Trends in the band-gap pressure coefficients and bulk moduli in different structures of ZnGa2S4, ZnGa2Se4 and ZnGa2Te4

We have performed a first-principles investigation for the family of compounds ZnGa2X4 (X = S, Se, Te). The properties of two possible structures, defect chalcopyrite and defect famatinite are both calculated. We reveal that ZnGa2S4 and ZnGa2Se4 have direct band gaps, while ZnGa2Te4 has an indirect band gap. The local density approximation band gaps are found to be very different in two structures, while the lattice parameters and bulk moduli are similar. We extend Cohen’s empirical formula for zinc-blende compounds to this family of compounds. The pressure coefficients are calculated and metallization pressures are discussed. We find that agi remains fairly constant when the group-Ⅵ element X is varied in ZnGa2X4 (Ⅱ-Ⅲ2 -Ⅵ4 ).     

Mechanical Properties and Electronic Structures of Cotunnite TiO2

Based on the first-principles plane-wave basis pseudopotential calculations, we investigate mechanical properties and electronic structures of the hardest known oxide, cotunnite TiO2. The calculated results show that cotunnite TiO2 has the highest bulk modulus （348 GPa） and hardness （32 GPa） among the high-pressure phases of TiO2, but its mechanical properties are not superior to those of c-BN. Moreover, the high hardness of cotunnite TiO2 can be understood from both the dense crystal structure （high valence electron density and short bond lengths） and the unusual mixtures of covalent and ionic bonding of Ti-O.     

Electronic Structure and Elastic Properties of Ti3AlC from First-Principles Calculations

We perform a first-principles study on the electronic structure and elastic properties of TiaA1C with an antiperovskite structure. The absence of band gap at the Fermi level and the finite value of the density of states at the Fermi energy reveal the metallic behavior of this compound. The elastic constants of Ti3AlC are derived yielding c11 = 356 GPa, c12 = 55 GPa, c44 = 157 GPa. The bulk modulus B, shear modulus G and Young＇s modulus E are determined to be 156, 151 and 342 GPa, respectively. These properties are compared with those of Ti3AlC2 and Ti2AlC with a layered structure in the Ti-Al-C system and FeaAlC with the same antiperovskite structure.     

Structural, Elastic and Electronic Properties of ReO2

Structural, elastic and electronic properties of ReO₂ are investigated by first-principles calculations based on density functional theory. The ground stateof ReO₂ has an orthorhombic symmetry which belongs to space group Pbcn with a=4.7868Å b=5.5736Å, and c=4.5322Å. The calculated bulk moduli are 322GPa, 353GPa, and 345GPa for orthorhombic, tetragonal, and monoclinic ReO₂, respectively, indicating that ReO₂ has a strong incompressibility. ReO₂ is a metal ductile solid and presents large elastic anisotropy. The obtained Debye temperatures are 850K for orthorhombic, 785K for tetragonal, and 791K for monoclinic ReO₂.     

Optical and structural properties of nanosized ZnGa2O4:Cr phosphor

Nanosized ZnGa₂O₄:Cr³⁺ powder is synthesized through hydrothermal method. The average particle size is 20 nm and they are spherical in shape. The excitation band from the charge transfer between Cr³⁺-O²⁻ shows a blueshift behavior due to quantum confinement effect. X-ray diffraction pattern, Fourier transform-infrared spectrum, and electron paramagnetic resonance signal indicate that nanosized ZnGa₂O₄:Cr³⁺ phosphor shows many defect-related energy states and heavy lattice distortion in comparison with bulk ZnGa₂O₄:Cr³⁺ phosphor. Many defect states result in more nonradiative loss and shorter decay time.     

Ab initio study of the structural,electronic, elastic and magnetic properties of Cu2GdIn,Ag2GdIn and Au2GdIn

We preformed first-principle calculations for the structural, electronic, elastic and magnetic properties of Cu₂GdIn, Ag₂GdIn and Au₂GdIn using the full-potential linearized augmented plane wave (FP-LAPW) scheme within the generalized gradient approximation by Wu and Cohen (GGA-WC), GGA+U, the local spin density approximation (LSDA) and LSDA+U. The lattice parameters, the bulk modulus and its pressure derivative and the elastic constants were determined. Also, we present the band structures and the densities of states. The electronic structures of the ferromagnetic configuration for Heusler compounds (X₂GdIn) have a metallic character. The magnetic moments were mostly contributed by the rare-earth Gd 4f ion.     

Effect of In-Doping on Electronic Structure and Optical Properties of Sr2TiO4

The effect of In doping on the electronic structure and optical properties of Sr2 TiO4 is investigated by a firstprinciples calculation of plane wave ultrasoft pseudopotentials based on density functional theory. The calculated results reveal that corner-shared TiO6 octahedra dominate the main electronic properties of Sr2TiO4 and the covalency of the Ti-O（1） bond in the ab plane is stronger than that of the Ti-O（2） bond along the c-axis. After In doping, there is a little lattice expansion in Sr2In0.125 Ti0.875 O4 and the interaction between the Ti-O bond near the impurity In atom is weakened. The binding energies of Sr2TiO4 and Sr2In0.125Ti0.875O4 estimated from the electronic structure calculations indicate that the crystal structure of Sr2In0.125 Ti0.875 O4 is still stable after doping, but its stability is lower than that of undoped Sr2TiO4. Moreover, the valence bands （VBs） of the Sr2In0.125Ti0.875O4 system consist of O 2p and In 4d states, and the mixing of O 2p and In 4d states makes the top VBs shift significantly to high energies, resulting in visible light absorption. The adsorption of visible light is of practical importance for the application of St2 TiO4 as a photocatalyst.     

Full-relativistic calculation of electronic structure of Zr2AlC and Zr2AlN

We have employed a full-relativistic version of an all-electron full-potential linearized-augmented plane-wave method in the local density approximation to investigate the electronic structure of nanolaminate Zr₂AlX (X=C and N). The Zr 4d electrons are treated as valence electrons. We have investigated the lattice parameters, bulk moduli, band structures, total and partial densities of states and charge densities. It is demonstrated that the strength and electrical transport properties in these materials are principally governed by the metallic planes.     

高压下SiO_2的第一性原理计算

基于密度泛函理论(DFT)的第一性原理,采用Hartree-Fork(HF)方法,分别计算了Si O2的α-石英结构、金红石结构以及氯化钙结构的总能量随体积的变化关系。利用Murnaghan状态方程,通过能量和体积拟合,得到了3种结构的体变模量及其对压强的一阶导数。计算结果表明,随着压强的增加,Si O2会从α-石英结构转变为金红石结构,与实验结果和其它理论结果一致;金红石结构与氯化钙结构之间不存在相变,可以共存。此外,对具有α-石英结构的Si O2的晶格常数、电子态密度和带隙随压强的变化关系进行了计算和分析,结果表明:加压作用下,能带向高能方向移动,Si─O键缩短,电子数转移增加,带隙展宽,电荷发生重新分布。     

Superconductivity in Hole-Doped （S1-xKx）Fe2As2

A series of layered （Sr1-xKx）Fe2As2 compounds with nominal x = 0-0.40 are synthesized by solid state reaction method. Similar to other parent compounds of iron-based pnictide superconductors, pure SrFe2As2 shows a strong resistivity anomaly near 210 K, which was ascribed to the spin-density-wave instability. The anomaly temperature is much higher than those observed in LaOFeAs and BaFe2As2, the two prototype parent compounds with ZrCuSiAs- and ThCr2Si2-type structures. K-doping strongly suppresses this anomaly and induces superconductivity. Like in the case of K-doped BaFe2As2, sharp superconducting transitions at Tc ～ 38 K is observed. We perform the Hall coefficient measurement, and confirm that the dominant carriers are hole-type. The carrier density is enhanced by a factor of 3 in comparison to F-doped LaOFeAs superconductor.     

Electronic Structure and Optical Properties of La-Doped SrTiO3 and Sr2TiO4 by Density Function Theory

The effect of La doping on the electronic structure and optical properties of SrTiO₃ and Sr₂TiO₄ is investigated by the first-principles calculation of plane wave ultrasoft pseudopotential based on the density function theory (DFT). The calculated results reveal that the electron doping in the case of Sr_0.875La_0.125TiO₃ and Sr_1.875La_0.125TiO₄ can be described within the rigid band model. The La³⁺ ions fully acts as electron donors in Sr_0.875La_0.125TiO₃ and Sr_1.875La_0.125TiO₄ systems and the Fermi level shifts further into the conduction bands (CBs) for Sr_1.875La_0.125TiO₄ compared to Sr_0.875La_0.125TiO₃. The two systems exhibit n-type degenerate semiconductor features. At the same time, the density of states (DOS) of the two systems shift towards low energies and the optical band gaps are broadened. The Sr_1.875La_0.125TiO₄ is highly transparent with the transmittance about 90% in the visible range, which is larger than that of Sr_0.875La_0.125TiO₃(85%). The wide band gap, small transition probability and weak absorption due to the low partial density of states (PDOS) of impurity in the Fermi level result in the optical transparency of the films...     

Luminescence enhancement of ZnGa2O4:Mn by Ge and Li doping

Structural and optical properties of ZnGa₂O₄:Ge⁴⁺ and ZnGa₂O₄:Ge⁴⁺, Li⁺, Mn²⁺ phosphors were investigated by using X-ray diffraction (XRD), photoluminescence (PL) and cathodoluminescence (CL) measurements. The XRD patterns show that Ge-doped ZnGa₂O₄ has a spinel phase and its lattice constant increases with respect to ZnGa₂O₄. Emission wavelength shifts from 400 to 360 nm in comparison with ZnGa₂O₄ when Ge is doped in ZnGa₂O₄ and a peak related with oxygen defect was observed in Ge-doped ZnGa₂O₄. The CL luminance of ZnGa₂O₄:Ge⁴⁺, Li⁺, Mn²⁺ phosphors is seven times brighter than that of ZnGa₂O₄:Mn²⁺. This drastic luminance improvement can be attributed to Ge doping in ZnGa₂O₄ acting as donor ion and Li doping resulting in increasing conductivity of ZnGa₂O₄. These results indicate that ZnGa₂O₄:Ge⁴⁺, Li⁺, Mn²⁺ phosphors hold promise for potential applications in field-emission display devices with high brightness operating in green spectral regions.     

Characterization of ZnGa2O4:Mn nanophosphor synthesized by the solvothermal method in 1,4-butanediol-water system

We characterized ZnGa₂O₄:Mn²⁺ (ZnGa₂O₄—zinc gallate) nanophosphor synthesized by the solvothermal method in 1,4-butanediol-containing water to increase the amount of Mn²⁺ ions incorporated in the ZnGa₂O₄ matrix without post-heat treatment. We investigated the influence of water content in the solvent on the photoluminescence (PL) intensity and the Mn amount, the latter being measured by X-ray fluorescence analysis and electron paramagnetic resonance spectroscopy. The PL intensity per Mn amount reached the maximum at the 50 wt% water content. The addition of water promotes repeated dissolution and precipitation, resulting in homogeneous Mn²⁺ distribution in the ZnGa₂O₄ matrix. This suggests that the solvothermal method in the 1,4-butanediol-water system is useful for increasing the amount of Mn²⁺ ions incorporated in the ZnGa₂O₄ matrix without post-heat treatment. At the water content >50 wt%, the decrease in PL intensity is attributed to the optical absorption of the by-product, MnOOH.     

The origin of emission color of reduced and oxidized ZnGa2O4 phosphors

The Ga-O octahedral structure of the reduced and the oxidized ZnGa₂O₄ phosphors was investigated using Reitveld refinement. The correlation between the structural change and the changing emission color was studied. The emission peak shifts to shorter wavelength because of the more contribution of a variation of ligand charge than that of bond length to crystal field. The blueshift behavior of the reduced ZnGa₂O₄ was also observed in Ge⁴⁺-doped ZnGa₂O₄. In addition, Li⁺ ions doping in ZnGa₂O₄ generate extra oxygen ions, and Li⁺-doped ZnGa₂O₄ shows the same emission color as the oxidized ZnGa₂O₄.     

Novel ultraviolet photoluminescence of ZnO/ZnGa2O4 composite layers

ZnO/ZnGa₂O₄ composite layers were synthesized by simple thermal oxidation of ZnS substrates with gallium in the air. The continuous-wave and time-resolved photoluminescence measurements for the composites were performed at room temperature. It is found that the visible deep level emission from ZnO in ZnO/ZnGa₂O₄ composite layer was almost suppressed. In addition, the UV emission with long lifetime was also observed in comparison with that of pure ZnO layer without ZnGa₂O₄.     

Elastic properties, thermal expansion coefficients and electronic structures of Ti0.75X0.25C carbides

Elastic properties, thermal expansion coefficients and electronic structures of Ti_0.75X_0.25C carbides (X=W, Mo, Ta, Nb, V, Hf, Zr, Cr and Al) were systematically investigated using ab initio density functional theory (DFT) calculations. The calculated elastic moduli, electronic structures and thermal expansion coefficients α(T) of pure TiC are in good agreement with experimental data and other DFT calculations. Based on a phenomenological formula, the trends of elastic properties and ductile/brittle behavior of Ti_0.75X_0.25C were analyzed. It was found that alloying elements W, Mo, Ta, Nb, V and Hf can increase elastic moduli, while Zr, Cr and Al reduce moduli. The nearly free electron model and Debye approximation were applied in the evaluation of α(T). The anharmonic effect was taken into account by including volume-dependent elastic moduli and Debye temperature. Results show that alloying additions of 3d V, 4d Zr and Mo slightly reduce α(T), while 3d Cr increases α(T), Al, 4d Nb, 5d Hf and W almost keep α(T) unchanged in Ti_0.75X_0.25C at high temperatures. The electronic structures of Ti_0.75X_0.25C were calculated and analyzed, and the electronic density of states was used to interpret variations of elastic properties and ductile/brittle behavior induced by alloying additions.     

Raman and X-Ray Investigation of Pyrope Garnet （Mg0.76Fe0.14Ca0.10）3Al2Si3O12 under High Pressure

The compressional behavlour of natural pyrope garnet is investigated by using angle-dlspersive synchrotron radiation x-ray diffraction and Raman spectroscopy in a diamond anvil cell at room temperature. The pressureinduced phase transition does not occur under given pressure. The equation of state of pyrope garnet is determined under pressure up to 25.3 GPa. The bulk modulus KTO is 199 GPa, with its first pressure derivative K′TO fixed to 4. The Raman spectra of pyrope garnet are studied. A new Raman peak nearly at 743 cm^-1 is observed in a bending vibration of the SiO4 tetrahedra frequency range at pressure of about 28 GPa. We suggest that the new Raman peak results from the lattice distortion of the SiO4 tetrahedra. All the Raman frequencies continuously increase with the increasing pressure. The average pressure derivative of the high frequency modes （650-1000 cm^-1） is larger than that of the low frequency （smaller than 650 cm^-1）. Based on these data, the mode Grǖneisen parameters for pyrope are obtained.     

Properties of a New Nonlinear Optical Crystal CdZn2B2O6

Cadmium dizinc diborate （CdZn2B2O6） single crystals have been grown for the first time. The crystal structure of CdZn2B2O6 is the same as that of the Cd3Zn3B4O12. The x-ray diffraction, infrared and Raman spectra, differential scanning calorimetry analysis and density indicate that the physical and chemical properties of both crystals are very similar. Especially, the nonlinear optical coefficients of CdZn2B2O6 and Cd3Zn3B4O12 crystals are 2.6 and 2.4 times as large as that of KH2PO4 crystal respectively. Chemical etching experiments indicated that these crystals are very stable in neutral solution and not hygroscopic in air at room temperature.     

Amorphization Induced High Magneto-Caloric Effect of Gd55Al20Ni25 Ternary Alloy

We report the amorphization induced high magneto-caloric effect （MCE） of recently developed Gd55Al15Ni30 bulk metallic glass （BMG）. The magnetic properties of the Gd55Al15Ni30 BMG are investigated in comparison with that of its crystalline counterpart. It is found that amorphization can increase the saturation magnetization and decrease the hysteresis of Gd55Al15Ni30 alloys, which indicate the possible enhancement of MCE. The magnetic entropy changes and the refrigerant capacity of the BMG as well as the crystalline samples is calculated directly from isothermal magnetic measurements. The results show the amorphization induced high MCE of the alloy and the excellent refrigerant efficiency of Gd55Al15Ni30 bulk metallic glass.     

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.