The structural, elastic and electronic properties of BiI3: First-principles calculations

The structural, elastic and electronic properties of BiI₃ are investigated using the first-principles pseudopotential calculations within the framework of density functional theory. The calculated equilibrium structural parameters agree well with the experimental values. The results show that rhombohedral R-3 structure is low enthalpy structure at zero pressure. R-3 structure will transform into SbI₃-type structure (space group P2₁/c) at about 7.0 GPa. At zero pressure, BiI₃ with R-3 symmetry meets the mechanical stability criteria, but BiI₃ with P-31 m symmetry is an unstable one mechanically. For R-3 structure, the obtained bulk, shear, and Young’s moduli are 25.6, 15.3 and 38.3 GPa, respectively. BiI₃ presents large elastic anisotropy. Debye temperature of R-3 structure calculated is 181 K. The metallization pressure of R-3 structure is about 133 GPa and that of predicted high pressure phase P2₁/c structure is about 61 GPa, indicating BiI₃’s potential application as a nuclear radiation detector under high pressure environment.     

Structural,elastic and mechanical properties of orthorhombic SrHfO3 under pressure from first-principles calculations

Structural, elastic and mechanical properties of orthorhombic SrHfO₃ under pressure have been investigated using the plane-wave ultrasoft pseudopotential technique based on the first-principles density functional theory. The calculated equilibrium lattice parameters and elastic constants of orthorhombic SrHfO₃ at zero pressure are in good agreement with the available experimental and calculational values. The lattice parameters, total enthalpy, elastic constants and mechanical stability of orthorhombic SrHfO₃ as a function of pressure were studied. With the increasing pressure, the lattice parameters and volume of orthorhombic SrHfO₃ decrease whereas the total enthalpy increases. Orthorhombic SrHfO₃ is mechanically stable with low pressure (<52.9 GPa) whereas that is mechanically instable with high pressure (>52.9 GPa). The bulk modulus, shear modulus, Young's modulus and mechanical anisotropy of orthorhombic SrHfO₃ as a function of pressure were analyzed. It is found that orthorhombic SrHfO₃ under pressure has larger bulk modulus, better ductility and less mechanical anisotropy than orthorhombic SrHfO₃ at 0 GPa.     

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.     

Structural and elastic properties of LaTiO3 under pressure

We investigate the structural and elastic properties of LaTiO₃ by the plane-wave pseudopotential density functional theory method. The lattice constants, bulk modulus and its pressure derivative are obtained. These properties in the equilibrium phase are well consistent with the available experimental data. The pressure dependence of the elastic constants, ductility, mechanical stabilities, sound velocity and Debye temperatures are investigated for the first time. From the ratio G/B, we conclude that LaTiO₃ is ductile at 0 GPa and becomes more ductile at high pressure. In addition, the anisotropy factors for every symmetry plane and axis as well as linear bulk modulus at diverse pressures have been obtained.     

Preparation of WO3 nanoparticles and application to NO2 sensor

WO₃ nanoparticles were prepared by evaporating tungsten filament under a low pressure of oxygen gas, namely, by a gas evaporation method. The crystal structure, morphology, and NO₂ gas sensing properties of WO₃ nanoparticles deposited under various oxygen pressures and annealed at different temperatures were investigated. The particles obtained were identified as monoclinic WO₃. The particle size increased with increasing oxygen pressure and with increasing annealing temperature. The sensitivity increased with decreasing particle size, irrespective of the oxygen pressure during deposition and annealing temperature. The highest sensitivity of 4700 to NO₂ at 1 ppm observed in this study was measured at a relatively low operating temperature of 50 °C; this sensitivity was observed for a sensor made of particles as small as 36 nm.     

Elasticity, electronic structure, chemical bonding and optical properties of monoclinic ZrO2 from first-principles

Structural parameters as well as elastic, electronic, bonding and optical properties of monoclinic ZrO₂ were investigated using the plane-wave ultrasoft pseudopotential technique based on the first-principles density-functional theory (DFT). The calculated structural properties and independent elastic constants of monoclinic ZrO₂ are in favorable agreement with previous work. We have derived the bulk and shear moduli, Young’s modulus and Poisson coefficients for monoclinic ZrO₂ and estimated the Debye temperature of monoclinic ZrO₂ from acoustic velocity. Electronic and bonding properties are studied from the calculation of band structure, densities of states and charge densities. Furthermore, in order to clarify the mechanism of optical transitions in monoclinic ZrO₂, the dielectric functions are calculated and analyzed by means of the electronic structure, which shows significant optical anisotropy in the components of polarization directions (1 0 0), (0 1 0) and (0 0 1).     

Structural and optical properties of Er, Yb co-doped Y2O3 thin films

Thin Er³⁺, Yb³⁺ co-doped Y₂O₃ films were grown on (1 0 0) YAG substrates by pulsed laser deposition. Ceramic targets having different active ion concentration were used for ablation. The influence of the rare-earth content and oxygen pressure applied during the deposition on the structural, morphological and optical properties of the films were investigated. The films deposited at the lower pressure, 1 Pa, and at 1/10 Er to Yb doping ratio are highly textured along the (1 1 1) direction of the Y₂O₃ cubic phase. In addition to the crystalline structure, these films possess smoother surface compared to those prepared at the higher pressure, 10 Pa. All other films are polycrystalline, consisting of cubic and monoclinic phases of Y₂O₃. The rougher surface of the films produced at the higher-pressure leads to higher scattering losses and different behavior of the reflectivity spectra. Optical anisotropy in the films of less than 0.004 was measured regardless of the monoclinic structure obtained. Waveguide losses of about 1 dB/cm at 633 nm were obtained for the films produced at the lower oxygen pressure.     

Structural, electronic and thermodynamic properties of cubic Zn3N2 under high pressure from first-principles calculations

The structural, electronic and thermodynamic properties of cubic Zn₃N₂ under hydrostatic pressure up to 80 GPa are investigated using the local density approximation method with pseudopotentials of the ab initio norm-conserving full separable Troullier-Martin scheme in the frame of density functional theory. The structural parameters obtained at ambient pressure are in agreement with experimental data and other theoretical results. The change of bond lengths of two different types of Zn-N bond with pressure suggests that the tetrahedral Zn-N bond is slightly less compressible than the octahedral bond. By fitting the calculated band gap, the first and second order pressure coefficients for the direct band gap ofthe Zn₃N₂ were determined to be 1.18×10⁻² eV/GPa and −2.4×10⁻⁴ eV/(GPa)², respectively. Based on the Mulliken population analysis, Zn₃N₂ was found to have a higher covalent character with increasing pressure. As temperature increases, heat capacity, enthalpy, product of temperature and entropy increase, whereas the Debye temperature and free energy decrease. The present study leads to a better understanding of how Zn₃N₂ materials respond to compression.     

The optical properties of HgS under high pressures

The DOS (density of states) and the optical properties of HgS under high pressure are studied with the first-principle computations. The change of the imaginary part, ε₂(ω), of the dielectric function shows that HgS tends to metallization with increasing pressure, and this well agrees with the band gap calculations and the conductivities measurement results in the previous work. Under the pressures below 15 GPa, ε₂(ω) is relatively anisotropic and tends to be more anisotropic with increasing pressure; while under the pressures above 15 GPa, the anisotropy decreases and finally becomes almost absolutely isotropic after the phase transition. The behavior of ε₂(ω) is strongly related to the structure change in the cinnabar to rocksalt phase transition process under high pressure.     

The electrical and magnetic properties of epitaxial orthorhombic YMnO3 thin films grown under various oxygen pressures

Orthorhombic YMnO₃ thin films were epitaxially grown on bare and LaNiO₃ buffered (0 0 1)-SrTiO₃ substrates by pulsed laser deposition under various oxygen pressures from 5 to 30 Pa. The crystal structure and microstructure of these films have been characterized by both X-ray diffractions and transmission electron microscopy. The leakage current, modeled as the space charge limited current (SCLC) mechanism, decreased significantly with the increase of oxygen content. It is further found that the magnetic property of films is greatly enhanced in YMnO₃ films grown under high oxygen pressure, which can be explained decreased oxygen vacancies. In addition, bipolar switching behavior was obtained only in the films grown under 30 Pa oxygen pressure, which is attributed to the decrease of voltage-driven oxygen vacancy migration.     

Effect of pressure on the energy band gaps of wurtzite GaN and AlN and electronic properties of their ternary alloys AlxGa1−xN

Using the Empirical Pseudopotential Method (EPM) combined with an improved Virtual Crystal Approximation (VCA), where the effect of compositional disorder is included as an effective periodic potential, we have calculated the electronic band structure of GaN and AlN under hydrostatic pressure up to 200 kbar and 160 kbar, respectively. The behavior of electronic properties of their alloys Al_xGa_1−xN in the wurtzite structure have been predicted at zero pressure, for the entire range of alloy concentrations.     

Effects of sputtering pressure on the field emission properties of N-doped SrTiO3 thin films coated on Si tip arrays

The influence of sputtering pressure on the electron emission properties of Si tips coated with N-doped SrTiO₃ ultrathin films was investigated. X-ray diffraction studies revealed that the N-doped SrTiO₃ films deposited at different pressures remain the perovskite structure. However, the threshold electric field of electron emission decreased markedly when the sputtering pressure is increased, and reached a minimum value of 17.37 V/μm while deposited at 1.6 Pa. The decrease in the threshold field is attributed to the narrowed band gap and the lowered surface energy of SrTiO₃ thin films with nitrogen doped, as confirmed using spectroscopic ellipsometry and water contact angle measurement. Furthermore, it is revealed using XPS that such sputtering pressure dependence is accompanied with the change of nitrogen bonding state in the films, which changes from poorly screened γ-N₂ state to atomic β-N state when the sputtering pressure is increased. A mechanism of bonding and band-forming was proposed for the enhanced electron emission with nitrogen incorporation in the sputtered SrTiO₃ films.     

First-principles study of structural,electronic, and optical properties of ZnSnO3

The structural, electronic, and optical properties of ZnSnO₃ were investigated using density functional theory within the generalized gradient approximation. The structure parameters obtained agree well with the experimental results. The electronic structures indicate that ZnSnO₃ is a semiconductor with a direct band gap of 1.0 eV. The calculated optical spectra can be assigned to contributions of the interband transitions from valence band O 2p levels to conduction band Sn 5s levels or higher conduction band Zn 3d levels in the low-energy region, and from O 2p to Sn 5p or Zn 4p conduction band in the high-energy region.     

First principles study of structural,phonon, optical,elastic and electronic properties of Y3Al5O12

Structural, phonon, optical, elastic and electronic properties of Y₃Al₅O₁₂ have been investigated by means of the first principles method with the Cambridge Serial Total Energy Package (CASTEP) code based on the density functional theory. The calculated lattice parameters, valence charge density, bond length and single crystal elastic properties at zero pressure are in good agreement with the available experimental data. The close agreement with the experimental values provides a good confirmation of the reliability of the calculations. Optical, elastic and phonon properties of Y₃Al₅O₁₂ under pressures are performed. The results that are obtained show the changes of optical and elastic properties under the influence of applied pressure, and proving the dynamical stability of YAG are destructed when applied pressure up to 7 GPa. Moreover, polycrystalline elastic moduli are deduced according to the Reuss assumption. Those elastic constants provide important parameters that describe reliability of both physical model and engineering application at the atomistic level. The result of the density of states explains the nature of the electronic band structure.     

Study of structural and optical properties of ZnO films grown by pulsed laser deposition

Wurtzite zinc oxides films (ZnO) were deposited on silicon (0 0 1) and corning glass substrates using the pulsed laser deposition technique. The laser fluence, target-substrate distance, substrate temperature of 300 °C were fixed while varying oxygen pressures from 2 to 500 Pa were used. It is observed that the structural properties of ZnO films depend strongly on the oxygen pressure and the substrate nature. The film crystallinity improves with decreasing oxygen pressure. At high oxygen pressure, the films are randomly oriented, whereas, at low oxygen pressures they are well oriented along [0 0 1] axis for Si substrates and along [1 0 3] axis for glass substrates. A honeycomb structure is obtained at low oxygen pressures, whereas microcrystalline structures were obtained at high oxygen pressures. The effect of oxygen pressure on film transparency, band gap E_g and Urbach energies was investigated.     

The high-resolution FTIR spectrum of the ν6 band of C2H3D

The absorption spectrum of the ν₆ band of C₂H₃D centered near 1125.27674 cm⁻¹ in the 1100-1250 cm⁻¹ region was recorded with an unapodized resolution of 0.0063 cm⁻¹ using a Fourier transform infrared (FTIR) spectrometer. A total of 947 infrared transitions of the A-B hybrid-type band were assigned and fitted to upper-state (ν₆ = 1) rovibrational constants using a Watson’s A-reduced Hamiltonian in the I^r representation up to eighth-order centrifugal distortion terms. The b-type infrared transitions of the band were analyzed for the first time. The root-mean-square deviation of the fit was 0.00062 cm⁻¹. The ground-state rovibrational constants up to eighth-order terms were also obtained by a fit of 617 combination differences from the present infrared measurements, simultaneously with 21 microwave frequencies with a root-mean-square deviation of 0.00055 cm⁻¹. From this work, the upper-state (ν₆ = 1) and ground-state constants of C₂H₃D were derived with the highest accuracy, so far. The a- and b-type transitions of the hybrid ν₆ band were found to be relatively free from local frequency perturbations. The ratio of the a- to b-type vibrational dipole transition moments (μ_a/μ_b) was found to be 1.05 ± 0.10. From the ν₆ = 1 rovibrational constants obtained, the inertial defect Δ₆ was calculated to be 0.3570 ± 0.0008 μŲ.     

In situ X-ray observation of phase transformation in Fe2O3 at high pressures and high temperatures

A laser-heated sample in a diamond anvil cell and synchrotron X-ray radiation was used to carry out structural characterization of the phase transformation of Fe₂O₃ at high pressures (30-96 GPa) and high temperature. The Rh₂O₃(II) (or orthorhombic perovskite) structure transforms to a new phase, which exhibits X-ray diffraction data that are indicative of a CaIrO₃-type structure. The CaIrO₃-type structure exhibited an orthorhombic symmetry (space group: Cmcm) that was stable at temperatures of 1200-2800 K and pressure of 96 GPa (the highest pressure used). Unambiguous assignment of such a structure requires experimental evidence for the presence of two Fe species. Based on the equation of state of gold, the phase boundary of the CaIrO₃-type phase transformation was P (GPa)=59+0.0022×(T−1200) (K).     

First-principles calculations of structural stability and mechanical properties of tungsten carbide under high pressure

The structural stability and mechanical properties of WC in WC-, MoC- and NaCl-type structures under high pressure are investigated systematically by first-principles calculations. The calculated equilibrium lattice constants at zero pressure agree well with available experimental and theoretical results. The formation enthalpy indicates that the most stable WC is in WC-type, then MoC-type finally NaCl-type. By the elastic stability criteria, it is predicted that the three structures are all mechanically stable. The elastic constants C_ij, bulk modulus B, shear modulus G, Young?s modulus E and Poisson?s ratio ν of the three structures are studied in the pressure range from 0 to 100 GPa. Furthermore, by analyzing the B/G ratio, the brittle/ductile behavior under high pressure is assessed. Moreover, the elastic anisotropy of the three structures up to 100 GPa is also discussed in detail.     

Elastic constants and anisotropy of RuB2 under pressure

The structural, elastic constants and anisotropy of RuB2 under pressure are investigated by first-principles calcula-tions based on the plane wave pseudopotential density functional theory method within the local density approximation (LDA) as well as the generalized gradient approximation (GGA) for exchange and correlation. The results accord well with the available experimental and other theoretical data. The elastic constants, elastic anisotropy, and Debye temperature Θ as a function of pressure are presented. It is concluded that RuB2 is brittle in nature at low pressure, whereas it becomes ductile at higher pressures. An analysis for the calculated elastic constant has been made to reveal the mechanical stability of RuB2 up to 100 GPa.     

Theoretical investigation on structural, magnetic and electronic properties of ferromagnetic GdN under pressure

The tight-binding linear muffin tin orbital (TB-LMTO) method within the local density approximation is used to calculate structural, electronic and magnetic properties of GdN under pressure. Both nonmagnetic (NM) and magnetic calculations are performed. The structural and magnetic stabilities are determined from the total energy calculations. The magnetic to ferromagnetic (FM) transition is not calculated. Magnetically, GdN is stable in the FM state, while its ambient structure is found to be stable in the NaCl-type (B₁) structure. We predict NaCl-type to CsCl-type structure phase transition in GdN at a pressure of 30.4 GPa. In a complete spin of FM GdN the electronic band picture of one spin shows metallic, while the other spin shows its semiconducting behavior, resulting in half-metallic behavior at both ambient and high pressures. We have, therefore, calculated electronic band structures, equilibrium lattice constants, cohesive energies, bulk moduli and magnetic moments for GdN in the B₁ and B₂ phases. The magnetic moment, equilibrium lattice parameter and bulk modulus is calculated to be 6.99 μ_B, 4.935 Å and 192.13 GPa, respectively, which are in good agreement with the experimental results.