Precursor effects of the Rhombohedral-to-Cubic Phase Transition in Indium Selenide

We report on the observation of precursor effects of the rhombohedral-to-cubic phase transition in Indium Selenide (InSe) with several experimental techniques. The pressure at which these precursor defects are first observed depends on the sensitivity of the experimental technique. In transport measurements, which are very sensitive to low defect concentrations, precursor effects are observed 5 to 6 GPa below the phase transition pressure whereas in X-ray diffraction measurements precursor effects are only observed 2 GPa below the phase transition pressure. We report optical absorption measurements, in which the precursor effects are shown by the growth and propagation of dark linear defects appearing 3 GPa below the phase transition pressure. On the base of a simple model of the stress field around edge dislocations, we attribute the darkening of the InSe samples to local phase transitions to a high-pressure modification along linear dislocations. These results agree with room-pressure and high-pressure Raman spectra of samples compressed up to 7-8 GPa, which show new phonon lines not corresponding to the low-pressure phase.     

InSe的高压电输运性质研究

高压下对InSe样品进行原位电阻率和霍尔效应测量. 电阻率测量结果显示, 样品在5–6 GPa区间呈现金属特性, 在12 GPa 的压力下发生由斜六方体层状结构到立方岩盐矿的结构相变, 且具有金属特性. 霍尔效应测量结果显示, 样品在6.6 GPa由p型半导体转变成n型半导体, 电阻率随着压力的升高而逐渐下降是由于载流子浓度升高引起的. 关键词： InSe 高压 电阻率 霍尔效应     

High density photoluminescence induced by laser pulse excitation in InSe under pressure

Abstract

We report on high density photoluminescence (HDPL) measurements in undoped indium selenide under pressure at 300 K. Direct electron-hole plasma (DEHP) stimulated emission, induced by high density excitation, has been observed in InSe from room pressure up to 5.1 GPa. Spontaneous and stimulated emission bands observed in the spectra have been analyzed within the framework of the band gap renormalization theory (BGR) in a multi-valley scenario. The pressure coefficients of the spontaneous and stimulated emission bands have led us to attribute these bands to transitions from different minima in the conduction band, which show different renormalization energies determined by the effective masses and electron densities in each valley. Under high excitation, the direct to indirect crossover is shown to occur at a lower pressure than that observed in absorption measurements, as a result of the different renormalization energies of each transition.     

Comparative Study on Pressure-Induced Structural Changes between C 6 O 2 I 4 and C 6 I 6

We have investigated the pressure effects on the structural properties of C 6 O 2 I 4 up to 39 GPa by powder x-ray diffraction measurements, which were compared with those of C 6 I 6 . The diffraction patterns of C 6 O 2 I 4 indicated a phase transition starting at 26.8 GPa. The mixed state of the low- and high-pressure phases continued up to 39 GPa well above an insulator-to-metal transition pressure of 33 GPa. The C 6 O 2 I 4 molecule remains planar structure in the low-pressure phase below 26.8 GPa in contrast to the non-planar molecular structure of C 6 I 6 at ambient and high pressures.     

High pressure studies up to 50GPa of CuO

Abstract

Copper oxide has been studied at high pressure up to 50 GPa. A monoclinic structure was compatible with the measurements at all pressures, and no phase change was observed. A bulk modulus, B₀, = 98 GPa, and its pressure derivative B′₀ = 5.6 was obtained.     

High-Pressure Behavior of Nano Titanium Dioxide

Nanocrystalline rutile Titanium dioxide has been studied by X-ray diffraction at ambient temperature up to 47.4 GPa. The material is found to transform to the monoclinic baddeleyite structure between 20 and 30 GPa, which is higher than the corresponding pressure range for bulk material. Upon decompression, the baddeleyite phase transforms to the f -PbO 2 phase at about 4-2 GPa. The experimental bulk moduli are 211(7) GPa for the rutile phase, 235(16) for the baddeleyite type and 212(25) GPa for the f -PbO 2 type phase. The results are compared with previous measurements of bulk rutile Titanium dioxide.     

On the high-pressure phase transition in

X-ray diffraction (XRD) experiments have been carried out on quartz-like GaPO₄ at high pressure and room temperature. A transition to a high pressure disordered crystalline form occurs at 13.5 GPa. Slight heating using a YAG infrared laser was applied at 17 GPa in order to crystallize the phase in its stability field. The structure of this phase is orthorhombic with space group Cmcm. The cell parameters at the pressure of transition are a =7.306?, b =5.887? and c =5.124?. Received: 7 October 1997 / Received in final form: 17 November 1997 / Accepted: 18 November 1997     

Raman spectroscopic and optical absorption study of the high pressure behaviour and polymorphism in KO2

Abstract

Raman scattering, visible absorption, and optical observation studies have been made on polycrystalline potassium superoxide (KO₂) in a diamond anvil cell as a function of pressure and temperature. Three new phases are observed. With increasing pressure at 298 K, KO₂ transforms from the well known modified CaC₂ structure (Phase II), to two new phases (VII, and VIII). The transformation from III to VII occurs at about 3.2GPa. Phase VII transforms to phase VIII at about 4.4GPa. However, in some samples phase VII does not occur and phase II transforms directly into phase VIII at about 4.2 GPa. These structural transformations are indicated by marked changes in the Raman spectrum. The transitions out of phase II are also marked by a discontinuous red shift in the optical absorption edge. From optical observations we have also determined the pressure and temperature dependence of the transitions from phase II to the high temperature cubic (B1) phase I as well as from the high pressure phases VII and VIII to a new nonbirefringent phase IX. This new phase IX has the cubic B2 (CsCl) structure as is shown by our recent X-ray synchrotron experiments.     

Pressure-Effect on Anatase Titanium Dioxide

Pressure-induced phase transition of anatase titanium dioxide was investigated by Raman, absorption spectroscopy and X-ray diffraction. The change in Raman and absorption spectra with pressure revealed that the transition from anatase to high pressure phase with f -PbO 2 structure (TiO 2 -II) occurred in the pressure range of 4.0-4.6 GPa for a single crystal. The X-ray powder diffraction patterns indicate the presence of superstructural lattice of anatase at pressures more than 3 GPa. The superstructure of anatase disappears on the release of the pressure. A sluggish transition to the high pressure phase is also observed. The anatase coexists with the high pressure phase at 5.2 GPa. The difference in the results between optical spectroscopy (single crystal) and X-ray diffraction (powder) will be due to crystalinity of the sample.     

High Pressure X-Ray Absorption and Diffraction Study of InAs

We have performed X-ray absorption (XAS) and diffraction (XRD) measurements at high pressure on samples of powdered InAs, up to 50 and 80 GPa, respectively. In the lower pressure range, our data are consistent with the following structural sequence: Zincblende M NaCl M Cmcm . The first order transition from the semiconducting Zincblende phase to the metallic NaCl phase is clearly seen by the shift in the absorption onset at the As K-edge and the strong modifications of the extended X-ray absorption fine structure (EXAFS) due to the changes in the local structure from a 4-fold to a 6-fold coordinated environment. XAS shows the high pressure phase to be locally site-ordered. The diffraction data, analized by Rietveld fitting, gives a volume discontinuity of j V/V 0 ～0.18 for the first order transition. There is no apparent volume discontinuity associated to the NaCl M Cmcm transition.     

Pressure induced phase transformations and band structure of different high pressure phases in tellurium

We report here high-pressure x-ray diffraction (XRD) studies on tellurium (Te) at room temperature up to 40 GPa in the diamond anvil cell (DAC). The XRD measurements clearly indicate a sequence of pressure-induced phase transitions with increasing pressure. The data obtained in the pressure range 1 bar to 40 GPa fit five different crystalline phases out of Te: hexagonal Te (I) → monoclinic Te(II) → orthorhombic Te (III) → Β-Po-type Te(IV) → body-centered-cubic Te(V) at 4, 6.2, 11 and 27 GPa, respectively. The volume changes across these transitions are 10%, 1.5%, 0.3% and 0.5%, respectively. Self consistent electronic band structure calculations both for ambient and high pressure phases have been carried out using the tight binding linear muffin tin orbital (TB-LMTO) method within the atomic-sphere approximation (ASA). Reported here apart from the energy band calculations are the density of states (DOS), Fermi energy (E _f) at various high-pressure phases. Our calculations show that the ambient pressure hexagonal phase has a band gap of 0.42 eV whereas high-pressure phases are found to be metallic. We also found that the pressure induced semiconducting to metallic transition occurs at about 4 GPa which corresponds to the hexagonal phase to monoclinic phase transition. Equation of state and bulk modulus of different high-pressure phases have also been discussed.     

Pressure dependence of zone-boundary phonons in AlSb

Abstract

We have investigated the effect of hydrostatic pressure on zone-boundary and other critical-point phonon frequencies of AlSb by second-order Raman scattering. A softening of the TA(X), TA(L) and (L/T)A([Sgrave]) modes has been observed for pressures up to the first phase transition at 7.7 GPa. The LA(L) as well as the optical TO at X-, L-, and LO at [Sgrave]-, X-points harden with increasing pressure. Mode Griineisen parameters of all the resolved modes were calculated. Reflectivity measurements indicate that the high pressure phase above 7.7 GPa is metallic.     

A high pressure Raman study of terbium molybdate

Abstract

Tb₂(MoO₄)₃ has been studied by Raman spectroscopy under hydrostatic pressure up to 9 GPa at room temperature. The measurements reveal two phase transitions, one at around 2 GPa and another one above 5 GPa. The first phase transition is associated with an increase in the coordination number of Mo while the second is probably a transition to an amorphous phase in which only a wide band originating from Mo-O vibrations remains. This behaviour is irreversible as the Raman spectrum of the initial structure is not recovered at atmospheric pressure.     

Shock metamorphism of the graphite quasimonocrystal

Abstract

Micro structure examination of graphite quasimonocrystal recovered after dynamic loading to pressure of 35-45 GPa was carried out. Only a small amount of cubic diamond and recrystalized graphite was detected. Most of the graphite (～80 vol.%) remained in initial high orientation, but transformed to fine, grained phase with crystalite size 0.1-1 microns. Relaxation time of the transformation (～ 10 ns) and the degree of the transformation (～ 70-80 vol.%) were determined by means of measurements of the electrical resistivity during loading up to 26 GPa and following computer simulation of the results. We proposed that two simultaneous processes take place at pressures higher than 20 GPa: i) relatively slow diffusive graphite to diamond transformation localized in the zones with defect structure: ii) highly oriented graphite transforms to a diamond like phase with density of about 3.2 g/cm³ at zero pressure. This, transformation has fast, martensitic kinetics and is reversible.     

Structural study of ND4Br at high pressure

Abstract

A structure of ND₄Br has been studied at pressures up to 9 GPa by means of time-of-flight neutron diffraction. A phase transition to the high pressure phase V was observed at P=8·2(5)GPa. It was found that the phase V has a tetragonal structure with an antiparallel ordering of ammonium ions, space group P4/nmm which is in strong resemblance with low temperature modification ND₄Br(III). Deuterium positional parameter as a function of pressure was obtained.     

High-pressure phases of thorium and uranium compounds with the rocksalt structure

Abstract

The high-pressure crystal structures of the actinide compounds ThX and UX (X= C, N, P, S, As, Se, Sb, Te) have been studied by X-ray diffraction using synchrotron radiation, in the pressure range up to about 60 GPa Distorted fcc structures were observed for UC (27 GPa), UN (29 GPa), UP (10/28 GPa), US (10 GPa) and ThS (20 GPa). No phase transition has been observed for ThC and ThN. Compounds with As, Se, Sb all transform to the CsCl structure. ThP transform to the CsCl structure at 30 GPa. ThTe has the CsCl structure at ambient pressure and no further phase transition has been observed. UTe transforms to the CsCl structure at 9 GPa.     

High-pressure phases of plutonium monoselenide studied by X-ray diffraction

Abstract

Plutonium monoselenide was studied under high pressure up to 47 GPa, at room temperature, using a diamond anvil cell in an energy dispersive X-ray diffraction facility. At ambient pressure, PuSe has the NaC1-type (B1) structure. The compound has been found to undergo a second-order crystallographic phase transition at around 20 GPa. This phase can be described as a distorted B1 structure, with a rhombohedral symmetry. PuSe transforms to a new phase at around 35 GPa, which can be indexed in the cubic CsCl-type (B2). The volume collapse at this phase transition is 11%. When releasing pressure, we observed a strong hysteresis to the inverse transformation down to 5 GPa. From the pressure-volume relationship, the bulk modulus has been determined to B ₀ = 98 GPa and its pressure derivative as B ₀ = 2.6. These results are compared to those obtained with other actinide monmictides and monochalcogenides.     

Effect of high pressure on metastable and stable intermediate hcp phases formed in the Ag-17at%Ge alloy

Abstract

A metastable hexagonal close-packed (hcp) phase obtained by rapid quenching from the melt has been compressed to 5.7 GPa and annealed up to 1023 K. The axial ratios (c/a) of the hcp structure at the initial state, the stable state annealed under high pressure (5.7 GPa, 673 K) and the quenched state from high pressure and high temperature condition are 1.630, 1.635 and 1.628, respectively.

The volume reduction of the hcp structure by application of high pressure gives rise to increase the c/a ratio, which corresponds to an apparent reduction in the number of valence electrons per atom (e/a) in the Hume-Rothery alloys.     

Phase diagram of GaAs

Abstract

Optical measurements in the diamond anvil cell (DAC) as well as thermodynamics, show cubic GaAs I to be unstable at 300 K, at 13 GPa. The thermodynamic phase line from GaAs I to the high pressure (H.P.) form(s) is at 11 ± 2 GPa. Large hyteresis makes the actual I→II transition observable only at 17.5 ± 1 GPa.     

Electrical properties of (PBS)0·59TiS2 crystals at high pressures up to 20GPa

Abstract

The measurements of thermoelectric power S and resistance p at high pressure synthetic diamond anvils cell were performed for (PbS)0·59TiS2 and TiS2 crystals. The phase transition was found at P?;2GPa accompanied by descend of ρ and |S| for (PbS)o·59TiS2. This transition is connected with structural change of PbS fragment from pseudocubic cell to orthorombic one and as consequence, with change of the electron concentration in Tis2-layers. From the electronic structure calculations for TiS2, the semiconductor-metal transition occurs at pressure P ≥ 4 GPa. Experimentally at this pressure range the decrease of ρ(P) was observed for (PbS)0·59TiS2 crystals.