First-principles study of structural and thermodynamic properties of osmium

We employ the first-principles plane wave pseudopotential density functional theory method to calculate the equilibrium lattice parameters of osmium and the thermodynamic properties of hcp structure osmium. The obtained lattice parameters are in good agreement with the experimental data investigated up to 58.2 GPa using radial X-ray diffraction (RXRD) together with lattice strain theory in a diamond-anvil cell and the available theoretical data of others. Through the quasi-harmonic Debye model, the dependencies of the normalized lattice parameters a/a₀ and c/c₀ on pressure P, the normalized primitive volume V/V₀ on pressure P, the Debye temperature Θ_D and the heat capacity C_V on pressure P and temperature T, as well as the variation of the thermal expansion α with temperature and pressure are obtained successfully.     

Pressure effect on structural,electronic and thermodynamic investigations of europium filled skutterudite EuFe4Sb12: LDA and LSDA approximations

Numerical calculations based on the full potential muffin-tin orbitals method (FP-LMTO) within the local density approximation (LDA) and the local spin-density approximation (LSDA) to investigate the structural, electronic and thermodynamic properties of filled skutterudite EuFe₄Sb₁₂ are presented. The electronic band structure and density of states profiles prove that this material is a conductor. The present investigation is also extended to the elastic constants, such as the bulk modulus B, anisotropy factor A, shear modulus G, young's modulus E, Poisson's ratio ν, and the B/G ratio with pressure in the range of 0–40 GPa. The sound velocities and Debye temperatures are also predicted from the above constants. The variations of the primitive cell volume, expansion coefficient α, bulk modulus B, heat capacity (C_p and C_v), Debye temperature θ_D, Helmholtz free energy A, Gibbs free energy G, entropy S, and internal energy U with pressure and temperature in the range 0–3000 K are calculated successfully.     

Effect of doping on cohesive and thermophysical properties of MgB2

The effects of doping Al and Mn on the cohesive and thermophysical properties of MgB₂ have been investigated using a Rigid Ion Model (RIM). The interatomic potential of this model includes contributions from the long-range Coulomb attraction and the short-range overlap repulsion and the van der Waals attraction. This model has been applied to describe the temperature dependence of the specific heat of MgB₂, Mg_1−xAl_xB₂ (x = 0.1–0.9) and Mg_1−xMn_xB₂ (x = 0.01–0.04) in the temperature range 5 K ⩽ T ⩽ 1000 K. The calculated results on cohesive energy (ϕ), Bulk modulus (B_T), molecular force constant (f), Restrahalen frequency (ν₀), Debye temperature (Θ_D) and Gruneisen parameter (γ) are also reported for these materials. Our results on Bulk modulus, Restrahalen frequency and Debye temperature are closer to the available experimental data. The comparison between our calculated and available experimental results on the specific heat at constant volume for MgB₂ and Mg_1−xAl_xB₂ (x = 0.1–0.4), particularly, at lower temperatures has shown almost an excellent agreement. The trend of variation of the specific heat with temperature is more or less similar in pure and doped MgB₂.     

Novel BTlGaN semiconducting materials for infrared opto-electronic devices

BTlGaN quaternary alloys are proposed as new semiconductor materials for infrared opto-electronic applications. The structural and opto-electronic properties of zinc blende B_xTl_yGa_1−x−yN alloys lattice matched to GaN with (0 ⩽ x and y ⩽ 0.187) are studied using density functional theory (DFT) within full-potential linearized augmented plane wave (FP-LAPW) method. The calculated structural parameters such as lattice constant a₀ and bulk modulus B₀ are found to be in good agreement with experimental data using the new form of generalized gradient approximation (GGA-WC). The band gaps of the compounds are also found very close to the experimental results using the recently developed Tran–Blaha-modified Becke–Johnson (TB-mBJ) exchange potential. A quaternary B_xTl_yGa_1−x−yN is expected to be lattice matched to the GaN substrate with concentrations x = 0.125 and y = 0.187 allows to produce high interface layers quality. It has been found that B incorporation into BTlGaN does not significantly affect the band gap, while the addition of dilute Tl content leads to induce a strong reduction of the band gap, which in turn increases the emission wavelengths to the infrared region. The refractivity, reflectivity and absorption coefficient of these alloys were investigated. BTlGaN/GaN is an interesting new material to be used as active layer/barriers in quantum wells suitable for realizing advanced Laser Diodes and Light-Emitting Diodes as new sources of light emitting in the infrared spectrum region.     

Insight into structural,mechanical, electronic and thermodynamic properties of intermetallic phases in Zr–Sn system from first-principles calculations

The structural, phase stabilities, mechanical, electronic and thermodynamic properties of intermetallic phases in Zr–Sn system are investigated by using first-principles method. The equilibrium lattice constants, enthalpy of formation (ΔH^form) and elastic constants are obtained and compared with available experimental and theoretical data. The configuration of Zr₄Sn is measured with reasonable precision. The ΔH^form of five hypothetical structures are obtained in order to find possible metastable phase for Zr–Sn system. The mechanical properties, including bulk modulus, shear modulus, Young's modulus and Poisson's ratio, are calculated by Voigt–Reuss–Hill approximation and the Zr₅Sn₄ and Zr₅Sn₃ show excellent mechanical properties. The electronic density of states for Zr₅Sn₄, Zr₅Sn₃ and cP8-Zr₃Sn are calculated to further investigate the stability of intermetallic compounds. Through the quasi-harmonic Debye model, the Debye temperature, heat capacity and thermal expansion coefficient under temperature of 0–300 K and pressure of 0–50 GPa for Zr₅Sn₃ and Zr₅Sn₄ are deeply investigated.     

Correlation between structural and superconducting properties of nano-granular disordered Nb thin films

We report on low temperature transport measurements on nano-granular Nb thin films deposited on Si (1 0 0) substrates using DC magnetron sputtering. The superconducting transition temperature (T_c) is found to decrease monotonically with the increase of the lattice parameter (a) irrespective of its thickness and grain size. The superconducting transition temperature is found to depend only on the lattice parameter whereas the normal state resistivity depends both on lattice parameter and the details of the sample morphology. We have modeled this T_c variation with lattice expansion in terms of Debye temperature reduction using Morse potential as the interatomic potential in Nb.     

Elastic and electronic properties of YNi2B2C under pressure from first principles

The elastic and electronic structure properties of YNi₂B₂C under pressure are investigated by performing the generalized gradient approximation (GGA) and local density approximation (LDA) correction scheme in the frame of density functional theory (DFT). The pressure dependences of the normalized lattice parameters a/a₀ and c/c₀, the ratio c/a, and the normalized primitive volume V/V₀ of YNi₂B₂C are also obtained. The lattice constants and bulk modulus obtained are in agreement with the available experimental and other theoretical data. We have also studied the pressure dependences of elastic properties. It is found that, as pressure increases, the elastic constants C₁₁, C₃₃, C₆₆, C₁₂, and C₁₃ increase, the variation of elastic constant C₄₄ is not obvious. Moreover, our compressional and shear wave velocities V_L=6.99 km/s and V_S=3.67 km/s as well as the Debye temperature Θ=549.7 K at 0 GPa compare favorably with the available experimental data. The pressure dependences of band structures, energy gap and density of states are also investigated.     

Improved electrical parameters of vacuum annealed Ni/4H-SiC (0 0 0 1) Schottky barrier diode

The reported work has been focused on the improvement of electrical parameters of Schottky diode using vacuum annealing at mild temperature in Ar gas ambient. Nickel Schottky barrier diodes were fabricated on 50 μm epitaxial layer of n-type 4H-SiC (0 0 0 1) substrate. The values of leakage current, Schottky barrier height (?_B), ideality factor (η) and density of interface states (N_SS) were obtained from experimentally measured current–voltage (I–V) and capacitance–voltage (C–V) characteristics before and after vacuum annealing treatment. The data revealed that ?_B, η and reverse leakage current for the as-processed diodes are 1.25 eV, 1.6 and 1.2 nA (at ?100 V), respectively, while for vacuum annealed diodes these parameters are 1.36 eV, 1.3 and 900 pA (at same reverse voltage). Improved characteristics have been resulted under the influence of vacuum annealing because of lesser number of minority carrier generation due to incessant reduction of number of available discrete energy levels in the bandgap of 4H-SiC substrate and lesser number of interface states density at Ni/4H-SiC (0 0 0 1) interface.     

Structural,vibrational study and superprotonic behavior of a new mixed dipotassium hydrogenselenate dihydrogenphosphate K2(HSeO4)1.5(H2PO4)0.5

Ongoing studies of the KHSeO₄–KH₂PO₄ system aiming at developing novel proton conducting solids resulted in the new compound K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO₄⁻ and disordered (H_xSe/P)O₄⁻ tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H⁺ protons hopping mechanism.     

Elastic stability and electronic structure of tantalum boride investigated via first-principles density functional calculations

The elastic properties, electronic structure and thermodynamic behavior of the TaB have been investigated for the first time in this work. Using first-principles plane-wave ultrasoft-pseudopotential density functional theory (DFT), the ground state properties and equation of state of TaB have been obtained. The average zero-pressure bulk modulus of TaB is 302 GPa. By analyzing the elastically anisotropic behavior and the relative structure parameters of TaB, we found that the crystal cell along the b-axis was more compressible than along the a and c axes. The calculated ratio of bulk modulus and shear modulus (B/G) for TaB is 1.58, demonstrating that TaB is rather brittle. From the elastic stiffness constants, we found that TaB in the Cmcm phase is mechanically stable. The calculated hardness of TaB is 28.6 GPa which is close to the previous data. Moreover, using the Gibbs 2 model, the thermodynamic properties such as the thermal expansion and Debye temperature of TaB have been obtained firstly. At the ambient temperature, the Debye temperatures of TaB are 792 K and 845 K from GGA calculation and LDA calculation, respectively.     

Theoretical investigations of structural, elastic and thermodynamic properties for PtN2 under high pressure

We have investigated structural and elastic properties of PtN₂ under high pressures using norm-conserving pseudopotentials within the local density approximation (LDA) in the frame of density-functional theory. Calculated results of PtN₂ are in agreement with experimental and available theoretical values. The a/a₀, V/V₀, ductility/brittleness, elastic constants C_ij, shear modulus C′, bulk modulus B, shear modulus G, Young's modulus E, Poisson's ratio σ and anisotropy factor A as a function of applied pressure are presented. Through the quasi-harmonic Debye model, we also study thermodynamic properties of PtN₂. The thermal expansion versus temperature and pressure, thermodynamic parameters X (X=Debye temperature or specific heat) with varying pressure P, and heat capacity of PtN₂ at various pressures and temperatures are estimated.     

Electret properties of ethylene–propylene random co-polymer

Thermally stimulated current (TSC) spectra were examined for ethylene–propylene (EP) random co-polymer at different charging voltages V_p with positive and negative polarities. Observed TSC spectra showed two well-separated TSC bands, B_L and B_H, which respectively appeared in the temperature regions below and above 100 °C. Observed V_p dependence of B_L was quite different from that of typical polypropylene homo-polymer: As V_p increased, B_L band grew keeping its peak position same at 65 °C, and the band shape unchanged, as if the traps responsible for the B_L band are a single set of traps with the same trap depth and capture cross section. The trap depth of B_L was about 1.9 eV and 1.7 eV for positively charged EP and talc-containing EP samples, respectively. EP samples also showed unique TSC bands above 100 °C: one is a narrow TSC band peaked at 120 °C and the other is an unusual TSC band which was non-vanishing even at 165 °C just before destruction of samples by their melting. Consequently, the utmost stable charge density in EP co-polymer above 100 °C was found to be 3.5 × 10^?4 C/m² and 6.0 × 10 ^?4 C/m² for positively and negatively charged samples, respectively. These equivalent surface charge densities are much larger than those of usual polypropylene homo-polymer.     

Crystal chemistry and physical properties of the ternary compounds RE5B4C5 (RE=Ce,Pr, Nd)

The ternary rare-earth metal boride carbides RE₅B₄C₅ (RE=Ce, Pr, Nd) were prepared by arc melting the mixtures of the pure elements and subsequent annealing at 1270 K. Their crystal structures were determined from single crystal X-ray diffraction data. They crystallize in the Ce₅B₄C₅ type of structure (space group Pna2₁, Z=8). Two new compounds were found, Pr₅B₄C₅: a=24.592(2) Å, b=8.4563(5) Å, c=8.4918(5) Å, R₁=0.043 (wR₂=0.076) for 2871 reflections with I_o?2σ(I_o)); for Nd₅B₄C₅: a=24.301(1) Å, b=8.3126(5) Å, c=8.3545(4) Å, R₁=0.035 (wR₂=0.069) for 3707 reflections with I_o?2σ(I_o)). Its structural arrangement consists of a three-dimensional framework of rare-earth atoms resulting from the stacking of slightly corrugated two-dimensional square nets, leading to voids filled with B₄C₄, B₃C₃, BC₂ finite chains and isolated carbon atoms. Ce₅B₄C₅ is an antiferromagnet at 5 K followed by a metamagnetic transition in elevated external fields. Pr₅B₄C₅ and Nd₅B₄C₅ are ferromagnets below T_C=12 and 15 K, respectively.     

Electronic and high pressure elastic properties of RECd and REHg (RE=Sc,La and Yb) intermetallic compounds

Structural, electronic, elastic and mechanical properties of Cd and Hg based rare earth intermetallics (RECd and REHg; RE=Sc, La and Yb) have been investigated using the full-potential linearized augmented plane-wave (FP-LAPW) method within the density-functional theory (DFT). The ground state properties such as lattice constant (a₀), bulk modulus (B) and its pressure derivative (B′) have been obtained using optimization method and are found in good agreement with the available experimental results. The calculated enthalpy of formation shows that LaHg has the strongest alloying ability and structural stability. The electronic band structures and density of states reveal the metallic character of these compounds. The structural stability mechanism is also explained through the electronic structures of these compounds. The chemical bonding between rare earth atoms and Cd, Hg is interpreted by the charge density plots along (1 1 0) direction. The elastic constants are predicted from which all the related mechanical properties like Poisson’s ratio (σ), Young’s modulus (E), shear modulus (G_H) and anisotropy factor (A) are calculated. The ductility/brittleness of these intermetallics is predicted. Chen’s method has been used to predict the Vicker’s hardness of RECd and REHg compounds. The pressure variation of the elastic constants is also reported in their B₂ phase.     

Elastic and thermodynamic properties of CaB6 under pressure from first principles

The elastic and thermodynamic properties of CsCl-type structure CaB₆ under high pressure are investigated by first-principles calculations based on plane-wave pseudopotential density functional theory method within the generalized gradient approximation (GGA). The calculated lattice parameters of CaB₆ under zero pressure and zero temperature are in good agreement with the existing experimental data and other theoretical data. The pressure dependences of the elastic constants, bulk modulus B (GPa), and its pressure derivative B′, shear modulus G, Young's modulus E, elastic Debye temperature Θ_B, Zener's anisotropy parameter A, Poisson ratios σ, and Kleinmann parameter ζ are also presented. An analysis for the calculated elastic constants has been made to reveal the mechanical stability of CaB₆ up to 100 GPa. The thermodynamic properties of the CsCl-type structure CaB₆ are predicted using the quasi-harmonic Debye model. The pressure-volume-temperature (P-V-T) relationship, the variations of the heat capacity C_V, Debye temperature Θ_D, and the thermal expansion α with pressure P and temperature T, as well as the Grüneisen parameters γ are obtained systematically in the ranges of 0-100 GPa and 0-2000 K.     

Antiferromagnetic phase transition in garnet-type AgCa2Mn2V3O12 and NaPb2Mn2V3O12

Ferrimagnetism has been extensively studied in garnets, whereas it is rare to find the antiferromagnet. Present work will demonstrate antiferromagnetism in the two Mn–V-garnets. Antiferromagnetic phase transition in AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ has been found, where the magnetic Mn²⁺ ions locate only on octahedral A site. The heat capacity shows sharp peak due to antiferromagnetic order with the Néel temperature T_N=23.8 K for AgCa₂Mn₂V₃O₁₂ and T_N=14.2 K for NaPb₂Mn₂V₃O₁₂. The magnetic entropy change over a temperature range 0–50 K is 13.9 J K^?1 mol-Mn²⁺-ions^?1 for AgCa₂Mn₂V₃O₁₂ and 13.6 J K^?1 mol-Mn²⁺-ions^?1 for NaPb₂Mn₂V₃O₁₂, which are in good agreement with calculated value of Mn²⁺ ion with spin S=5/2. The magnetic susceptibility shows the Curie–Weiss behavior over the range 29–350 K. The effective magnetic moment μ_eff and the Weiss constant θ are μ_eff=6.20 μ_B Mn²⁺-ion^?1 and θ=?34.1 K (antiferromagnetic sign) for AgCa₂Mn₂V₃O₁₂ and μ_eff=6.02 μ_B Mn²⁺-ion^?1 and θ=?20.8 K for NaPb₂Mn₂V₃O₁₂.     

Stabilization of high spin FCC Fe in (Fe/Pd)n multilayers

Polycrystalline (Fe/Pd)_n multilayers are grown onto sapphire substrates at room temperature in a UHV system. The number of periods n=40 and the thickness of Pd layers of t_Pd=4 nm are kept constant, whereas the thickness of the Fe layers is varied from 1.5 to 5 nm. Structural properties are studied by in situ reflection high energy diffraction (RHEED), scanning tunnelling microscopy (STM) and ex situ by X-ray diffraction at small angles and large angles. Analyzing the experimental data using the program SUPREX we obtain interplanar distances of d_Fe=2.03±0.01 Å for an Fe layer thickness larger than about 2.5 nm as expected for (1 1 0) planes of BCC Fe. For Fe layers with thicknesses less than about 2.5 nm the interplanar distance is d_Fe=2.1±0.01 Å, which is close to the distance between (1 1 1) planes of FCC Fe with a lattice parameter of a=3.64 Å. Magnetic susceptibility measurements at temperatures between 1.5 and 300 K for (Fe/Pd)_n multilayers with FCC Fe yield a magnetic moment per Fe atom of μ=2.7±0.1 μ_B, which is about 20% larger compared to μ=2.2 μ_B for BCC Fe. We show that the occurrence of the large magnetic moment originates from FCC Fe being in the high spin (HS) state rather than from polarization effects of Pd at Fe/Pd interfaces.     

Annealing effects on the crystal structure and physical properties of FeSe1−xTex (0.6 ≦ x ≦ 1) single crystals

Annealing effects of FeSe_1?xTe_x (0.6 ≦ x ≦ 1) single crystals have been investigated from measurements of the powder X-ray diffraction and specific heat. Through the annealing, several peaks of powder X-ray diffraction have become sharp and a clean jump of the specific-heat at the superconducting (SC) transition temperature, T_c, has been observed for x = 0.6–0.9, indicating bulk superconductivity. For annealed single-crystals of x = 0.6–0.8, the SC condensation energy, U₀, and the SC gap, Δ₀, at 0 K have been estimated as ～1.8 J/mol and 2.3–2.5 meV, respectively. The value of 2Δ₀/k_BT_c is 3.9–4.5, indicating a little strong-coupling superconductivity. Both the electronic specific-heat coefficient in the normal state, γ_n, and the residual electronic specific-heat coefficient in the SC state, γ₀, have been found to show significant x dependence. The values of γ_n are much larger than those estimated from the band calculation.     

Experimental and theoretical studies on bis(glycine) lithium nitrate (BGLiN): A physico-chemical approach

Good quality and bulk size single crystal (size: 20×13×8 mm³) of bis(glycine) lithium nitrate (BGLiN) was grown by a slow evaporation solution technique from the aqueous solutions at constant temperature i.e. 27 °C using synthesized materials. Crystal system and lattice parameters were determined by single crystals as well as powder X-ray diffraction analysis. The lattice parameters of the titled compound are a=10.0223 Å, b=5.0343 Å, c=17.0510 Å, and V=860.312 Å³ and it crystallized in an orthorhombic system with space group Pca2₁ obtained by single crystal XRD. Elemental composition was confirmed by energy dispersive X-ray spectroscopic analysis. Optical absorption spectrum was recorded and various optical parameters such as optical transmission (~60%), and optical band gap (4.998 eV) were calculated. Photoluminescence study shows that the grown crystal is free from major defects. Crystalline perfection of the grown crystal was assessed and found good. Ground state optimized geometry has been obtained by using DFT with 6-31G(d,p) basis set. HOMO and LUMO energy gap was found to be 6.01 eV and dipole moment was 1.65 D.     

Magnetostriction and magnetization measurements on a DyNi2B2C single crystal in a magnetic field

In order to investigate the interactions between lattice properties, magnetic ordering and superconductivity of DyNi₂B₂C, thermal expansion, magnetostriction and magnetization measurements were performed for T=2–15 K and for μ₀H=0–3 T on a single crystal in the crystallographic [1 1 0] direction. A magnetic phase diagram is derived that shows two phases (AF1 and AF2) in the narrow region between the zero-field antiferromagnetic AF and the induced ferromagnetic state FM. Moreover, it is characterized by a large-field hysteresis. This behaviour can be described by a two domain magnetic state. The metamagnetic structure AF1 with about a quarter of the saturated magnetization is responsible for suppressing the superconductivity in DyNi₂B₂C because of its ferromagnetic component.