Predictions of pressure-induced structural transition,mechanical and thermodynamic properties of α-and β-Si₃N₄ ceramics:ab initio and quasi-harmonic Debye modeling

The plane-wave pseudo-potential method within the framework of ab initio technique is used to investigate the structural and elastic properties of α-and β-Si3N4.The ground-state parameters accord quite well with the experimental data.Our calculation reveals that α-Si3N4 can retain its stability to at least 40 GPa when compressed at 300 K.The α→β phase transformation would not occur in a pressure range of 0-40 GPa and a temperature range of 0-300 K.Actually,the α→β transition occurs at 1600 K and 7.98 GPa.For α-and β-Si3N4,the c axes are slightly more incompressible than the a axes.We conclude that β-Si3N4 is a hard material and ductile in nature.On the other hand,β-Si3N4 is also found to be an ionic material and can retain its mechanical stability in a pressure range of 0-10 GPa.Besides,the thermodynamic properties such as entropy,heat capacity,and Debye temperature of α-and β-Si3N4 are determined at various temperatures and pressures.Significant features in these properties are observed at high temperature.The calculated results are in good agreement with available experimental data and previous theoretical values.Many fundamental solid-state properties are reported at high pressure and high temperature.Therefore,our results may provide useful information for theoretical and experimental investigations of the Si3N4 polymorphs.     

First-principles study of the structural,mechanical and electronic properties of ZnX2O4（X=Al,Cr and Ga）

This paper performs first-principles calculations to study the structural,mechanical and electronic properties of the spinels ZnAl2O4 ,ZnGa2O4 and ZnCr2O4 ,using density functional theory with the plane-wave pseudopotential method. Our calculations are in good agreement with previous theoretical calculations and the available experimental data. The studies in this paper focus on the evolution of the mechanical properties of ZnAl2O4 ,ZnGa2O4 and ZnCr2O4 under hydrostatic pressure. The results show that the cubic phases of ZnAl2O4 ,ZnGa2O4 and ZnCr2O4 become unstable at about 50 GPa,40 GPa and 25 GPa,respectively. From analysis of the band structure of the three compounds at equilibrium volume,it obtains a direct band gap of 4.35 eV for ZnAl2O4 and 0.89 eV for ZnCr2O4 ,while ZnGa2O4 has an indirect band gap of 2.73 eV.     

mechanical and thermodynamic properties of α-and β-Si3N4 ceramics： ab initio and quasi-harmonic Debye modeling

The plane-wave pseudo-potential method within the framework of ab initio technique is used to investigate the structural and elastic properties of α-and β-Si3N4. The ground-state parameters accord quite well with the experimental data. Our calculation reveals that α-Si3N4 can retain its stability to at least 40 GPa when compressed at 300 K. The α → β phase transformation would not occur in a pressure range of 0-40 （3Pa and a temperature range of 0 300 K. Actually, the α → β transition occurs at 1600 K and 7.98 GPa. For α-and β-Si3N4, the c axes are slightly more incompressible than the a axes. We conclude that β-Si3N4 is a hard material and ductile in nature. On the other hand, β-Si3N4 is also found to be an ionic material and can retain its mechanical stability in a pressure range of 0 - 010 GPa. Besides, the thermodynamic properties such as entropy, heat capacity, and Debye temperature of α-and β-Si3N4 are determined at various temperatures and pressures. Significant features in these properties are observed at high temperature. The calculated results are in good agreement with available experimental data and previous theoretical values. Many fundamental solid-state properties are reported at high pressure and high temperature. Therefore, our results may provide useful information for theoretical and experimental investigations of the Si3N4 polymorphs.     

Phase transition and thermodynamic properties of ThO2：Quasi-harmonic approximation calculations and anharmonic effects

The thermodynamic properties and the phase transition of ThO2 from the cubic structure to the orthorhombic structure are investigated using the first-principles projector-augmented wave method. The vibrational contribution to Helmholtz free energy is evaluated from the first-principles phonon calculations. The anharmonic contribution to quasi-harmonic free energy is accounted for by using an effective method(2010 Phys. Rev. B 81 172301). The results reveal that at ambient temperature, the phase transition from the cubic phase to the orthorhombic phase occurs at 26.45 GPa, which is consistent with the experimental and theoretical data. With increasing temperature, the transition pressure decreases almost linearly. By comparing the experimental results with the calculation results, it is shown that the thermodynamic properties of ThO2 at high temperature improve substantially after including the anharmonic correction to quasi-harmonic free energy.     

Photoluminescence properties of rare earth doped α-Si3N4

The photoluminescence properties of Eu²⁺, Ce³⁺ and Tb³⁺ doped α-Si₃N₄ have been studied and a possible structural model has been proposed on the basis of the Rietveld refinement of X-ray powder diffraction data. Nearly single phase rare earth doped α-Si₃N₄ was synthesized by a solid state reaction at 1600 °C in N₂-H₂ atmosphere starting from amorphous Si₃N₄ and rare earth oxides or nitrides. Because of small crystal field splitting of the 5d levels, the excitation and emission bands of Eu²⁺ and Ce³⁺ are positioned at higher energies as isolated ions in comparison with that in Ca-α-Sialon. Both Eu²⁺- and Ce³⁺-doped α-Si₃N₄ show blue band emission peaking at about 470 and 450 nm, respectively, under UV excitation. α-Si₃N₄:Tb³⁺ exhibits dominant green line emission mainly arising from ⁵D₄→⁷F_J (J=6-3) with weak ⁵D₃→⁷F_J (J=6-3) transitions of Tb³⁺ when excited by UV light. The thermal stability of α-Si₃N₄:Eu²⁺ is comparable with that of Ca-α-Sialon:Eu²⁺ and is much better than that of α-Si₃N₄:Ce³⁺.     

First-principles calculations on the electronic and vibrational properties of β-V2O5

Using a first-principles approach based on density functional theory,this paper studies the electronic and dynamical properties of β-V2O5.A smaller band gap and much wider split-off bands have been observed in comparison with αV2O5.The Ramanand infrared-active modes at the Γ point of the Brillouin zone are evaluated with LO/TO splitting,where the symbol denotes the longitudinal and transverse optical model.The nonresonant Raman spectrum of a βV2O5 powder sample is also computed,providing benchmark theoretical results for the assignment of the experimental spectrum.The computed spectrum agrees with the available experimental data very well.This calculation helps to gain a better understanding of the transition from αto β-V2O5.     

Effects of Single Vacancy on Electronic and Optical Properties for γ-Si3N4

基于密度泛函理论的广义梯度近似方法研究了中性单点缺陷γ-Si₃N₄的能量、电子结构和光学性质. N缺陷的结合能和形成能比Si(8)和Si(4)位的都低,显示γ-Si₃N₄中N缺陷更易形成. 分析了各种缺陷情况下相应的态密度. Si缺陷能形成p型半导体,N缺陷使材料形成间接带隙的n型半导体. Si缺陷情况下,物质有相对大的静态介电常数,在可见光区和红外区,吸收和反射得到显著改善,但是N缺陷却没什么影响.     

α-, β-和γ-Si3N4 高压下的电子结构和相变: 第一性原理研究

本文采用第一性原理框架下的赝势平面波方法结合振动类德拜模型研究了α,β和γ-Si₃N₄在高温下的点阵常数,弹性常数和弹性模量.研究发现三种同质异相体的体模量都很高.β-Si₃N₄在低温下表现出脆性,在高温下则表现出延展性.γ-Si₃N₄在低温和高温下都是脆性的共价化合物.β → γ 相变的相界斜率为正值,说明在较高温度时合成γ-Si₃N₄所需的压强也较高.α → γ 相变的相界可以表示成 P=16.29- 1.835-10^-2 T+9.33945-10^-5T²-2.16759-10^-7T³+2.91795-10^-10T⁴.本文还分析了Si₃N₄同质异相体在高压下的态密度和能带.在α-Si₃N₄中主要是Si-s, p和N-s,p的轨道杂化对晶体的稳定性起作用.α和β-Si₃N₄都具有Γ_V-Γ_C类型的间接带隙(分别是4.9~eV和4.4~eV)而γ-Si₃N₄具有直接带隙(3.9~eV). 研究还发现α-Si₃N₄和β-Si₃N₄的价带顶分别沿着Γ-M和Γ-A方向.本文的计算结果和已有的实验数据是一致的.     

Influence of cobalt on the structural and magnetic Inhomogeneities, phase transitions, and magnetoresistive properties of La0.6Sr0.2Mn1.2 ? x Co x O3 ± δ

The structure and properties of magnetoresistive ceramics La_0.6Sr_0.2Mn_{1.2 − x} Co _x O3 ± δ (x = 0−0.3) sintered at a temperature of 1200°C are investigated using x-ray diffraction, resistance, and magnetic (χ _ac , M, ⁵⁵Mn NMR) measurements. It is shown that the samples contain the rhombohedral (R c) perovskite (90%) and tetragonal (I4₁/amd) hausmannite (10%) phases. The lattice parameters of these phases decrease with an increase in the cobalt content x. The real perovskite structure involves point defects (anion and cation vacancies) and nanostructured defects of the cluster type. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra confirms the high-frequency electron-hole exchange between Mn³⁺ and Mn⁴⁺ ions and a local inhomogeneity of their environment by other ions and defects of the point and cluster types. An increase in the Co content leads to an increase in the electrical resistivity, an enhancement of the magnetoresistance (MR) effect, and a decrease in the magnetic susceptibility and the temperatures of the metal-semiconductor (T _ms ) and ferromagnetic-paramagnetic (T _C) phase transitions due to the suppression of the exchange interaction between Mn³⁺ and Mn⁴⁺ ions by vacancies and clusters. The introduction of cobalt results in a decrease in the ferromagnetic component and the activation energy. The magnetoresistance effect in the vicinity of the phase transition temperatures T _ms and T _C is associated with the scattering of charge carriers from intracrystallite inhomogeneities of the lattice, and the low-temperature magnetoresistance effect is governed by the tunneling at the intercrystalline boundaries. Original Russian Text ? A.V. Pashchenko, V.P. Pashchenko, A.A. Shemyakov, N.G. Kisel’, V.K. Prokopenko, Yu.F. Revenko, A.G. Sil’cheva, V.P. Dyakonov, H. Szymczak, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 7, pp. 1257–1262.