or rotational modes of the hydrogen molecules under low temperature and high pressure.

Pressure-induced structural, magnetic, and transport transitions in the two-legged ladder Sr3Fe2O5.

The layered compound SrFeO(2) with an FeO(4) square-planar motif exhibits an unprecedented pressure-induced spin state transition (S = 2 to 1), together with an insulator-to-metal (I-M) and an antiferromagnetic-to-ferromagnetic (AFM-FM) transition. In this work, we have studied the pressure effect on the structural, magnetic, and transport properties of the structurally related two-legged spin ladder Sr(3)Fe(2)O(5). When pressure was applied, this material first exhibited a structural transition from Immm to Ammm at P(s) = 30 ± 2 GPa. This transition involves a phase shift of the ladder blocks from (1/2,1/2,1/2) to (0,1/2,1/2), by which a rock-salt type SrO block with a 7-fold coordination around Sr changes into a CsCl-type block with 8-fold coordination, allowing a significant reduction of volume. However, the S = 2 antiferromagnetic state stays the same. Next, a spin state transition from S = 2 to S = 1, along with an AFM-FM transition, was observed at P(c) = 34 ± 2 GPa, similar to that of SrFeO(2). A sign of an I-M transition was also observed at pressure around P(c). These results suggest a generality of the spin state transition in square planar coordinated S = 2 irons of n-legged ladder series Sr(n+1)Fe(n)O(2n+1) (n = 1, 2, 3, ...). It appears that the structural transition independently occurs without respect to other transitions. The necessary conditions for a structural transition of this type and possible candidate materials are discussed.

Compression behaviors of binary skutterudite CoP3 in noble gases up to 40 GPa at room temperature.

The binary skutterudite CoP(3) has a large void at the body-centered site of each cubic unit cell and is, therefore, called a nonfilled skutterudite. We investigated its room-temperature compression behavior up to 40.4 GPa in helium and argon using a diamond-anvil cell. High-pressure in situ X-ray diffraction and Raman scattering measurements found no phase transition and a stable cubic structure up to the maximum pressure in both media. A fitting of the present pressure-volume data to the third-order Birch-Murnaghan equation of state yields a zero-pressure bulk modulus K(0) of 147(3) GPa [pressure derivative K(0)' of 4.4(2)] and 171(5) GPa [where K(0)' = 4.2(4)] in helium and argon, respectively. The Grüneisen parameter was determined to be 1.4 from the Raman scattering measurements. Thus, CoP(3) is stiffer than other binary skutterudites and could therefore be used as a host cage to accommodate large atoms under high pressure without structural collapse.

B1-to-B2 structural transitions in rock salt intergrowth structures.

The rock salt (B1) structure of binary oxides or chalcogenides transforms to the CsCl (B2) structure under high pressure, with critical pressures P(s) depending on the cation to anion size ratio (R(c)/R(a)). We investigated structural changes of A(2)MO(3) (A = Sr, Ca; M = Cu, Pd) comprising alternate 7-fold B1 AO blocks and corner-shared MO(2) square-planar chains under pressure. All of the examined compounds exhibit a structural transition at P(s) = 29-41 GPa involving a change in the A-site geometry to an 8-fold B2 coordination. This observation demonstrates, together with the high pressure study on the structurally related Sr(3)Fe(2)O(5), that the B1-to-B2 transition generally occurs in these intergrowth structures. An empirical relation of P(s) and the R(c)/R(a) ratio for the binary system holds well for the intergrowth structure also, which means that P(s) is predominantly determined by the rock salt blocks. However, a large deviation from the relation is found in LaSrNiO(3.4), where oxygen atoms partially occupy the apical site of the MO(4) square plane. We predict furthermore the occurrence of the same structural transition for Ruddlesden-Popper-type layered perovskite oxides (AO)(AMO(3))(n), under higher pressures. For investigating the effect on the physical properties, an electrical resistivity of Sr(2)CuO(3) is studied.

Phase changes of CO2 hydrate under high pressure and low temperature.

High pressure and low temperature experiments with CO(2) hydrate were performed using diamond anvil cells and a helium-refrigeration cryostat in the pressure and temperature range of 0.2-3.0 GPa and 280-80 K, respectively. In situ x-ray diffractometry revealed that the phase boundary between CO(2) hydrate and water+CO(2) extended below the 280 K reported previously, toward a higher pressure and low temperature region. The results also showed the existence of a new high pressure phase above approximately 0.6 GPa and below 1.0 GPa at which the hydrate decomposed to dry ice and ice VI. In addition, in the lower temperature region of structure I, a small and abrupt lattice expansion was observed at approximately 210 K with decreasing temperature under fixed pressures. The expansion was accompanied by a release of water content from the sI structure as ice Ih, which indicates an increased cage occupancy. A similar lattice expansion was also described in another clathrate, SiO(2) clathrate, under high pressure. Such expansion with increasing cage occupancy might be a common manner to stabilize the clathrate structures under high pressure and low temperature.

Discovery of ferromagnetic-half-metal-to-insulator transition in K2Cr8O16.

The hollandite chromium oxide K2Cr8O16 has been synthesized in both powder and single-crystal form under high pressure. Combining electrical resistivity, magnetic susceptibility, and x-ray diffraction, we found that K2Cr8O16 is a ferromagnetic metal (or half-metal) with T(C)=180 K and shows a transition to an insulator at 95 K without any apparent structural change but retaining ferromagnetism. K2Cr8O16 is quite unique in three aspects: It has a rare mixed valence of Cr3+ and Cr4+; it has a metal (or half-metal)-to-insulator transition in a ferromagnetic state; and the resulting low-temperature phase is a rare case of a ferromagnetic insulator. This discovery could open a new frontier on the relation of magnetism and conducting properties in strongly correlated electron systems.

Structural changes and preferential cage occupancy of ethane hydrate and methane-ethane mixed gas hydrate under very high pressure.

High-pressure experiments of ethane hydrate and methane-ethane mixed hydrates with five compositions were performed using a diamond anvil cell in a pressure range of 0.1-2.8 GPa at room temperature. X-ray diffractometry and Raman spectroscopy showed structural changes as follows. The initial structure, structure I (sI), of ethane hydrate was retained up to 2.1 GPa without any structural change. For the mixed hydrates, sI was widely distributed throughout the region examined except for the methane-rich and lower pressure regions. For the ethane-rich and intermediate composition regions (73 mol % ethane sample and 53% sample), sI was maintained up to 2.1 GPa. With increasing methane component (34% and 30% samples), sI existed at pressures from 0.1 to about 1.0 GPa. Hexagonal structure (sH) appeared in addition to sI at 1.3 GPa for the 34% sample and at 1.1 GPa for the 30% sample. By further increasing the methane component (22% sample), structure II (sII) existed solely up to 0.3 GPa. From 0.3 to 0.6 GPa, sII and sI coexisted, and from 0.6 to 1.0 GPa only sI existed. At 1.2 GPa sH appeared, and sH and sI coexisted up to 2.1 GPa. Above 2.1 GPa, ethane hydrate and all of the mixed hydrates decomposed into ice VI and ethane fluid or methane-ethane fluid, respectively. The Raman study revealed that occupation of the small cages by ethane molecules occurred above 0.1 GPa in ethane hydrate and continued up to decomposition at 2.1 GPa, although it is thought that ethane molecules are contained only in the large cage.

Structural changes of filled ice Ic structure for hydrogen hydrate under high pressure.

High-pressure experiments of hydrogen hydrate, filled ice Ic structure, were performed using a diamond-anvil cell in the pressure range of 0.1-80.3 GPa at room temperature. In situ x-ray diffractometry (XRD) revealed that structural changes took place at approximately 35-40 and 55-60 GPa, and that the high-pressure phase of hydrogen hydrate survived up to at least 80.3 GPa. Raman spectroscopy showed that the changes in vibrational mode for the hydrogen molecules in hydrogen hydrate occurred at around 40 and 60 GPa, and these results were consistent with those of the XRD. At about 40 GPa, the intermolecular distance of host water molecules consisting the framework attained the critical distance of symmetrization of the hydrogen bond for water molecules, which suggested that symmetrization of the hydrogen bond occurred at around 40 GPa. The symmetrization might introduce some structural change in the filled ice Ic structure. In addition, the existence of the high-pressure phase above 55-60 GPa implies that a denser structure than that of filled ice Ic may exist in hydrogen hydrate.

Hydrogenation of iron in the early stage of Earth's evolution.

Density of the Earth's core is lower than that of pure iron and the light element(s) in the core is a long-standing problem. Hydrogen is the most abundant element in the solar system and thus one of the important candidates. However, the dissolution process of hydrogen into iron remained unclear. Here we carry out high-pressure and high-temperature in situ neutron diffraction experiments and clarify that when the mixture of iron and hydrous minerals are heated, iron is hydrogenized soon after the hydrous mineral is dehydrated. This implies that early in the Earth's evolution, as the accumulated primordial material became hotter, the dissolution of hydrogen into iron occurred before any other materials melted. This suggests that hydrogen is likely the first light element dissolved into iron during the Earth's evolution and it may affect the behaviour of the other light elements in the later processes.

Quantitative Rietveld texture analysis of CaSiO(3) perovskite deformed in a diamond anvil cell.

The Rietveld method is used to extract quantitative texture information from a single synchrotron diffraction image of a CaSiO(3) perovskite sample deformed in axial compression in a diamond anvil cell. The image used for analysis was taken in radial geometry at 49 GPa and room temperature. We obtain a preferred orientation of {100} lattice planes oriented perpendicular to the compression direction and this is compatible with [Formula: see text] slip.

A new polymorph of FeAlO3 at high pressure.

Synchrotron X-ray diffraction measurements confirmed that a new polymorph of FeAlO3 could be synthesized at about 1800 K and 72 GPa. This phase can be indexed on an orthorhombic cell and transforms into the trigonal form on release of pressure. The c/a ratio of about 2.71 of the trigonal phase suggests corundum structure of FeAlO3 rather than LiNbO3 or ilmenite structure. This conclusion also suggests that the high-pressure orthorhombic phase could be the Rh2O3(II) structure rather than the GdFeO3-type perovskite structure.

High-pressure generation using double stage micro-paired diamond anvils shaped by focused ion beam.

Micron-sized diamond anvils with a 3 µm culet were successfully processed using a focused ion beam (FIB) system and the generation of high pressures was confirmed using the double stage diamond anvil cell technique. The difficulty of aligning two second-stage micro-anvils was solved via the paired micro-anvil method. Micro-manufacturing using a FIB system enables us to control anvil shape, process any materials, including nano-polycrystalline diamond and single crystal diamond, and assemble the sample exactly in a very small space between the second-stage anvils. This method is highly reproducible. High pressures over 300 GPa were achieved, and the pressure distribution around the micro-anvil culet was evaluated by using a well-focused synchrotron micro-X-ray beam.

Electrical conductivity of ice VII.

It was discovered that a peak appears near a pressure of Pc = 10 GPa in the electrical conductivity of ice VII as measured through impedance spectroscopy in a diamond anvil cell (DAC) during the process of compression from 2 GPa to 40 GPa at room temperature. The activation energy for the conductivity measured in the cooling/heating process between 278 K and 303 K reached a minimum near Pc. Theoretical modelling and molecular dynamics simulations suggest that the origin of this unique peak is the transition of the major charge carriers from the rotational defects to the ionic defects.

Helium penetrates into silica glass and reduces its compressibility.

SiO(2) glass has a network structure with a significant amount of interstitial voids. Gas solubilities in silicates are expected to become small under high pressure due to compaction of voids. Here we show anomalous behaviour of SiO(2) glass in helium. Volume measurements clarify that SiO(2) glass is much less compressible than normal when compressed in helium, and the volume in helium at 10 GPa is close to the normal volume at 2 GPa. X-ray diffraction and Raman scattering measurements suggest that voids are prevented from contracting when compressed in helium because helium penetrates into them. The estimated helium solubility is very high and is between 1.0 and 2.3 mol per mole of SiO(2) glass at 10 GPa, which shows marked contrast with previous models. These results may have implications for discussions of the Earth's evolution as well as interpretations of various high-pressure experiments, and also lead to the creation of new materials.

Quenchable high-density amorphous polymorphs of zirconium tungstate.

Zirconium tungstate turns amorphous above 2 GPa. Amorphous-Zr(WO(4))(2) is studied in situ using synchrotron x-ray diffraction and Raman spectroscopy at high pressure. The height and the position of the first peak of the structure factor as a function of pressure exhibit discontinuous changes suggesting an amorphous to amorphous transformation around 19 GPa. The pressure dependence of the Raman mode frequencies of the tungstate tetrahedra also exhibits a change at the same pressure. The high-density amorphous form appears to have higher oxygen coordination as compared to the low-density amorphous form.

Development of loading system for liquid hydrogen into diamond-anvil cells under low temperature.

A loading system for hydrogen gas into the diamond-anvil cell has been developed. The loading of hydrogen gas is performed under low temperature by using liquid helium as a cooling medium. Also, a compression apparatus has been developed to load gaseous materials into various diamond-anvil cells. The present loading system and compression apparatus have been used successfully to form hydrogen hydrate. The present loading system can also be used to load other gaseous materials as a pressure medium.