Pressure-induced phase transition of wulfenite

The in-situ high-pressure structures of wulfenite have been investigated by means of angular dispersive X-ray diffraction with diamond anvil cell and synchrotron radiation. In the pressure up to 22.9 GPa, a pressure-induced scheelite-to-fergusonite transition is observed at about 10.6 GPa. The pressure dependence for the lattice parameters of wulfenite is reported, and the axial compression coefficients Ka₀=－1.36×10^－3 GPa^－1 and Kc₀= －2.78×10^－3 GPa^－1 are given. The room-temperature isothermal bulk modulus is also obtained by fitting the P-V data using the Murnaghan equation of state.

     

Pressure-induced phase transition and structural properties of CrO2

The structural properties and pressure-induced phase transitions of CrO₂ have been investigated using the pseudopotential plane-wave method based on the density functional theory (DFT). The rutile-type (P4₂/mnm), CaCl₂-type (Pnnm), pyrite-type (Pā3), and CaF₂-type (Fm-3m) phases of CrO₂ have been considered. The structural properties such as lattice parameters, bulk moduli and its pressure derivative are consistent with the available experimental data. The second-order phase-transition pressure of CrO₂ from the rutile phase to CaCl₂ phase is 10.9?GPa, which is in good agreement with the experimental result. The sequence of these phases is rutile-type?→?CaCl₂-type?→?pyrite-type?→?CaF₂-type with the phase-transition pressures 10.9, 23.9, and 144.5?GPa, respectively. The equation of state of different phases has also been presented. It is more difficult to compress with the increase of pressure for different phases of CrO₂.     

Phase transition of ZnS at high pressures and temperatures

The high-pressure behaviour of zinc sulphide, ZnS, has been investigated, using an in situ X-ray powder diffraction technique in a diamond anvil cell, at pressures and temperatures up to 35 GPa and 1000 K, respectively. The pressure-induced phase transition from a zincblende (B3) to a rocksalt (B1) structure was observed. This transition occurred at 13.4 GPa and at room temperature, and a negative dependence on temperature for this transition was confirmed. The transition boundary was determined to be P (GPa) = 14.4 ? 0.0033 × T (K).     

Hexagonal germanium formed via a pressure‐induced phase transformation of amorphous germanium under controlled nanoindentation

We have studied the stable end phase formed in amorphous germanium (a‐Ge) films that have been subjected to a pressure‐induced phase transformation under indentation loading using a large (20 µm) spherical indenter. After indentation the samples have been annealed at room temperature to remove any residual unstable R8 and BC8 phases. Raman spectroscopy indicates a single broad peak centred around 292 cm^–1 and we have used first principles density functional perturbation theory calculations and simulated Raman spectra for nano‐crystalline diamond cubic germanium (DC‐Ge) to help identification of the final phase as hexagonal diamond germanium (HEX‐Ge). Transmission electron microscopy and selected area diffraction analysis confirmed the presence of a dominant HEX‐Ge end phase. These results help explain significant inconsistencies in the literature relating to indentation‐induced phase transitions in DC‐ and a‐Ge. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Pressure-induced phase transition in transition metal trifluorides

As a fundamental thermodynamic variable, pressure can alter the bonding patterns and drive phase transitions leading to the creation of new high-pressure phases with exotic properties that are inaccessible at ambient pressure. Using the swarm intelligence structural prediction method, the phase transition of TiF₃, from R—3c to the Pnma phase, was predicted at high pressure, accompanied by the destruction of TiF₆ octahedra and formation of TiF₈ square antiprismatic units. The Pnma phase of TiF₃, formed using the laser-heated diamond-anvil-cell technique was confirmed via high-pressure x-ray diffraction experiments. Furthermore, the in situ electrical measurements indicate that the newly found Pnma phase has a semiconducting character, which is also consistent with the electronic band structure calculations. Finally, it was shown that this pressure-induced phase transition is a general phenomenon in ScF₃, VF₃, CrF₃, and MnF₃, offering valuable insights into the high-pressure phases of transition metal trifluorides.     

A fast method to diagnose phase transition from amorphous to microcrystalline silicon

A series of hydrogenated silicon thin films were prepared by the radio frequency plasma enhanced chemical vapor deposition method (RF-PECVD) with various silane concentrations. The influence of silane concentration on structural and electrical characteristics of these films was investigated to study the phase transition region from amorphous to microcrystalline phase. At the same time, optical emission spectra (OES) from the plasma during the deposition process were monitored to get information about the plasma properties, Raman spectra were measured to study the structural characteristics of the deposited films. The combinatorial analysis of OES and Raman spectra results demonstrated that the OES can be used as a fast method to diagnose phase transition from amorphous to microcrystalline silicon. At last the physical mechanism, why both OES and Raman can be used to diagnose the phase transition, was analyzed theoretically.     

H2， He混合稀释生长微晶硅锗薄膜

采用H₂,He混合气体稀释等离子辅助反应热化学气相沉积法生长微晶硅锗薄膜,并在生长过程中对等离子体进行光发射光谱在线监测.结果表明：混合气体稀释法可以有效提高等离子体中的原子氢数目,降低等离子体中的电子温度;用XRD和光暗电导率表征样品的微结构和光电特性时发现,通过优化混合稀释气体中He和H₂气体的比例,能够减少薄膜中的缺陷态,促进薄膜<220>择优取向生长,有效改善微晶硅锗薄膜结构,提高光电吸收性能. 关键词： 化学气相沉积 微晶硅锗薄膜 光发射光谱 X射线衍射     

Pressure-induced phase transitions in single-crystalline Cu4Bi4S9 nanoribbons

In situ angle dispersive synchrotron X-ray diffraction and Raman scattering measurements under pressure are em- ployed to study the structural evolution of Cu4Bi4S9 nanoribbons, which are fabricated by using a facile solvothermal method. Both experiments show that a structural phase transition occurs near 14.5 GPa, and there is a pressure-induced re- versible amorphization at about 25.6 GPa. The electrical transport property of a single Cu4Bi4S9 nanoribbon under different pressures is also investigated.     

The phase transition and optimal synthesis temperature of LiNiO2

The phase transition of LiNiO₂ has been studied by using impedance spectroscopy, DTA, and X-ray diffraction methods. At 720°C the hexagonal phase changes in air to the cubic phase. The phase transition process is rather slow and partially reversible. A peculiar conductivity behavior was observed. From 324°C the conductivity deviates from Arrhenius behavior and is temperature-invariant until 613°C. Subsequently, it decreases rapidly with increase of the temperature. This phenomenon is related to the occupation of Ni²⁺ in Li⁺ positions. The optimal sintering temperature for LiNiO₂ is suggested to be 700°C.     

Pressure-induced molecular dissociation in iodine at low temperatures

Abstract

Synchrotron x-ray diffraction experiments at low temperatures have revealed that even at 35K the molecular dissociation starts taking place at P_S=21.5 and finishes at P_f=26.1GPa. An extrapolation of the phase boundary thus obtained at several temperatures intersects the T=4K line at P_S=21.6 and P_f=26.3GPa. This result, inferring the monatomic structure to be realized at P=30GPa and T=4K, leads to a discrepancy against the recent Mössbauer result obtained at the same point in the P-T phase diagram.     

A pressure induced phase transition in pyroxene

Abstract

Two monoclinic pyroxenes of composition Ca(Fe,Mg)Si₂O₆ were studied up to 10 GPa using X-ray powder diffraction and ⁵⁷Fe Mössbauerspectroscopy. The results are indicative of a phase transition at 4 GPa.     

Pressure-induced phase transition and structural behavior of MgO at high temperatures: a model study

A realistic interaction potential model approach by including temperature effects is developed to study phase transition, elastic properties and thermo-physical properties at very high pressures and temperatures. This approach is effectively able to explain the inter-atomic interaction involved at high temperature and high pressure as it includes the three-body interactions. Earlier works overlooked the three-body interactions at high temperature and pressures. Moreover, the phase-transition pressures of MgO crystal at high temperatures including the three-body interaction are computed for the first time. Elastic behavior, anisotropic factor and Debye temperature of MgO at high pressures and temperatures are also reported.     

Pressure-induced structural phase transition in RbAu

Using the first principle method based on density functional theory, the structural and elastic properties calculations of RbAu have been performed. The results demonstrate that RbAu is stable in the CsCl structure (B2) at ambient pressure, which is in well agreement with the experimental results. And there exists a structural phase transition from CsCl-type structure (B2) to NaTi-type structure (B32) at the transition pressure of approximate 6 GPa. The pressure effects on the elastic properties are discussed and the elastic property calculation indicates elastic instability maybe provide phase transition driving force according to the variations relation of the elastic constant versus pressure.     

In situ Raman and photoluminescence study on pressure‐induced phase transition in C60 nanotubes

Single crystalline C₆₀ nanotubes having face‐centered‐cubic structure with diameters in the nanometer range were synthesized by a solution method. In situ Raman and photoluminescence spectroscopy under high pressure were employed to study the structural stabilities and transitions of the pristine C₆₀ nanotubes. A phase transition, probably because of the orientational ordering of C₆₀ molecules, from face‐centered‐cubic structure to simple cubic structure occurred at the pressure between 1.46 and 2.26 GPa. At above 20.41 GPa, the Raman spectrum became very diffuse and lost its fine structure in all wavenumber regions, and only two broad and asymmetry peaks initially centered at 1469 and 1570 cm^–1 were observed, indicating an occurrence of amorphization. This amorphous phase remained to be reversible until 31.1 GPa, and it became irreversible to the ambient pressure after the pressure cycle of 34.3 GPa was applied. Copyright © 2012 John Wiley & Sons, Ltd.     

Pressure effect on phase transition in ferroelectic polymers

Pressure effects of phase transition behaviour in two kinds of ferroelectric polymers of poly(vinylidene fluoride), PVDF, and copolymers of vinylidene fluoride and trifluoroethylene, (VDF/TrFE), are discussed. In the case of PVDF, several high-pressure treatments including a high-pressure annealing and a uniaxial compression were shown to induce a crystal transformation from a non-polar Form II crystal to a polar Form I crystal, which has ferroelectric characteristics and high piezoelectric activity. In addition, substantial pressure effects on ferroelectric phase transition points as well as crystal structures were observed for (VDF/TrFE) copolymers with different VDF contents. The most significant pressure effects were observed for copolymer samples with unstable ferroelectric structures at atmospheric pressure. From high-pressure X-ray and Raman scattering studies, these pressure effects were suggested to originate from the pressure-induced conformational transition from gauche to trans in the molecular chains.     

Equal compressibility structural phase transition of molybdenum at high pressure

We have studied the high-pressure compression behavior of molybdenum up to 60 GPa by synchrotron radial x-ray diffraction (RXRD) in a diamond anvil cell (DAC). It is found that all diffraction peaks of molybdenum undergo a split at around 27 GPa, and we believe that a phase transition from a body-centered cubic structure to a rhombohedral structure at room pressure has occurred. The slope of pressure-volume curve shows continuity before and after this phase transition, when fitting the pressure-volume curves of the body-centered cubic structure at low pressure and the rhombohedral structure at high pressure. A bulk modulus of 261.3 (2.7) GPa and a first-order derivative of the bulk modulus of 4.15 (0.14) are obtained by using the nonhydrostatic compression data at the angle ψ = 54.7° between the diffracting plane normal and stress axis.     

X ray absorption spectroscopy investigation of phase transition in Ge,GaAs and GaP

Abstract

The phase transitions of GaAs, GaP and Ge under pressure have been investigated by x-ray absorption spectroscopy (XAS). At the onset of the transition the Debye-Waller factor increases and the x-ray absorption near edge structure (XANES) is progressively modified. A mixing of the low and high pressure phase can be determined by XAS as well as amorphization of the sample on pressure release.     

The β-γ phase transition in titanite and the isosymmetric analogue in malayaite

X-ray diffraction technique and hard mode infrared spectroscopy were used to study the thermal behaviour of synthetic titanite, CaTiSiO₅, two natural titanite samples and iso-structural malayaite, CaSnSiO₅. Both pure minerals show a thermal anomaly near 500 K. Specific heat measurements show an intermediate phase in synthetic titanite. Impurities in titanite tend to suppress the discontinuity near 500 K. The β-γ transition near 820 K is not affected by Fe and Al defects in the natural material. Infrared studies in malayaite show a change of the temperature dependence of the phonon frequencies. X-ray experiments show weak structural rearrangements with heating but no evidence of a symmetry breaking phase transition near 500 K The character of the 500 K anomaly in malayaite is more similar to the β-γ transition (825 K) than the α-β Mtransition (496 K) in synthetic titanite.     

Specific heat of amorphous silicon at low temperatures

The heat capacity of amorphous silicon has been measured between 2 and 50 K using an a.c. calorimetry technique. A comparison with heat capacity measurements of crystalline silicon shows a reduction of the Debye temperature by a factor 0.82 and of the position of the maximum in $\text{c}\text{T}{}^3$ by a factor of 0.77. This behaviour indicates a general reduction in frequency of the transversal-acoustic modes with respect to the corresponding modes of crystalline silicon.