Electronic and Lattice Vibrational Properties of Cubic SrHfO<Subscript>3</Subscript> from First-Principles Calculations

The electronic structure and lattice vibrational properties of cubic SrHfO₃ were investigated by first-principles calculations based on density functional theory in the framework of the local density approximation (LDA), generalized gradient approximation (GGA), and density functional perturbation theory (DFPT), respectively. The calculated equilibrium lattice constant of cubic SrHfO₃ is in good agreement with available experimental and theoretical results. The results show that cubic SrHfO₃ is an insulator with an indirect LDA (GGA) band gap of 3.6 (3.7) eV. Use of the screened exchange local density approximation (sX-LDA) as a functional in successive band calculation has also been performed. The band gap is predicted to be 6.27 eV within sX-LDA, in excellent agreement with the gap value of 6.1 ± 0.1 eV obtained from x-ray photoelectron spectroscopy. The phonon dispersion curves and LO–TO splitting of cubic SrHfO₃ were also calculated. Negative phonon frequencies were observed along the M–Γ–R–M line in the Brillouin zone, indicating instability of the SrHfO₃ structure, consistent with previous theoretical investigation.     

Structural,Mechanical and Thermodynamic Properties of Cu<Subscript>2</Subscript>CoXS<Subscript>4</Subscript> (X = Si,Ge, Sn) Studied by Density Functional Theory

We have investigated the Structural, mechanical and thermodynamic properties of Cu₂CoXS₄ (X = Si, Ge, Sn) by using the density functional theory method. In this paper, we used GGA-PBE functional to find the equilibrium structural parameters and to calculate the elastic properties. The Mulliken population analysis indicates the bonds between S atoms and other three atoms in Cu₂CoXS₄ (X = Si, Ge, Sn) exhibit the feature of covalent bond. Furthermore, the calculated elastic constants prove the mechanical stability of Cu₂CoXS₄ (X = Si, Ge, Sn) in I\(\bar 4\)2m structure. The results are given for B/G and A ^U reveal Cu₂CoXS₄ (X = Si, Ge, Sn) can behave as a ductile and elastic material. Finally, the heat capacity, thermal expansion, entropy and Debye temperature are also reported at the different pressures (0~50 GPa) and temperatures (0~1000 K).     

Synthesis and Electronic Properties of the Misfit Layer Compound [(PbSe)<Subscript>1.00</Subscript>]<Subscript>1</Subscript>[MoSe<Subscript>2</Subscript>]<Subscript>1</Subscript>

An ultralow-thermal-conductivity compound with the ideal formula [(PbSe)_1.00]₁[MoSe₂]₁ has been successfully crystallized across a range of compositions. The lattice parameters varied from 1.246 nm to 1.275 nm, and the quality of the observed 00ℓ diffraction patterns varied through the composition region where the structure crystallized. Measured resistivity values ranged over an order of magnitude, from 0.03 Ω m to 0.65 Ω m, and Seebeck coefficients ranged from −181 μV K⁻¹ to 91 μV K⁻¹ in the samples after the initial annealing to form the basic structure. Annealing of samples under a controlled atmosphere of selenium resulted in low conductivities and large negative Seebeck coefficients, suggesting an n-doped semiconductor. Scanning transmission electron microscopy cross-sections confirmed the interleaving of bilayers of PbSe with Se-Mo-Se trilayers. High-angle annular dark-field images revealed an interesting volume defect, where PbSe grew through a region where a layer of MoSe₂ would be expected in the perfect structure. Further studies are required to correlate the density of these defects with the observed electrical properties.     

Understanding Ferromagnetic Phase Stability,Electronic and Transport Properties of BaPaO<Subscript>3</Subscript> and BaNpO<Subscript>3</Subscript> from <Emphasis Type="Italic">Ab-Initio</Emphasis> Calculations

An extensive study of rare-earth perovskite BaPaO₃ and BaNpO₃ has been performed by first-principles tactics based on density functional theory (DFT), because the delocalized f-electrons play an important role in the band structure formation, to reveal their impact on the overall physical and chemical properties; it has turned out to be an interesting theme. Along with critical radii and thermoelectric properties, two different theories are employed to calculate the structural properties. The DFT and empirically calculated lattice constants are in rational accord with the experimental results. The critical radius calculations show that the BaPaO₃ lattice has a smaller oxygen migration activation energy than the BaNpO₃. In addition, we discuss the band profile and magnetic moments for these materials, which demonstrate the half-metallic ferromagnetism with a direct energy gap of 3.91 eV for BaPaO₃ and an indirect gap of 3.79 eV for BaNpO₃. More interestingly, the integral magnetic moments are in accordance with the Slater–Pauling rule.     

First-Principles Study of Structural,Electronic, Optical,and Thermal Properties of BeSiSb<Subscript>2</Subscript> and MgSiSb<Subscript>2</Subscript>

Structural, electronic, optical, and thermal properties of ternary II–IV–V₂ (BeSiSb₂ and MgSiSb₂) chalcopyrite semiconductors have been calculated using the full-potential linearized augmented plane wave scheme?in the generalized gradient approximation. The optimized equilibrium structural parameters (a, c, and u) are in good agreement with theoretical results obtained using other methods. The band structure and density of states reveal that BeSiSb₂ has an indirect (Γ–Z) bandgap of about 0.61 eV, whereas MgSiSb₂ has a direct (Γ–Γ) bandgap of 0.80 eV. The dielectric function, refractive index, and extinction coefficient were calculated to investigate the optical properties, revealing that BeSiSb₂ and MgSiSb₂ present very weak birefringence. The temperature dependence of the volume, bulk modulus, Debye temperature, and heat capacities (C _v and C _p) was predicted using the quasiharmonic Debye model at different pressures. Significant differences in properties are observed at high pressure and high temperature. We predict that, at 300 K and 0 GPa, the heat capacity at constant volume C _v, heat capacity at constant pressure C _P, Debye temperature θ _D, and Grüneisen parameter γ will be about 94.91 J/mol K, 98.52 J/mol K, 301.30 K, and 2.11 for BeSiSb₂ and about 96.08 J/mol K, 100.47 J/mol K, 261.38 K, and 2.20 for MgSiSb₂, respectively.     

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.     

Electronic Processes in CdIn<Subscript>2</Subscript>Te<Subscript>4</Subscript> Crystals

The results of investigations of electrical, optical, and photoelectric properties of CdIn₂Te⁴ crystals, which were grown by the Bridgman method are presented. It is shown that electrical conductivity is determined mainly by electrons with the effective mass m_n = 0.44m₀ and the mobility 120–140 cm²/(V s), which weakly depends on temperature. CdIn₂Te₄ behaves as a partially compensated semiconductor with the donor-center ionization energy E_d = 0.38 eV and the compensation level K = N_a/N_d = 0.36. The absorption-coefficient spectra at the energy hν < E_g = 1.27 eV are subject to the Urbach rule with a typical energy of 18–25 meV. The photoconductivity depends on the sample thickness. The diffusion length, the charge-carrier lifetime, and the surface-recombination rate are determined from the photoconductivity spectra.     

Thermoelectric Properties of Zr<Subscript>3</Subscript>Mn<Subscript>4</Subscript>Si<Subscript>6</Subscript> and TiMnSi<Subscript>2</Subscript>

The Seebeck coefficient, electrical resistivity, and thermal conductivity of Zr₃Mn₄Si₆ and TiMnSi₂ were studied. The crystal lattices of these compounds contain relatively large open spaces, and, therefore, they have fairly low thermal conductivities (8.26 Wm⁻¹ K⁻¹ and 6.63 Wm⁻¹ K⁻¹, respectively) at room temperature. Their dimensionless figures of merit ZT were found to be 1.92 × 10⁻³ (at 1200 K) and 2.76 × 10⁻³ (at 900 K), respectively. The good electrical conductivities and low Seebeck coefficients might possibly be due to the fact that the distance between silicon atoms in these compounds is shorter than that in pure semiconductive silicon.     

Electronic and Optical Modeling of Solar Cell Compounds CuGaSe<Subscript>2</Subscript> and CuInSe<Subscript>2</Subscript>

We present dielectric-function-related optical properties such as absorption coefficient, refractive index, and reflectivity of the semiconducting chalcopyrites CuGaSe₂ and CuInSe₂. The optical properties were calculated in the framework of density functional theory (DFT) using linear combination of atomic orbitals (LCAO) and full-potential linearized augmented plane wave (FP-LAPW) methods. The calculated spectral dependence of complex dielectric functions is interpreted in terms of interband transitions within energy bands of both chalcopyrites; for example, the lowest energy peak in the e₂ (w) varepsilon_{2} (omega ) spectra for CuGaSe₂ corresponds to interband transitions from Ga/Se-4p → Ga-4s while that for CuInSe₂ emerges as due to transition between Se-4p → In-5s bands. The calculated dielectric constant, e₁ (0) varepsilon_{1} (0) , for CuInSe₂ is higher than that of CuGaSe₂. The electronic structure of both compounds is reasonably interpreted by the LCAO (DFT) method. The optical properties computed using the FP-LAPW model (with scissor correction) are close to the spectroscopic ellipsometry data available in the literature.     

Theoretical Study of Electronic Structure and Thermoelectric Properties of Doped CuAlO<Subscript>2</Subscript>

The doping level dependence of thermoelectric properties of delafossite CuAlO₂ has been investigated in the constant scattering time (τ) approximation, starting from the first principles of electronic structure. In particular, the lattice parameters and the energy band structure were calculated using the total energy plane-wave pseudopotential method. It was found that the lattice parameters of CuAlO₂ are a = 2.802 Å and c = 16.704 Å, and the internal parameter is u = 0.1097. CuAlO₂ has an indirect band gap of 2.17 eV and a direct gap of 3.31 eV. The calculated energy band structures were then used to calculate the electrical transport coefficients of CuAlO₂. By considering the effects of doping level and temperature, it was found that the Seebeck coefficient S(T) increases with increasing acceptor doping (A _d) level. The values of S(T) in our experiments correspond to an A _d level at 0.262 eV, which is identified as the Fermi level of CuAlO₂. Based on our experimental Seebeck coefficient and the electrical conductivity, the constant relaxation time is estimated to be 1 × 10^?16 s. The power factor is large for a low A _d level and increases with temperature. It is suggested that delafossite CuAlO₂ can be considered as a promising thermoelectric oxide material at high doping and high temperature.     

Thermoelectric Properties of Sb-Doped Mg<Subscript>2</Subscript>Si<Subscript>0.3</Subscript>Sn<Subscript>0.7</Subscript>

Mg₂(Si_0.3Sn_0.7)_1−y Sb _y (0 ≤ y ≤ 0.04) solid solutions were prepared by a two-step solid-state reaction method combined with the spark plasma sintering technique. Investigations indicate that the Sb doping amount has a significant impact on the thermoelectric properties of Mg₂(Si_0.3Sn_0.7)_1−y Sb _y compounds. As the Sb fraction y increases, the electron concentration and electrical conductivity of Mg₂(Si_0.3Sn_0.7)_1−y Sb _y first increase and then decrease, and both reach their highest value at y = 0.025. The sample with y = 0.025, possessing the highest electrical conductivity and one of the higher Seebeck coefficient values among all the samples, has the highest power factor, being 3.45 mW m⁻¹ K⁻² to 3.69 mW m⁻¹ K⁻² in the temperature range of 300 K to 660 K. Meanwhile, Sb doping can significantly reduce the lattice thermal conductivity (κ _ph) of Mg₂(Si_0.3Sn_0.7)_1−y Sb _y due to increased point defect scattering, and κ _ph for Sb-doped samples is 10% to 20% lower than that of the nondoped sample for 300 K < T < 400 K. Mg₂(Si_0.3Sn_0.7)_0.975Sb_0.025 possesses the highest power factor and one of the lower κ _ph values among all the samples, and reaches the highest ZT value: 1.0 at 640 K.     

Electronic Structures and Transport Properties of Single-Filled CoSb<Subscript>3</Subscript>

Band structure and density of states (DOS) of CoSb₃ single-filled by seven kinds of atoms (R_0.125Co₄Sb₁₂) are calculated by the density functional method. The results for the electronic structures in turn determine the electrical transport and thermal performance. It is found that the band structure of R_0.125Co₄Sb₁₂ shows no significant changes compared with that of CoSb₃, and the results indicate that void filling with a small quantity of R atoms does not change the bond formation in CoSb₃. However, the partial DOS reveals that there could be interaction of Sn, Tl, In, and Yb atoms with CoSb₃. The results for the electrical transport properties and thermal properties show that Sn, Tl, and In atoms increase the Seebeck coefficient and La, Eu, and Yb atoms are helpful for increasing the electron concentration and decreasing the thermal conductivity further. According to our calculations and Yang’s principle, double-filled CoSb₃ with atomic combinations of (In, Ca), (In, Ba), (Sn, Eu), and (Sn, La) may exhibit good thermoelectric performance.     

Thermoelectric Properties of Mn-Doped Ca<Subscript>5</Subscript>Al<Subscript>2</Subscript>Sb<Subscript>6</Subscript>

Ca₅Al₂Sb₆ is a relatively inexpensive Zintl compound exhibiting promising thermoelectric efficiency at temperatures suitable for waste heat recovery. Motivated by our previous studies of Ca₅Al₂Sb₆ doped with Na and Zn, this study focuses on doping with Mn²⁺ at the Al³⁺ site. While Mn is a successful p-type dopant in Ca₅Al₂Sb₆, we find that incomplete dopant activation yields lower hole concentrations than obtained with either previously investigated dopant. High-temperature Hall effect and Seebeck coefficient measurements show a transition from nondegenerate to degenerate semiconducting behavior in Ca₅Al_2−x Mn _x Sb₆ samples (x = 0.05, 0.1, 0.2, 0.3, 0.4) with increasing Mn content. Ultimately, no improvement in zT is achieved via Mn doping, due in part to the limited carrier concentration range achieved.     

Optical Properties of K<Subscript>2</Subscript>O-Li<Subscript>2</Subscript>O-WO<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> Glasses: Evidence of Mixed Alkali Effect

Glass with compositions xK₂O-(30 ? x)Li₂O-10WO₃-60B₂O₃ for 0 ≤ x ≤ 30 mol.% have been prepared using the normal melt quenching technique. The optical reflection and absorption spectra were recorded at room temperature in the wavelength range 300–800 nm. From the absorption edge studies, the values of the optical band gap (E _opt) and Urbach energy (ΔE) have been evaluated. The values of E _opt and ΔE vary non-linearly with composition parameter, showing the mixed alkali effect. The dispersion of the refractive index is discussed in terms of the single oscillator Wemple Di-Domenico model.     

Microwave Dielectric Properties of ZnO-2TiO<Subscript>2</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> Ceramics with BaCu (B<Subscript>2</Subscript>O<Subscript>5</Subscript>) Addition

The influence of BaCu(B₂O₅) (BCB) addition on the sintering temperature and microwave dielectric properties of ZnO-2TiO₂-Nb₂O₅ (ZTN) ceramic has been investigated using dilatometry, x-ray diffraction, scanning electron microscopy, and microwave dielectric measurements. A small amount of BCB addition to ZTN can lower the sintering temperature from 1100°C to 900°C. The reduced sintering temperature was attributed to the formation of the BCB liquid phase. The ZTN ceramics containing 3.0 wt.% BCB sintered at 900°C for 2 h have good microwave dielectric properties of Q × f = 19,002 GHz (at 6.48 GHz), ε _r = 45.8 and τ _f  = 23.2 ppm/°C, which suggests that the ceramics can be applied in multilayer microwave devices, provided that Ag compatibility exists.     

Fabrication and Electromagnetic Properties of Conjugated NH<Subscript>2</Subscript>-CuPc@Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>

Conjugated amino-phthalocyanine copper containing carboxyl groups/magnetite (NH₂-CuPc@Fe₃O₄) has been fabricated from FeCl₃·6H₂O and NH₂-CuPc via a simple solvothermal method and its electromagnetic properties investigated. Scanning electron microscopy and transmission electron microscopy revealed that the NH₂-CuPc@Fe₃O₄ was a waxberry-like nanomaterial with NH₂-CuPc molecules effectively embedded in the interior of Fe₃O₄ particles in the form of beads. Introduction of NH₂-CuPc effectively improved the complementarity between the dielectric and magnetic losses of the system, resulting in excellent electromagnetic performance. The minimum reflection loss of the as-prepared composite reached ?33.4 dB at 7.0 GHz for coating layer thickness of 4.0 mm and bandwidth below ?10.0 dB (90% absorption) of up to 3.8 GHz. These results indicate that introduction of NH₂-CuPc results in a composite with potential for use as an electromagnetic microwave absorption material.     

Density-Functional Study of the Electronic Structure and Optical Properties of Transparent Conducting Oxides In<Subscript>4</Subscript>Sn<Subscript>3</Subscript>O<Subscript>12</Subscript> and In<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript>

The electronic structure and optical properties of In₄Sn₃O₁₂ and In₄Ge₃O₁₂ are studied by the projector-augmented-wave method based on the density-functional theory within the generalized gradient approximation. The cation ordering of the two compounds is explored by means of first-principles calculations. It is found that the valence-band maximum of the materials is determined by the d states of metal elements and O-2p states; the conduction-band minimum is occupied by an admixture of the O-2p states, In-5s states, and Sn-5s or Ge-4s states, respectively. The two compounds are direct-bandgap semiconductors. The low intensity of the absorption coefficient, reflectivity, and loss function shows that they are good transparent conducting oxides.     

First-Principles Study of Electronic Structure,Mechanical, and Thermoelectric Properties of Ternary Palladates CdPd<Subscript>3</Subscript>O<Subscript>4</Subscript> and TlPd<Subscript>3</Subscript>O<Subscript>4</Subscript>

Ternary palladates CdPd₃O₄ and TlPd₃O₄ have been studied theoretically using the generalized gradient approximation (GGA), modified Becke–Johnson, and spin–orbit coupling (GGA–SOC) exchange–correlation functionals in the density functional theory (DFT) framework. From the calculated ground-state properties, it is found that SOC effects are dominant in these palladates. Mechanical properties reveal that both compounds are ductile in nature. The electronic band structures show that CdPd₃O₄ is metallic, whereas TlPd₃O₄ is an indirect-bandgap semiconductor with energy gap of 1.1 eV. The optical properties show that TlPd₃O₄ is a good dielectric material. The dense electronic states, narrow-gap semiconductor nature, and Seebeck coefficient of TlPd₃O₄ suggest that it could be used as a good thermoelectric material. The magnetic susceptibility calculated by post-DFT treatment confirmed the paramagnetic behavior of these compounds.     

Transport Properties and Cationic Substitutions in Sr<Subscript>2</Subscript>IrO<Subscript>4</Subscript>

We realized cationic substitutions in Sr₂IrO₄ and measured resistivity, thermoelectric power, and the Hall coefficient. A two-carrier model, reflecting the presence of thermally activated carriers at high temperature, qualitatively explains the behavior of the Hall coefficient of Sr_1.95La_0.05IrO₄ in comparison with Sr₂IrO₄. Concerning the substitution of Ir by different transition metals, Pt with 5d orbitals does not affect the transport properties, contrary to Ti and Rh with 3d and 4d orbitals, respectively. This may be explained by strong spin–orbit coupling involved in Ir and Pt, in comparison with 3d or 4d transition metals.