Photoemission studies of single crystals of titanium carbide

The electron distribution in the valence band from single crystals of titanium carbide has been studied by photoelectron spectroscopy with photon energies h?ω = 16.8, 21.2, 40.8 and 1486.6 eV. The most conspicious feature of the electron distribution curves for TiC is a hybridization between the titanium 3d and carbon 2p states at ca. 3–4-eV binding energy, and a single carbon 2s band at ca. 10 eV. By taking into account the strong symmetry and energy dependence of the photoionization crosssections, as well as the surface sensitivity, we have identified strong emission from a carbon 2p band at ? 2.9-eV energy. Our results are compared with several recent energy band structure calculations and other experimental data. Results from pure titanium, which have been used for reference purposes, are also presented.The valence band from single crystals of titanium carbide have been studied by means of photoelectron spectroscopy, with photon energies ranging from 16.8 to 1486.6 eV.By taking into account effects such as the symmetry and energy dependence of the photoionization cross-sections and surface sensitivity, we have found the valence band of titanium carbide to consist of two peaks. The upper part of the valence band at 3–4 eV below the Fermi level consists of a hybridization between Ti 3d and C 2p states. The C 2p states observed in our spectra were mainly excited from a band about 2.9 eV below the Fermi level. The APW^5–9, MAPW¹⁰ and EPM¹¹ band structure calculations predict a flat band of p-character between the symmetry points X′₄ and K₃, most likely responsible for the majority of C 2p excitations observed. The C 2s states, on the other hand, form a single band centered around ?10.4 eV.The results obtained are consistent with several recent energy band structure calculations^{5–11, 13} that predict a combined bonding of covalent, ionic and metallic nature.     

Theoretical investigations of NiTiSn and CoVSn compounds

The structural, elastic and electronic properties of NiTiSn and CoVSn half-Heusler compounds have been calculated using the full-potential linear muffin-tin orbital (FP-LMTO) method. The computed equilibrium lattice constants are in excellent agreement with the available experimental and theoretical data. The elastic constants C_ij are calculated using the total energy variation with strain technique. The polycrystalline elastic moduli (namely: the shear modulus, Young's modulus, Poisson's ratio, Lamé's coefficients, sound velocities and the Debye temperature) were derived from the obtained single-crystal elastic constants. The ductility mechanism for the studied compounds is discussed via the elastic constants C_ij and their related parameters. The electronic band structure calculations show that the conduction band minimum (CBM) is located at the X point for both compounds, whereas the valence band maximum (VBM) is located at the Г point for NiTiSn and at the L point for CoVSn, resulting in indirect energy band gaps of 0.46 and 0.75 eV for NiTiSn and CoVSn, respectively. The pressure and volume dependences of the energy band gaps have been calculated.     

Band gap tuning of defective silicon carbide nanotubes under external electric field: Density functional theory

We have theoretically investigated the effect of applying longitudinal and transverse electric field on silicon carbide nanotubes with different orientations of Stone Wales defects. We found that each type of Stone Wales defects maintained different formation energy. We have also successfully proved that the orientation of Stone Wales defects in silicon carbide nanotubes response quite differently upon applying external electric field, whereas, two important and interesting phenomena were observed. First, the semiconductor-metal phase transition occurred in silicon carbide nanotubes as well as the three types of Stone Wales defects. However, clear band gap variations were observed in all silicon carbide nanotubes under study. Second, the band gap variations in pristine silicon carbide nanotubes and nanotubes with different orientations of Stone Wales defects have the same trend, even though all silicon carbide nanotubes have clear band gap values under different strengths of the applied external electric field. However, band gap tuning under longitudinal electric field is less significant compared to band gap tuning under the transverse electric field.     

Mechanical properties of vanadium carbide and a ternary vanadium tungsten carbide

Ab initio total energy calculations are performed on non-stoichiometric vanadium carbide with supercells representing vacancy concentrations of V C_0.875 and V C_0.75. The V C_0.875 supercell retains a cubic symmetry whilst in the case of the V C_0.75 supercell C vacancies located in close proximity have the lowest energy configuration and the cubic lattice slightly distorts to a monoclinic symmetry. Using a stress–strain calculational procedure, the elastic constants of both the cubic and the monoclinic systems are deduced. In all cases C vacancies decrease the elastic moduli.A similar analysis is then applied to consider when W is incorporated into VC. In this case it is found that the elastic moduli increase with W content suggesting that a V-W-C alloy could have significant potential as a novel hard material.     

Mechanical stability and optoelectronic behavior of BeXP2 (X=Si and Ge) chalcopyrite

We have conducted a first-principles study on the structural, electronic, optical and elastic properties of BeSiP₂ and BeGeP₂ chalcopyrite compounds. Using the density functional theory (DFT), implemented in both full potential linear muffin-tin orbital (FP-LMTO) and Vienna Ab initio simulation (VASP) packages. The FP-LMTO is used for the determination of the structural, electronic and optical properties, while the VASP is used to determine the elastic constants that give indications about the material stability. The obtained equilibrium structural parameters are in good agreement with available results. An investigation of the band gap indicates that our compounds possess a semiconductor behavior with direct band gap for BeSiP₂ and with an indirect band gap for BeGeP₂. The energy band gaps decreased by changing Be atoms from Si to Ge. We have calculated the dielectric function ε(ω). The obtained results show that these materials are promising semiconductors for photovoltaic applications. For the elastic properties, the single-crystal elastic constants C_ij, shear anisotropic factors A, as well as polycrystalline bulk, shear and Young's modulus (B, G and E) and Poisson's ratio v have been predicted. The generalized elastic stability criteria for a tetragonal crystal are well satisfied, indicating that BeSiP₂ and BeGeP₂ are mechanically stable in the chalcopyrite structure.     

Valence band structure of single crystal titanium carbide,studied by soft X-ray and ultraviolet photoelectron spectroscopy

Valence states of single crystal titatium carbide (TiC_x, X?0.88) have been studied with photon energies ranging from far ultraviolet (u.v.) to soft X-ray. The valence band consists of two peaks located at 3 and 10 eV below the Fermi level. This is in good agreement with recent APW band structure calculations that predict a strong hybridization of the Ti 3d and C 2p bands and a C 2s band at lower energy.     

Surface and bulk valence band photoemission of silicon carbide

Surface and bulk valence band photoemission spectra have been obtained for silicon carbide using Zr M-zeta (151.4eV) and Mg Kα_1,2 (1253.6eV) excitation, respectively. The data have been corrected for various broadening effects using a deconvolution procedure. Spectra for single-crystal hexagonal α-SiC and for epitaxial films of cubic β-SiC on Si (1 0 0) are compared with the results of band structure calculations. Differences in the spectra for various surface reconstructions suggest the existence of surface resonances, but no surface states are observed in the bulk optical bandgap.     

An ab initio study of the electronic structure and elastic properties of the newly discovered ternary carbide

The electronic structure and elastic properties of the newly discovered ternary layered carbide Ti₄GaC₃ were investigated by means of the first-principle plane-wave pseudopotential total energy calculation method based on density functional theory. The computed results, including lattice constants and internal coordinates, are in good agreement with experimental values. The elastic moduli of ideal polycrystalline Ti₄GaC₃ were predicted from the individual elastic constants by Voigt approximation. The band structure shows that the electrical conductivity is metallic and anisotropic, with a high density of states at the Fermi energy. The elastic properties are anisotropic, related to the Ti–Ga bonds being relatively weaker than the Ti–C bonds.     

The properties of boron carbide/silicon heterojunction diodes fabricated by Plasma-Enhanced Chemical Vapor Deposition

p-n heterojunction diodes have been fabricated from boron carbide (B_1–x C _x ) and n-type Si(111). Boron carbide thin films were deposited on Si(111) using Plasma-Enhanced Chemical Vapor Deposition (PECVD) from nido-pentaborane (B₅H₉) and methane (CH₄). Composition of boron carbide thin films was controlled by changing the relative partial pressure ratio between nido-pentaborane and methane. The properties of the diodes were strongly affected by the composition and thickness of boron carbide layer and operation temperatures. Boron carbide/silicon heterojunction diodes show rectifying properties at temperatures below 300° C. The temperature dependence of reverse current is strongly dependent upon the energy of the band gap of the boron carbide films.     

Accounting for nonstoichiometry of niobium carbide NbC y upon milling to a nanocrystalline state

The dependence of the size of particles in the prepared nanocrystalline powders on the composition of nonstoichiometric compounds within their homogeneity intervals has been considered in terms of the high-energy ball milling model. It has been shown that the effect of nonstoichiometry on the milling manifests itself in the concentration dependences of the main characteristics (parameters of the crystal structure, energy of interatomic bonds, elastic properties) of the milled nonstoichiometric compound. The results of model calculations performed for nonstoichiometric cubic niobium carbides NbC _y have been compared with the experimental data on milling of the NbC_0.93 carbide.     

Polytypism of silicon carbide and Schottky barriers

The results obtained in our previous work [4] are revised taking into account the dependence of the electron affinity on the polytype of silicon carbide SiC. The dependence of the energy level of vacancies in a polytype of silicon carbide on the band gap is determined from the data on the Schottky barrier height and is explained in the framework of a simple two-band model.     

高温高压下碳化钨晶体的结构、力学、电子、光学以及热力学性能的第一性原理计算

本文利用密度泛函理论中的广义梯度近似对碳化钨晶体的三种结构(碳化钨相、闪锌矿相以及纤锌矿相)进行了优化,得到能量最低的稳定构型,并在此基础上计算了它的力学、电子、光学和高温高压下的热力学性质.研究表明:在0～300 GPa压力范围内,碳化钨相具有最高的稳定性.同时,高压下碳化钨相的弹性常数满足Born-Huang准则,且0 GPa和300 GPa下的声子色散没有虚频,证明了高压下碳化钨相的静力学稳定性和动力学稳定性.电子性质表明了碳化钨的金属性.光学性质表明碳化钨在高能区很难吸收光.热力学性质的研究表明:体积比V/V_0对压强的变化更敏感;高温时C_V曲线近似一条直线;给定压强下热膨胀系数α在600 K温度以上增长非常缓慢;压强对德拜温度Θ_D的影响较大;在低压下格林艾森系数γ的变化较大.     

Full potential calculation of structural, elastic properties and high-pressure phase of binary noble metal carbide: ruthenium carbide

We present in this paper the results of an ab initio theoretical study within the local density approximation (LDA) to determine in rock-salt (B1), cesium chloride (B2), zinc-blende (B3), and tungsten carbide (WC) type structures, the structural, elastic constants, hardness properties and high-pressure phase of the noble metal carbide of ruthenium carbide (RuC).The ground state properties such as the equilibrium lattice constant, elastic constant, the bulk modulus, its pressure derivative, and the hardness in the four phases are determined and compared with available theoretical data. Only for the three phases B1, B3, and WC, is the RuC mechanically stable, while in the B2 phase it is unstable, but in B3 RuC is the most energetically favourable phase with the bulk modulus 263 GPa, and at sufficiently high pressure (P_t=19.2 GPa) the tungsten carbide (WC) structure would be favoured, where ReC-WC is meta-stable.The highest bulk modulus values in the B3, B2, and WC structures and the hardnesses of H(B3)=36.94 GPa, H(B1)=25.21 GPa, and H(WC)=25.30 GPa indicate that the RuC compound is a superhard material in B3, and is not superhard in B1 and WC structures compared with the H(diamond)=96 GPa.     

FP-LMTO calculations of the structural,elastic, thermodynamic,and electronic properties of the ideal-cubic perovskite BiGaO3

Using the first-principles full-potential linear muffin-tin orbital method within the local density approximation, we have studied the structural, elastic, thermodynamic, and electronic properties of the ideal-cubic perovskite BiGaO₃. It is found that this compound has an indirect band gap. The valence band maximum (VBM) is located at Γ-point, whereas the conduction band minimum (CBM) is located at X-point. The pressure and volume dependences of the energy band gaps have been calculated. The elastic constants at equilibrium are also determined. We derived the bulk and shear moduli, Young’s modulus, and Poisson’s ratio. The thermodynamic properties are predicted through the quasi-harmonic Debye model, in which the lattice vibrations are taken into account. The variation of the bulk modulus, heat capacities, and Debye temperature with pressure and temperature are successfully obtained.     

Behavior of disordered boron carbide under stress

Gibbs free-energy calculations based on density functional theory have been used to determine the possible source of failure of boron carbide just above the Hugoniot elastic limit (HEL). A range of B4C polytypes is found to be stable at room pressure. The energetic barrier for shock amorphization of boron carbide is by far the lowest for the B12(CCC) polytype, requiring only 6 GPa approximately = P(HEL) for collapse under hydrostatic conditions. The results clearly demonstrate that the collapse of the B12(CCC) phase leads to segregation of B12 and amorphous carbon in the form of 2-3 nm bands along the (113) lattice direction, in excellent agreement with recent transmission electron microscopy results.     

High pressure effect on structural and mechanical properties of some LnO (Ln=Sm, Eu, Yb) compounds

The structural and mechanical properties of LnO (Ln=Sm, Eu, Yb) compounds have been investigated using a modified interionic potential theory, which includes the effect of Coulomb screening. We predicted a structural phase transition from NaCl (B₁)- to CsCl (B₂)-type structure and elastic properties in LnO compounds at very high pressure. The anomalous properties of these compounds have been correlated in terms of the hybridisation of f-electrons of the rare earth ion with conduction band and strong mixing of f-states of lanthanides with the p-orbital of neighbouring chalcogen ion. For EuO, the calculated transition pressure, bulk modulus and lattice parameter are close to the experimental data. The nature of bonds between the ions is predicted by simulating the ion-ion (Ln-Ln and Ln-O) distances at high pressure. The second order elastic constants along with shear modulus and Young's modulus, elastic anisotropy and Poisson's ratio are also presented for these oxides.     

Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.     

Towards a nonlinear elastic representation of finite compression and instability of boron carbide ceramic

A nonlinear constitutive model invoking third-order anisotropic elasticity is developed for boron carbide single crystals subjected to potentially large compressive stresses. The model makes use of limited available published data from various experimental and theoretical (i.e., quantum or ab initio) studies. The model captures variations in second-order tangent elastic moduli and loss of elastic mechanical stability with increasing compression. In particular, reduced stability of boron carbide single crystals compressed normal to the c-axis (i.e., [0001]-direction) relative to higher stability in spherical compression is represented. Different stability criteria proposed in the literature are examined for boron carbide under spherical and uniaxial compression; model predictions show that the most critical criterion corresponds to a vanishing eigenvalue of a particular tangent stiffness matrix (i.e., incremental modulus) derived exactly in the present work. Model constants are proposed for CCC (less elastically stable) and polar CBC (more elastically stable) polytypes of boron carbide. Application of the model to a homogeneously strained polycrystal provides support for the hypothesis that failure (e.g., amorphization) follows a loss of elastic stability of favorably oriented grains at shock pressures on the order of 18–20?GPa. Additional experiments or atomic simulations are suggested that would resolve currently indeterminate features of the nonlinear elastic model.     

Elasticity and inelasticity of biomorphic carbon,silicon carbide,and SiC/Si composite produced on the basis of medium density fiberboard

The amplitude and temperature dependences of the Young’s modulus and the internal friction (ultrasonic absorption) of biomorphic carbon, silicon carbide, and SiC/Si composite produced from medium density fiberboard (MDF) by pyrolysis (carbonization), followed by infiltration of molten silicon into the prepared carbon preform have been studied in the temperature range 100–293 K in air and under vacuum. The measurements have been performed by the acoustic resonance method with the use of a composite vibrator for longitudinal vibrations at frequencies of approximately 100 kHz. The data obtained by acoustic measurements of the amplitude dependences of the elastic modulus have been used for evaluating the microplastic properties of samples under study. It has been shown that the Young’s modulus, the decrement of elastic vibrations, and the conventional microyield strength of the MDF samples differ from the corresponding data for previously studied similar materials produced from natural eucalyptus, beech, sapele, and pine woods. In particular, the desorption of environmental molecules at small amplitudes of vibrations, which is typical of biomorphic materials based on natural wood, is almost absent for the MDF samples. The results obtained have been explained by different structures and the influence of pores and other defects, which, to a large extent, determine the mechanical characteristics of the biomaterials under investigation.     

Growth of silicon carbide films via C60 precursors

Epitaxial silicon carbide films are grown on Si(100) and Si(111) substrates at surface temperatures between 950 and 1250 K via c₆₀ precursors. Films have been grown up to thicknesses greater than 1 μm. The growth rate of the SiC film is not limited by the surface reaction rate of C₆₀ with silicon at these temperatures, rather by the arrival rate of the reactants Si (by diffusion) or C₆₀. This results in rapid film growth. Films have been characterized by low energy electron diffraction, X-ray diffraction, and Auger depth profiling. X-ray diffraction suggests the growth of β-SiC in the temperature range investigated. Auger depth profiling shows the film is stoichiometric. Selective crystalline silicon carbide growth is achieved on patterned silicon-silicon oxide samples.