The structural and optical properties of ZnO bulk and nanocrystals under high pressure

The elastic properties of high-quality ZnO crystals and nanopowder of grain size of about 65 nm are studied for both wurtzite (low pressure) and rock-salt high pressure phases. The measured values of bulk moduli for wurtzite and rock-salt phases of bulk ZnO crystals are equal to 156±13 and 187±20 GPa, respectively, and considerably larger for ZnO nanocrystals. The phase transition begins at a pressure of about 9 GPa and it is completed at a pressure of about 13.8 GPa for bulk crystals, whereas the values of pressure at which the phase transition occurs are lower for nanocrystals. A carefull Rietveld analysis of the obtained data does not exhibit the presence of any intermediate phases between low pressure wurtzite and high pressure rock-salt phases of ZnO. The phase transition is accompanied by a strong decrease in the near-band-gap photoluminescence intensity. In addition, the pressure coefficient of the near-band-gap luminescence in ZnO nanocrystals exhibits strong deviation from the linearity observed in bulk crystals. An analysis of the results shows that defects present in the nanopowdered sample are responsible for the observed effects.     

Pressure-volume relations and bulk modulus under pressure of tetrahedral compounds

The pressure-volume relation and the compression effect on the bulk modulus of tetrahedral compounds such as GaP, InP, ZnS, ZnSe, ZnTe and CdTe are investigated from the electronic theory of solids by using our recently presented binding force, which includes mainly covalent interactions in the pseudopotential formalism and partially ionic interactions. The calculated results of the pressure-volume relations involving the pressure-induced phase transition are useful when comparing with the experimental data under high pressure. The calculated bulk modulus of these compounds increases as the crystal volume decreases. Further, the pressure derivative of bulk modulus is not constant and decreases with the reduction of the crystal volume.     

Isothermal bulk modulus and its first pressure derivative of NaCl at high pressure and high temperature

The isothermal bulk modulus and its first pressure derivative of NaCl are investigated using the classical molecular dynamics method and the quasi-harmonic Debye model. To ensure faithful molecular dynamics simulations, two types of potentials, the shell-model (SM) potential and the two-body rigid-ion Born-Mayer-Huggins-Fumi-Tosi (BMHFT) potential, are fully tested. Compared with the SM potential based simulation, the molecular dynamics simulation with the BMHFT potential is very successful in reproducing accurately the measured bulk modulus of NaCl. Particular attention is paid to the prediction of the isothermal bulk modulus and its first pressure derivative using the reliable potential and to the comparison of the SM and the BMHFT potentials based molecular dynamics simulations with the quasi-harmonic Debye model. The properties of NaCl in the pressure range of 0-30 GPa at temperatures up to the melting temperature of 1050 K are investigated.     

Isothermal bulk modulus and its first pressure derivative of NaCl at high pressure and high temperature

The isothermal bulk modulus and its first pressure derivative of NaCl are investigated using the classical molecular dynamics method and the quasi-harmonic Debye model.To ensure faithful molecular dynamics simulations,two types of potentials,the shell-model(SM) potential and the two-body rigid-ion Born-Mayer-Huggins-Fumi-Tosi(BMHFT) potential,are fully tested.Compared with the SM potential based simulation,the molecular dynamics simulation with the BMHFT potential is very successful in reproducing accurately the measured bulk modulus of NaCl.Particular attention is paid to the prediction of the isothermal bulk modulus and its first pressure derivative using the reliable potential and to the comparison of the SM and the BMHFT potentials based molecular dynamics simulations with the quasi-harmonic Debye model.The properties of NaCl in the pressure range of 0-30 GPa at temperatures up to the melting temperature of 1050 K are investigated.     

Emission of Cu-related complexes in ZnO:Cu nanocrystals

Photoluminescence (PL), its temperature dependence, scanning electronic microscopy (SEM) and X ray diffraction (XRD) have been applied for the comparative study of varying the emission, morphology and crystal structure of ZnO and ZnO:Cu nanocrystals (NCs) versus technological routines, as well as the dependence of ZnO:Cu NC parameters on the Cu concentration. A set of ZnO and ZnO Cu NCs was prepared by the electrochemical (anodization) method at a permanent voltage and different etching durations with follows thermal annealing at 400 °C for 2 h in ambient air. The size of ZnO NCs decreases from 300 nm×540 nm down to 200 nm×320 nm with etching duration increasing. XRD study has confirmed that thermal annealing stimulates the ZnO oxidation and crystallization with the formation of wurtzite ZnO crystal lattice. XRD method has been used for monitoring the lattice parameters and for confirming the Cu doping of ZnO Cu NCs. In ZnO Cu NCs four defect related PL bands are detected with the PL peaks at 1.95–2.00 eV (A), 2.15-2.23  eV (B), 2.43–2.50 eV (C) and 2.61–2.69 eV (D). Highest PL intensities of orange, yellow and green emissions have been obtained in ZnO Cu NCs with the Cu concentration of 2.28 at%. At Cu concentration increasing (≥2.28 at%) the PL intensities of the bands A, B, C decrease and the new PL band peaked at 2.61–2.69 eV at 10 K appears in the PL spectrum. The variation of PL intensities for all PL bands versus temperature has been studied and the corresponding activation energies of PL thermal decay have been estimated. The type of Cu-related complexes is discussed using the correlation between the PL spectrum transformation and the variation of XRD parameters in ZnO Cu NCs.     

Amorphization of cuprite,Cu2O,due to chemical decomposition under high pressure

JETP Letters - Using synchrotron radiation and a diamond-anvil cell, a structural study of the phase transformations in Cu2O is carried out from diffraction data obtained in situ while heating at a...     

Melting and isothermal bulk modulus of the rocksalt phase of ZnO with molecular dynamics simulation

The Buckingham potential has been employed to simulate the melting of the rocksalt phase of ZnO over a wide pressure–temperature range and isothermal bulk modulus with shell model molecular dynamics method. The melting curve from molecular dynamics simulations is in good agreement with the results obtained from Lindemann melting equation in the pressure below 7 GPa. The calculated null compression bulk modulus is compared with the available experimental data and other theoretical results. At extended temperature ranges, the isothermal bulk modulus has also been predicted up to 3000 K.     

Thermal expansivity and bulk modulus of ZnO with NaCl-type cubic structure at high pressures and temperatures

The thermal expansivity and bulk modulus of ZnO with NaCl-type cubic structure were estimated by using the constant temperature and pressure molecular dynamics technique with effective pair potentials which consist of the Coulomb, dispersion, and repulsion interaction at high pressures and temperatures. It is shown that the calculated thermodynamic parameters including linear thermal expansion coefficient, isothermal bulk modulus and its pressure derivative are in good agreement with the available experimental data and the latest theoretical results. At an extended pressure and temperature ranges, linear thermal expansion coefficient and isothermal bulk modus have also been predicted. The thermodynamic properties of ZnO with NaCl-type cubic structure are summarized in the pressure 0–150 GPa ranges and the temperature up to 3000 K.     

Structural stability and phase transitions in K8Si46 clathrate under high pressure

The structural stability of type-I K8Si46 clathrate has been investigated at high pressure by synchrotron x-ray diffraction. In contrast to that observed in the Na-doped structure-II analogue [A. San-Miguel, Phys. Rev. Lett. 83, 5290 (1999)]], no phase separation into the beta-Sn Si structure was identified at 11 GPa. Instead, K8Si46 is found to undergo a transition to an isostructural positional disordered phase at around 15 GPa. Ab initio phonon band structure calculations reveal a novel phenomenon of phonon instabilities of K atoms in the large cavities is responsible for this transition. Above 32 GPa, the new structure transforms into an amorphous phase.     

Isothermal compressibility and bulk modulus for methanol under the effect of pressure and temperatures

It has been demonstrated that the spinodal model produces very well the isothermal compressibility of liquid methanol for a wide range of pressures and temperatures. We have used the pseudospinodal model further to determine pressure derivatives, first-order as well as second-order of isothermal compressibility and bulk modulus for liquid methanol in the range of pressures (0–100 MPa) and temperatures (208.17 K–298.16 K). The results have been found to present close agreement with the available experimental data. We have also calculated the values of densities as a function of pressure and temperature for methanol using the Stacey equation of state.     

First-principle study of phase stability,electronic structure and thermodynamic properties of cadmium sulfide under high pressure

By employing first principle and a quasi-harmonic Debye model, we study the phase stability, phase transition, electronic structure and thermodynamic properties of cadmium sulfide (CdS). The results indicate that CdS is a typical ionic crystal and that the zinc-blende phase in CdS is thermodynamically unstable. Moreover, the heat capacity of the wurtzite and rocksalt phases of CdS decreases with pressure and increases with temperature, obeying the rule of the Debye T³ law at low temperature and the Dulong–Petit limit at high temperature.     

Structural stability, phase transformations and band-tuning of actinide and rare earth based intermetallics under high pressure: a perspective

When a solid is subjected to external pressure, it can undergo either structural transformation or remain stable in its parent structure. The sequence of structural transformations, when mapped for similar materials, viz., isostructural, isoelectronic and so on, can be used to create a map showing the evolution of structures under pressure for such materials. Such maps are useful in predicting high pressure phases. The structural transitions and the stability of materials as a function of pressure are intricately connected to their electronic structure. Many a times it is advantageous to know the stability of the material under pressure just by calculating its electronic structure. This can be accomplished only if several homologues materials are studied and the stability criteria arrived at by correlating their electronic structure with their structural stability under pressure. Further, as a function of pressure, the electronic structure changes can lead to enhancement in certain desired electronic, physical or mechanical properties. Several examples are known, wherein, pressure tuning of the band structure leads to improved properties. In this paper, we have discussed the above mentioned areas and presented a perspective of the above using the results of our own studies on f-electron based intermetallics (f-IMCs).     

Study of temperature dependence of density, bulk modulus, shear modulus and thermal pressure for mantle minerals

The temperature dependence of different parameters i.e. density ρ(T), bulk modulus K_T(T), shear modulus G_T(T) and thermal pressure ΔP_th for mantle minerals i.e. X₂SiO₄ (X=Mg, Fe, Co, Mn) have been studied in high temperature range on the basis of semi-phenomenological isobaric equation of state. The calculated values of these parameters are showing good agreements with experimental value in case of each mantle minerals.     

极端条件下锆的动力学稳定性研究

过渡金属Zr具有优良的物理、化学及力学性能, 具有广泛的应用价值. 主要通过新近发展的自洽晶格动力学方法, 充分考虑声子间的相互作用, 成功获得了β-Zr的高温高压声子色散曲线, 预测了β-Zr在相图中能够稳定存在的区域, 进一步比较α-Zr, ω-Zr和β-Zr的自由能, 获得了α-β 及ω-β 相变的相边界, 构建了Zr的参考相图. 同时, 也获得了β-Zr的高温状态方程及热膨胀系数, 能够为构建Zr的全区物态方程提供有益的参考.     

高温高压下钼的结构稳定性研究

以钼为代表的一系列过渡金属,在高温高压的相变及结构稳定性研究是实验和理论研究的热点.钼在常温常压下是bcc结构,但是在高温高压下可能的相结构一直未能确定.本文首先预测了几种高压下的结构,并计算了其自由能及力学性质.针对可能的hcp结构,我们通过新近发展的自洽晶格动力学方法,充分考虑声子间相互作用,成功获得了hcp结构高温高压声子色散曲线,结果表明hcp相在热力学及动力学上都是能够稳定存在的结构,是一种可能的高压相.     

Dynamical stability and phase transition of ZrC under pressure

A comprehensive first principles study of structural, elastic, electronic, and phonon properties of zirconium carbide (ZrC) is reported within the density functional theory scheme. The aim is to primarily focus on the vibrational properties of this transition metal carbide to understand the mechanism of phase transition. The ground state properties such as lattice constant, elastic constants, bulk modulus, shear modulus, electronic band structure, and phonon dispersion curves (PDC) of ZrC in rock-salt (RS) and high-pressure CsCl structures are determined. The pressure-dependent PDCs are also reported in NaCl phase. The phonon modes become softer and finally attain imaginary frequency with the increase of pressure. The lattice degree of freedom is used to explain the phase transition. Static calculations predict the RS to CsCl phase transition to occur at 308?GPa at 0?K. Dynamical calculations lower this pressure by about 40?GPa. The phonon density of states, electron–phonon interaction coefficient, and Eliashberg's function are also presented. The calculated electron–phonon coupling constant λ and superconducting transition temperature agree reasonably well with the available experimental data.     

Ab initio study on crystal structure and phase stability of ZrC_2 under high pressure

The structural stabilities and crystal evolution behaviors of the hyper stoichiometric compound ZrC₂(carbon rich;C/Zr> 1.0) are studied under ambient and high pressure conditions using first-principles calculations in combination with the particle-swarm optimization algorithm.Six viable structures of ZrC₂ in P21/c,Cmmm,Cmc2₁,P4₂/nmc,Immm and P6/mmm symmetries are identified.These structures are dynamically stable as their phonon spectra have no imaginary modes at zero pressure or at the selected high-pressure points.Among them,the P21/c phase represents the ground state structure,whereas P21/c,P4₂/nmc,Immm and P6/mmm phases are part of the phase transition series.The phase order and critical pressures of the phase transition are determined to be approximately 300 GPa according to the equation of states and enthalpy.Furthermore,the mechanical and electronic properties are investigated.The P21/c and Cmc2₁ phases display a semi-metal nature,whereas the P4₂/nmc,Immm,P6/mmm and Cmmm phases exhibit a metallic nature.Moreover,the present study reveals considerable information regarding the structural,mechanical and electronic properties of ZrC₂,thereby providing key insights into its material properties and evaluating its behavior in practical applications.     

X-ray absorption study of Cu,Zn SOD under high pressure

Abstract

We have investigated Cu, Zn Superoxide Dismutase (Cu, Zn SOD) metal sites at high pressure using X-ray absorption. XAS (X-ray Absorption Spectroscopy) gives information on local structure and it is particularly suited to metal site investigation. To the best of our knowledge, this is the first time that protein conformational states have been investigated using the high pressure XAS technique. Cu, Zn SOD catalyses the dismutation of toxic oxygen radicals produced in cells; this reaction occurs at the copper metal site. Structural changes around the copper, induced by pressure, can be directly related to protein substates. Their characterisation is thus important in the understanding of protein activity.

The high-pressure device was a Paris-Edinburgh large volume cell.

Experiments were performed on lyophilised Cu, Zn SOD between 0 and 48 kbar at the copper and zinc K-edges. The two metal local atomic environments have a different behaviour as pressure increases: copper exhibits a more flexible environment; on the contrary, zinc shows small structural modifications. We have identified a state, formed between 3 and 8 kbar, which is stable up to 48 kbar.