Density functional perturbation theory calculations of vibrational and thermodynamic properties of Zn1−xBexO alloys

The elastic, phonon and thermodynamic properties of Zn_1−xBe_xO alloy are investigated by performing density functional theory (DFT) and density functional perturbation theory (DFPT) calculations. The calculated lattice parameters decreases with the increase of Be content that is in good agreement with the available theoretical and experimental data. The effect of Be composition on elastic constants was investigated for Zn_1−xBe_xO alloys. Phonon dispersion curves show that Zn_1−xBe_xO are dynamically stable. Thermodynamic properties, including Helmholtz free energy, enthalpy, entropy and heat capacity, were evaluated under quasi-harmonic approximation using the calculated phonon density of states. Finally, the results show that Zn_1−xBe_xO alloys with lower Be content are more thermodynamically stable. The agreement between the present results and the known data that are available only for ZnO and BeO is generally satisfactory.     

First principles study of the electronic structures and magnetic properties of transition metal-doped cubic indium nitride

First principles density functional calculations, using a full potential linearized augmented plane wave (FP-LAPW) method in local spin density approximation(LSDA), have been performed in order to investigate the structural, electronic and magnetic properties of In_1−xTM_xN(TM=Cr,Fe,Mn,V) in zinc-blende phase. Dependence of structural parameter values on the composition x have been analyzed in the x=0.25, x=0.50, and x=0.75, we found the existence of deviation from Vegard׳s law. Calculated electronic structure and the density of states of these alloys are discussed in terms of the contribution of TM 3d, N 2p, and In 3d states. The magnetic moment of In_1−xTM_xN has been studied by increasing the concentration of TM atom. The contribution of TM atom is the most important source of the total magnetic moment in these alloys, while it is minor in In and N.     

Ab Initio Calculations of Phonon Dispersion in ZnGa<Subscript>2</Subscript>Se<Subscript>4</Subscript>

In the context of density functional theory, the phonon density of states and phonon dispersion are calculated for ZnGa₂Se₄. The temperature dependence of the heat capacity of ZnGa₂Se₄ in the temperature range 5–400 K is obtained. The calculated frequencies and symmetries of phonon modes in the center of the Brillouin zone are in good agreement with experimental data obtained by Raman spectroscopy and infrared spectroscopy.     

Effect of Ionic Radius and Resultant Two-Dimensionality of Phonons on Thermal Conductivity in M<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CoO<Subscript>2</Subscript> (M = Li,Na, K) by Perturbed Molecular Dynamics

Phonon thermal conductivity calculations for Li _x CoO₂, Na _x CoO₂, and K _x CoO₂ (x = 1, 0.5) have been carried out by perturbed molecular dynamics to clarify the dependence of thermal conductivity on alkali-metal vacancy concentration in these materials. While thermal conductivity decreased for all compounds upon introduction of alkali-metal vacancies, the magnitude of the decrease is strongly dependent on the size of the alkali-metal ion. Further numerical analyses using fictitious physical parameters reveal that, with increasing ionic radius, the two-dimensionality of the phonons in the CoO₂ layers, which are responsible for overall thermal conductivity, is enhanced, resulting in lower thermal conductivity in vacancy-free compounds as well as ineffectiveness of alkali-metal vacancies in lowering thermal conductivity. In contrast, for systems with smaller alkali-metal ionic radius, even though higher thermal conductivity is predicted when no vacancies are present, vacancies are quite effective in significantly lowering thermal conductivity by modifying phonon states in the CoO₂ layers, more so than in systems with larger alkali-metal vacancies.     

The effects of short-range order and natural microinhomogeneities on the FIR optical properties of CdxHg1−xTe

Possible types and formation mechanisms for the correlated cation distributions in Cd_xHg_1?xTe alloys, including short-range order (SRO) in the mixed sublattice and composition microinhomogeneities (MI), are discussed. The impact of SRO (ordering or clustering) on phonons is studied in the framework of the coherent potential approximation. It is shown that two peaks of the spectral density of phonon states with $\overrightarrow q $ =0 (HgTe-like and CdTe-like modes) move toward and away from their positions in end member crystals due to clustering and ordering, respectively. Short-range ordering also activates (HgTe-like and CdTe-like states of the Brillouin zone edge, but this effect is small. The effects of composition MI on the dielectric response due to phonons are considered and an effective dielectric function is calculated using the modified Maxwell-Garnett approach. It is shown that separate inclusions of different composition produce extra modes of the Fröhlich type in FIR spectra of Cd_xHg_1?x Te. It is argued that this is a more plausible explanation of the experimenatally observed ‘cluster’ mode (133 cm^?1 in Raman and 135 cm^?1 in FIR spectra) than one which previously appeared in the literature and involves atomic ordering in the mixed sublattice.     

Calculation of the Schottky barrier and current–voltage characteristics of metal–alloy structures based on silicon carbide

A simple but nonlinear model of the defect density at a metal–semiconductor interface, when a Schottky barrier is formed by surface defects states localized at the interface, is developed. It is shown that taking the nonlinear dependence of the Fermi level on the defect density into account leads to a Schottky barrier increase by 15–25%. The calculated barrier heights are used to analyze the current–voltage characteristics of n-M/p-(SiC)_1–x(AlN)_x structures. The results of calculations are compared to experimental data.     

Electronic Band-Structure Calculations of Ba8Me x Si46-x Clathrates with Me = Mg,Pd, Ni,Au, Ag,Cu, Zn,Al, Sn

Clathrate materials of AlSi, CuSi or NiSi type consisting of abundant elements have a realistic chance of becoming useful thermoelectrics in the near future, because the rattling effect due to their crystal cage structure provides a large figure of merit ZT even in experiments measured under large temperature gradients. In the search for better thermoelectrics, new element combinations in the clathrate type I structure with cubic space group Pm3n were calculated using VASP ab initio software. Predictions of the Seebeck coefficient were made by checking the electronic band structure and density of states for a large variety of input data. For x values around 4 to 6 in the structural formula Ba₈Me _x Si_46?x the substituents Cu, Au, and Ag are best for good thermoelectric behavior, which is discussed in this paper as a result of the low electron–phonon interaction parameter.     

Electronic structure of Zn-substituted germanium clathrates

The result of the calculations of the electronic structure for Ba₈Zn _x Ge_{46 ? x} (x = 4, 6, 8) clathrates are presented. Band structures, total and partial electron densities of states in clathrates were obtained. The effect of the number of substituted atoms on the electron energy spectrum was considered. The linearized augmented plane wave method was used in the calculations.     

Electron-phonon interaction in short-period (GaAs) m (AlAs) n (001) superlattices

The deformation potentials of electron scattering at short-wavelength phonons for intervalley transitions in the conduction band of short-period (GaAs) _m (AlAs) _n (001) (m, n = 1, 2, 3) superlattices are determined by the electron density functional method. The dependences of the electron and phonon states and deformation potentials on the layer thickness in the superlattices are analyzed. The results of ab initio calculations are in good agreement with the data of empirical calculation of the deformation potentials integrated over phonons, but differ from data on the corresponding potentials for partial scattering channels because of approximations of the phenomenological model of interatomic binding.     

Heat-transfer phenomena in alloys

The phonon heat conductivity k _ph in Bi_{1 − x} Sb _x (x = 0.04–0.12) alloys is investigated in the temperature range of 6–60 K. The results are compared with the theory of solids at low temperatures, and the basic sources of phonon scattering are revealed. It is shown that phonon scattering at local mass changes dominates over other sources. The dependences of k _ph on composition are considered at temperatures of 60 and 90 K, and it is found that the normal N processes substantially affect the phonon scattering under these conditions. The donor-impurity effect on heat conductivity of Bi_0.88Sb_0.12 is considered, and the heat resistance caused by the phonon scattering at impurity centers is singled out.     

Selenium alloying of indium sulfide: Ab-initio study of structural,electronic and optical features

In the framework of density functional calculations and using the Linear Augmented Plane Waves with local orbital method (LAPW+lo), we have investigated the structural, electronic and optical properties of indium sulfoselenide (InS_1−xSe_x). The present study confirms that InS_1−xSe_x are indirect band gap materials. The non-linear dependence concentration x of the theoretical forbidden energy band is clearly visible and the microscopic origins of gap bowing are identified and calculated. In order to identify the angular momentum characteristics of the bands structure, the total and partial densities of states (DOS and PDOS) are analyzed. The feature bonding is also investigated from charge density study. Using the projected total densities of states (DOS) and the bands structure, we have calculated the linear optical properties, namely, the complex dielectric function ε(ω), refractive index n(ω), absorption coefficient α(ω) and the electron energy loss L(ω). In particular, we take into account the effect of Se composition on anisotropy, real part of the dielectric function and refractive index. The present alloy is found to be a challenging material in optoelectronic, medical and photovoltaic devices. Good agreements are found with the available experimental and theoretical results.     

The short-wavelength edge of intrinsic photoluminescence in diluted GaN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>As<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript> alloys

It is suggested that the analysis of the short-wavelength edge of intrinsic photoluminescence in diluted GaN _x As_{1 − x} alloys at room temperature be used to study the specific features of the energy dependence of the density of states in the conduction band. It is found that, in the GaN _x As_{1 − x} alloys with x ≥ 0.002, this dependence is inconsistent with the model of the anticrossing band and suggests that there are extra states. These states are thought to be the states formed in nitrogen clusters and interacting with the conduction band. The energy of these states is at least 1.45 eV above the top of the valence band.     

InxAl1-xN/AlN/GaN高电子迁移率晶体管的电学特性

通过自洽求解薛定谔和泊松方程研究了In_xAl_1-xN/AlN/GaN结构的电学特性。通过研究In_xAl_1-xN内部极化效应随铟组分的变化发现,当铟组分为0.41时,总的极化效应为零。通过计算发现,二维电子气密度随着铟组分的增加而减小。对于AlN的厚度存在一个临界值：当AlN的厚度小于临界值时,二维电子气密度随着In_xAl_1-xN厚度的增加而增加;然而,当AlN的厚度大于临界值时,二维电子气密度随着In_xAl_1-xN厚度的增加而减少。对于晶格匹配的In_0.18Al_0.82N/AlN/GaN结构,AlN的厚度临界值为2.8nm。通过计算还发现,AlN厚度临界值随着铟组分的增加而减少。     

Electronic and Lattice Vibrational Properties of BaSi<Subscript>2</Subscript> from Density Functional Theory Calculations

BaSi₂ is a potential thermoelectric material because of its very low thermal conductivity. Using the full-potential linearized augmented plane-wave method and semiclassical Boltzmann theory, thermoelectric transport properties of BaSi₂ have been investigated. The calculations show that the thermoelectric properties can be remarkably improved by optimizing the carrier concentration. The linear response method within the framework of density functional theory was employed to investigate the underlying physics of heat transport. There are rather flat optical dispersion curves and low frequency of acoustic phonon modes in the phonon band structure of BaSi₂. The low-lying optical phonon branch at the Γ point of the Brillouin zone (BZ) corresponds to rigid-unit vibration of the Si tetrahedron. The rigid-unit vibration mode confines the acoustic phonon modes and scatters the heat-carrying acoustic modes, leading to the low lattice thermal conductivity.     

High-Pressure Synthesis and Thermal Conductivity of Semimetallic θ-Tantalum Nitride

The lattice thermal conductivity (κ_ph) of metals and semimetals is limited by phonon-phonon scattering at high temperatures and by electron-phonon scattering at low temperatures or in some systems with weak phonon-phonon scattering. Following the demonstration of a phonon band engineering approach to achieve an unusually high κ_ph in semiconducting cubic-boron arsenide (c-BAs), recent theories have predicted ultrahigh κ_ph of the semimetal tantalum nitride in the θ-phase (θ-TaN) with hexagonal tungsten carbide (WC) structure due to the combination of a small electron density of states near the Fermi level and a large phonon band gap, which suppress electron-phonon and three-phonon scattering, respectively. Here, measurements on the thermal and electrical transport properties of polycrystalline θ-TaN converted from the ε phase via high-pressure synthesis are reported. The measured thermal conductivity of the θ-TaN samples shows weak temperature dependence above 200 K and reaches up to 90 Wm⁻¹K⁻¹, one order of magnitude higher than values reported for polycrystalline ε-TaN and δ-TaN thin films. These results agree with theoretical calculations that account for phonon scattering by 100 nm-level grains and suggest κ_ph increase above the 249 Wm⁻¹ K⁻¹ value predicted for single-crystal WC when the grain size of θ-TaN is increased above 400 nm.     

High Thermoelectric Performance in the Wide Band‐Gap AgGa1‐xTe2 Compounds: Directional Negative Thermal Expansion and Intrinsically Low Thermal Conductivity

A deficiency of Ga in wide band‐gap AgGa_1‐xTe₂ semiconductors (1.2 eV) can be used to optimize the electrical transport properties and reduce the thermal conductivity to achieve ZT > 1 at 873 K. First‐principles density functional theory calculations and a Boson peak observed in the low temperature heat capacity data indicate the presence of strong coupling between optical phonons with low frequency and heat carrying acoustical phonons, resulting in a depressed maximum of Debye frequency in the first Brillouin zone and low phonon velocities. Moreover, the Ag? Te bond lengths and Te? Ag? Te bond angles increase with rising temperature, leading to a significant distortion of the [AgTe₄]^7? tetrahedra, but an almost unmodified [GaTe₄]^5? tetrahedra. This behavior results in lattice expansion in the ab‐plane and contraction along the c‐axis, corresponding to the positive and negative Gruneisen parameters in the phonon spectral calculations. This effect gives rise to the large anharmonic behavior of the lattice. These factors together with the low frequency vibrations of Ag and Te atoms in the structure lead to an ultralow thermal conductivity of 0.18 W m^?1 K^?1 at 873 K.     

N‐Doped CsTaWO6 as a New Photocatalyst for Hydrogen Production from Water Splitting Under Solar Irradiation

Photocatalysts for efficient solar hydrogen production are highly sought after. Here a new type of nitrogen‐doped tantalum tungstenate (CsTaWO₆) material, which demonstrates excellent visible light absorption and improved photocatalytic activity, is demonstrated. X‐ray diffraction (XRD) patterns reveal that the defect pyrochlore‐type structure of CsTaWO₆ remained intact upon nitrogen doping. UV‐vis spectra indicate that nitrogen doping in the compound results in a red‐shift of the absorption edge from 358 nm to 580 nm, thus offering significantly increased visible light absorption. X‐ray photoelectron spectroscopy (XPS) further indicates that [Ta/W]–N bonds were formed by inducing nitrogen to replace a small amount of oxygen in the material, resulting in a compound of CsTaWO_6‐xN_x. The explanation of the experimental results is supported by density functional theory calculations. The density of states (DOS) and the projected DOS after substitutional doping of nitrogen in CsTaWO₆ indicated that N‐doping reduces the bandgap significantly from 3.8 to 2.3 eV due to N 2p and O 2p orbital mixing. The role of the new N 2p states is also investigated by studying the production of the ?OH radicals in the visible light region (>420 nm). In CsTaWO_6‐xN_x, the N 2p orbitals are the main contributors to the top of the valence band, causing bandgap narrowing while the bottom of conduction band, due to Ta 4d orbitals, remains almost unchanged. Compared with its undoped counterpart, nitrogen‐doped CsTaWO_6‐xN_x exhibits a nearly 100% increase in solar hydrogen production efficiency.     

Far infrared measurements of bulk and surface phonons in GaAs/AlAs superlattices

We have used far-infrared oblique-incidence reflection spectroscopy to study bulk phonon polaritons, and attenuated total reflection (ATR) spectroscopy to study surface phonon polaritons, in long-period GaAs/Al_xGa_1?xAs and short-period GaAs/AlAs superlattices. Results on the former are in good agreement with an effective-medium bulk-slab model of the dielectric tensor of the superlattice; results on the latter are analysed in terms of a model that contains dielectric-tensor contributions from the confined optic phonons.     

Far infrared optical properties of high Tc superconductors LnBa2Cu3Ox (Ln=Y,Ho, Er,Sm, GD,Dy, Eu,Pr)

Systematic measurements of the far infrared reflection spectra of high T_c superconductors LnBa₂Cu₃O_x for various Ln as shown in the title were performed. Infrared reflection spectra of tetragonal LnBa₂Cu₃O_x exhibit Reststrahlen vibration near 640, 590, 530, 355 and 250 cm^?1, common to these materials, and the spectra of the orthorhombic LnBa₂Cu₃O_x exhibit the characteristics of free carriers except PrBa₂Cu₃O_x with weak phonon structures near 617, 570, 317 and 285 cm^?1. PrBa₂Cu₃O_x is not a superconductor, and it has no characteristic broad band due to free carriers for all x in the range of 6 to 7. Lattice dynamical calculation was performed by the use of the shell model and the calculated results express quite well the characteristic features of infrared experiments.     

Extended Antibonding States and Phonon Localization Induce Ultralow Thermal Conductivity in Low Dimensional Metal Halide

Thermal conductivity, which measures the ease at which heat passes through a crystalline solid, is controlled by the nature of the chemical bonding and periodicity in the solid. This necessitates an in-depth understanding of the crystal structure and chemical bonding to tailor materials with notable lattice thermal conductivity (κ_L). Herein, the nature of chemical bonding and its influence on the thermal transport properties (2–523 K) of all-inorganic halide perovskite Cs₃Bi₂I₉ are studied. The κ_L exhibits an ultralow value of ≈0.20  W m⁻¹K⁻¹ in 30–523 K temperature range. The antibonding states just below the Fermi level in the electronic structure arising from the interaction between bismuth 6s and iodine 5p orbitals, weakens the bond and causes soft elasticity in Cs₃Bi₂I₉. First-principles density functional theory (DFT) calculations reveal highly localized soft optical phonon modes originating from Cs-rattling and dynamic double octahedral distortion of 0D [Bi₂I₉]³⁻ in Cs₃Bi₂I₉. These low energy nearly flat optical phonons strongly interact with transverse acoustic modes creating an ultrashort phonon lifetime of ≈1 ps. While the presence of extended antibonding states gives rise to soft anharmonic lattice; Cs rattling provides sharp localized optical phonon modes, which altogether result in strong lattice anharmonicity and ultralow κ_L.