First principles investigation of barium chalcogenide ternary alloys

The ab initio full potential linearized augmented plane wave (FP-LAPW) method within density functional theory was applied to study the effect of composition on the structural, electronic, thermodynamic and optical properties of BaS_1−xO_x, BaS_1−xSe_x and BaS_1−xTe_x ternary alloys. The effect of composition on lattice parameter, bulk modulus, band gap, refractive index and dielectric function was investigated. The microscopic origins of the gap bowing were explained by using the approach of Zunger and co-workers. The thermodynamic stability of these alloys was investigated by calculating the excess enthalpy of mixing ΔH_m as well as the phase diagram. In addition to FP-LAPW method, the composition dependence of the refractive index and the dielectric constant was studied by different models.     

Relationship between photoluminescence and structural properties of the sputtered Zn1−xCdxO films on Si substrates

Zn_1−xCd_xO (x=0.2, 0.4) alloyed crystal thin films have been deposited on Si(1 1 1) substrates at different temperatures by using dc reactive magnetron sputtering technique. The Zn_1−xCd_xO films are of highly (0 0 2)-preferred orientation possessing the hexagonal wurtzite structure of pure ZnO. At 450 °C, the films have better crystal quality and photoluminescent characteristics. For the films with x=0.2 and 0.4, the corresponding near-band-edge (NBE) energies are 3.10 and 3.03 eV, respectively, both have red-shifts compared with that of ZnO (3.30 eV). For the substrate temperatures lower or higher than 450 °C, the other NBE emission peak appears, the X-ray diffraction intensity of (0 0 2) peak decreases and the related FWHM increases. With the Cd addition up to x=0.4 both the XRD and PL intensity of the Zn_1−xCd_xO films decrease sharply in comparison with x=0.2.     

Doping-induced microstructural, textural and optical properties of In2Ti1−xVxO5+δ semiconductors and their role in the photocatalytic splitting of water

The physicochemical properties of V-doped indium titanates (In₂Ti_1−xV_xO_5+δ, 0.0 ≤ x ≤ 0.2) were investigated by using XPS, powder XRD, UV–vis, SEM and luminescence spectroscopy techniques. The Rietveld refinement of XRD data revealed that even though the V-containing samples were isostructural with In₂TiO₅ (orthorhombic space group Pnma), a systematic x-dependent variation was noticeable in the Ti–O bond lengths in [TiO₆] octahedral units, cell parameters and in the value of δ. XPS results confirmed the coexistence of V⁵⁺ and V⁴⁺ states, leading thereby to an enhancement in oxygen non-stoichiometry in the doped samples. A loading-dependent progressive shift from 400 to 750 nm was also observed in the onset of the absorption edge, indicating a significant narrowing of the band gap. Furthermore, the samples with higher V-content were comprised of the grain clusters having larger size and an irregular shape. The UV–vis, photoluminescence and thermoluminescence studies indicate that the doping-induced lattice defects may give rise to certain closely spaced acceptor/donor energy levels in between the band gap of host matrix. The indium titanates are found to serve as stable photocatalysts for water splitting under visible light, where oxygen was the major reaction product. The role of microstructural and morphological properties in the photocatalytic activity is discussed.     

Microstructures and thermoelectric properties of p-type pseudo-binary AgxBi0.5Sb1.5−xTe3 (x = 0.05–0.4) alloys prepared by cold pressing

The p-type pseudo-binary Ag_xBi_0.5Sb_1.5−xTe₃ (x = 0.05–0.4) alloys were prepared by cold pressing. The thermal conductivities (κ) were calculated from the values of heat capacities, densities and thermal diffusivities measured, and range approximately from 0.66 to 0.56 (W K^− 1 m^− 1) for the Ag_xBi_0.5Sb_1.5−xTe₃ alloy with molar fraction x being 0.4. Combining with the electrical properties obtained in the previous study, the maximum dimensionless figure of merit ZT of 1.1 was obtained at the temperature of 558 K.     

Optical and other physical characteristics of Ge–Se–Cd thin films

Amorphous Ge₂₀Se_80−xCd_x thin films with different compositions (x = 0, 2.5, 5, 7.5 and 10 at.%) were deposited onto glass substrates by thermal evaporation. The reflection spectra, R(λ), of the films at normal incidence were obtained in the spectral region from 400 to 2500 nm. Based on the use of the maxima and minima of the interference fringes, a straightforward analysis proposed by Minkov has been applied to derive the optical constants and the film thickness for the Ge₂₀Se_80−xCd_x thin films. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple and DiDomenico model. Tauc relation for the allowed non-direct transition describes the optical transition in the studied films. With increasing cadmium content the refractive index increases while the optical band gap decreases. The optical band gap decreases from 2 to 1.5 eV with increasing cadmium content from 0 to 10 at.%. The chemical-bond approach has been applied successfully to obtain the excess of Se–Se homopolar bonds and the cohesive energy of the Ge₂₀Se_80−xCd_x system.     

Microhardness of the YbAg<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>In<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>4</Subscript> alloy system

We report Vickers microhardness measurements on flux grown single crystals of the YbAg_xIn_{1 − x}Cu₄ alloy system. Although sample dependent, the microhardness exhibits a clear concentration dependence: in general, it decreases with x. The lattice parameter as a function of x exhibits a similar behavior. For x < 0.5, where the lattice parameter is almost constant, the microhardness exhibits a weak enhancement. Similar concentration dependence of the lattice parameter, resistivity and microhardness allows us to conclude that the microhardness reflects the evolution of the YbAg_xIn_{1 − x}Cu₄ alloy system towards more metallic character with increasing x.     

Structure and optical properties of InN and InAlN films grown by rf magnetron sputtering

The structure and optical properties of InN and In-rich InAlN films grown by magnetron sputtering were investigated. The XRD results show that these films are highly c-axis oriented. The film morphology and microstructure of these films were observed by AFM and SEM which reveals that the films grown in island growth mode. Optical properties of these films were studied by absorption method. The band gap energy of the InN film grown under substrate temperature of 400 °C is 1.38 eV. By studying the E _g values of InN films deposited under different substrate temperature, the Burstein-Moss effect on band gap of InN was examined. The significant band gap bowing of our In-rich InAlN films was found to be correlated with the In contents. The bowing parameter of 3.68 eV was obtained which is in agreement with previous theoretical predictions.     

Crystal, electronic and luminescence properties of Eu-doped Sr2Al2−xSi1+xO7−xNx

The crystal and electronic structures, as well as the luminescence properties of Sr₂Al_2−xSi_1+xO_7−xN_x:Eu²⁺ are reported. First-principles calculations energetically confirm that the Al and Si atoms are in partial ordering in the 2a and 4e sites in Sr₂Al₂SiO₇. In addition, the band structure calculation shows that Sr₂Al₂SiO₇ has an indirect band gap with an energy gap of about 4.07 eV, which is in good agreement with the experimental data (5.3 eV) obtained from the diffuse reflection spectrum. The crystal structure of Sr₂Al₂SiO₇ can be modified by Si–N substitution for Al–O in the lattice with a maximum solubility of about x=0.6. The average bond length of Eu_Sr^-(O,N) slightly increases although the lattice parameters decrease with the incorporation of Si–N in Sr₂Al₂SiO₇:Eu²⁺. Under excitation in the visible spectral region, Sr₂Al_2−xSi_1+xO_7−xN_x:Eu²⁺ emits blue to yellow light with a broad emission band in the range of 480–570 nm, varying with both the Eu concentration and the x value. The red shift of the emission band of Eu²⁺ is associated with an increase in the crystal-field splitting and the covalency, which arise from the incorporation of nitrogen as well as the energy transfer between the Eu ions at high Eu concentrations. Moreover, the Eu ions have a strong effect on both the concentration quenching and the thermal quenching in Sr₂Al_2−xSi_1+xO_7−xN_x. The temperature dependence of photoluminescence indicates that Sr₂Al_2−xSi_1+xO_7−xN_x:Eu²⁺ shows strong thermal quenching due to the dominant nonradiative process at room temperature.     

Effect of oxygen pressure of SiOx buffer layer on the electrical properties of GZO film deposited on PET substrate

The present work was made to investigate the effect of oxygen pressure of SiO_x layer on the electrical properties of Ga-doped ZnO (GZO) films deposited on poly-ethylene telephthalate (PET) substrate by utilizing the pulsed-laser deposition at ambient temperature. For this purpose, the SiO_x buffer layers were deposited at various oxygen pressures ranging from 13.3 to 46.7 Pa. With increasing oxygen pressure during the deposition of SiO_x layer as a buffer, the electrical resistivity of GZO/SiO_x/PET films gradually decreased from 7.6 × 10^− 3 to 6.8 × 10^− 4 Ω·cm, due to the enhanced mobility of GZO films. It was mainly due to the grain size of GZO films related to the roughened surface of the SiO_x buffer layers. In addition, the average optical transmittance of GZO/SiO_x/PET films in a visible regime was estimated to be ~ 90% comparable to that of GZO deposited onto a glass substrate.     

Thermally activated rotation of Co1−xO particles within zirconia grains

Yttria partially stabilized zirconia (Y-PSZ) and Co_1−xO powders in 4:1 molar ratio were sintered and then annealed at 1300 and 1600°C to investigate the orientation change of Co_1−xO particles within Y-PSZ grains. Transmission electron microscopic observations indicated the Co_1−xO particles remained nonepitaxy in Y-PSZ grains after annealing at 1300°C for 300 h. When fired at 1600°C for 1–100 h, submicro-sized Co_1−xO particles (denoted as C) reached parallel epitaxy relationship, i.e. [100]_C//[100]_Z, [010]_C//[010]_Z and another relationship, i.e. [111]_C//[100]_Z, //[011]_Z with respect to the host zirconia grain (denoted as Z) nearly free of tetragonal precipitates. On the other hand, larger intragranular Co_1−xO particles (>1 μm in diameter) failed to reach epitaxial orientations even subject to prolonged annealing (100 h) at 1600°C. The temperature and size dependence of orientation change of the intragranular particle is in accordance with theoretical consideration of Brownian type rotation of the particle above a critical temperature for anchorage release at interface.     

Effects of Ho2O3 addition on defects of BaTiO3

Effects of Ho₂O₃ addition on defects of BaTiO₃ ceramic have been studied in terms of electrical conductivity at 1200 °C as a function of oxygen partial pressure (P_O2°) and oxygen vacancy concentration. The substitution of Ho³⁺ for the Ti site in Ba(Ti_1−xHo_x)O_3−0.5x resulted in a significant shift of conductivity minimum toward lower oxygen pressures and showed an acceptor-doped behavior. The solubility limit of Ho on Ti sites was confirmed less than 3.0 mol% by measuring the electrical conductivity and the lattice constant. Oxygen vacancy concentrations were calculated from the positions of P_O2° in the conductivity minima and were in good agreement with theoretically estimated values within the solubility limit. The Curie point moved to lower temperatures with increasing the oxygen vacancy concentration and Ho contents.     

Molecular simulation study of the structural properties in InxGa1−xAs alloys: Comparison between Valence Force Field and Tersoff potential models

The thermodynamic and structural properties of compound semiconductor alloys have been generally modelled using either the Valence Force Field model or the Tersoff potential model. This work compares the properties, such as lattice constant and bond length, of the In_xGa_1−xAs alloy as predicted by Monte Carlo simulations in the semigrand isothermal isobaric ensemble using both the potential models, with experimental data. The lattice constants are expected to follow the Vegard’s law at any given temperature. Valence Force Field model predicts bond length data which follows the experimentally determined values at 300 K; whereas the Tersoff model forecasts that the virtual crystal approximation will be followed. The VFF model, with its experimentally determined parameters, is found to be better for modelling the alloy at room temperature. The Tersoff model, with its fitted parameters, on the other hand predicts the effect of temperature on the microscopic structure of the alloy better. The parameters of the Tersoff potential characterizing the In–Ga interactions can be further improved to predict bond lengths more accurately.     

Synthesis,structural and optical characterization of Ni-doped ZnO nanoparticles

Nanocrystalline Zn_1−x Ni _x O (x = 0.00, 0.02, 0.04, 0.06, 0.08) powders were synthesized by a simple sol–gel autocombustion method using metal nitrates of zinc, nickel and glycine. Structural and optical properties of the Ni-doped ZnO samples annealed at 800 °C are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive analysis using X-rays (EDAX), UV–visible spectroscopy and photoluminescence (PL). X-ray diffraction analysis reveals that the Ni-doped ZnO crystallizes in a hexagonal wurtzite structure and secondary phase (NiO) was observed with the sensitivity of XRD measurement with the increasing nickel concentration (x ≥ 0.04). The lattice constants of Ni-doped ZnO nanoparticles increase slightly when Ni²⁺ is doped into ZnO lattice. The optical absorption band edge of the nickel doped samples was observed above 387 nm (3.20 eV) along with well-defined absorbance peaks at around 439 (2.82 eV), 615(2.01 eV) and 655 nm (1.89 eV). PL measurements of Ni-doped samples illustrated the strong UV emission band at ~3.02 eV, weak blue emission bands at 2.82 and 2.75 eV, and a strong green emission band at 2.26 eV. The observed red shift in the band gap from UV–visible analysis and near band edge UV emission with Ni doping may be considered to be related to the incorporation of Ni ions into the Zn site of the ZnO lattice.     

Physical properties of transparent conducting Cd–Te–In–O thin films: Outlining a thermodynamic system for transparent conducting oxides

Cd–Te–In–O thin films are grown by pulsed laser deposition using a composite target of CdTe powder embedded in an indium matrix. Oxygen pressures range from 2.00 to 6.67 Pa at a substrate temperature of 420 °C. The structure, optical transmission and sheet resistance of the films are measured. Substitutional compounds with In_2 − 2x(Cd,Te)_2xO₃ stoichiometry are found at high oxygen pressures. A ternary phase diagram of the CdO–In₂O₃–TeO₂ system shows the relationship between the structure and the stoichiometry of the films. To evaluate film performance, a figure of merit is proposed based on the relationship between the integral photonic flux and the sheet resistance. The best figure of merit values corresponds to a sample prepared at 3.8 Pa O₂ that consists of (In₂O₃)_0.3(CdTe₂O₅)_0.7 and exhibits an optical band gap of 3.0 eV. This sample is a suitable substrate for electrodeposition due to its good electrochemical stability.     

Principal band gaps and bond lengths of the alloy (AlxGa1−x)1−zInzPyAs1−y lattice matched to GaAs

The principal band gaps (E(Γ),E(L), and E(X)) and bond lengths (d(x,y,z))of the alloy (Al_xGa_1−x)_1−zIn_zP_yAs_1−y (where, 0 < x + z < 1, and 0 < y < 1) are calculated over the entire composition range based on the first order correlated function expansion (CFE) scheme. Defining the lattice strain parameter as , it is found that a good quality of alloy (defining ? < ∼ 0.5%) can be obtained in the composition region : 0 < x < ∼ 0.3, 0 < y < ∼ 0.2 and 0 < z < ∼ 0.1. The first order CFE lattice matching relations and corresponding band gaps for the alloy on the GaAs substrate are also determined. It is found that the principal band gaps of the alloy (Al_xGa_1−x)_1−zIn_zP_yAs_1−y lattice matched to GaAs covers band gap ranges: 1.45 eV E < (Γ) 2.69 eV, 1.80 eV < E(L) < 2.38 eV, and 1.97 eV < E(X) < 2.20 eV, while the direct band gap covers from 1.45 eV to 2.05 eV. Our theoretical prediction was compared with the existing experimental data.     

Ab initio calculations of electronic structures of LiYF4 crystals containing F-type color centers

The electronic structures of LiYF₄ crystals containing F, F⁻, and M color centers (F₂ center) with the lattice structure optimized are studied within the framework of the density functional theory. The calculation indicated that F, F⁻, and M color centers have donor energy levels in the forbidden band. The electronic transition energies from the donor level to the bottom of the conduction band are 3.74 eV, 2.85 eV, and 2.42 eV, respectively, which correspond to the 331 nm, 436 nm, and 513 nm absorption bands. It is predicted that the absorption bands observed at 330 nm, 440 nm, and 505 nm could arise from the F, F⁻, and M centers, respectively, in LiYF₄ crystals.     

Ca4REO(BO3)3 crystals for green and blue microchip laser generation: from crystal growth to laser and nonlinear optical properties

We have taken advantage of congruent melting behavior of the nonlinear rare-earth oxoborate Ca₄REO(BO₃)₃ family to perfect a process of collective fabrication of self-frequency doubling microchip laser based on Nd:GdCOB (Ca₄Gd_1−xNd_xO(BO₃)₃) crystals. The process goes from Czochralski boule to 1 × 3 mm² chips perfectly oriented (better than 0.1°) to the phase matching direction (θ=90°, φ=46°) in the XY principal plane, with dielectric mirrors directly deposited on both faces of the chips. 20 mW of self-frequency doubling output power at 530 nm was performed under 800 mW of diode laser as incident pump power at 812 nm. In addition, new compositions from the solid solution Ca₄Gd_1−xY_xO(BO₃)₃ (Gd_1−xY_xCOB) (x=0.13, 0.16, 0.44) have been grown by the Czochralski pulling method, in order to achieve noncritical phase matching (NCPM) second harmonic generation of ⁴F_3/2 → ⁴I_9/2 Nd³⁺ doped laser hosts. Three types of laser wavelengths have been chosen: Nd:YAP (YAlO₃) at 930 nm, Nd:YAG (Y₃Al₅O₁₂) at 946 nm, and Nd:ASL (Nd_ySr_1−x La_x−yMg_x Al_12−xO₁₉) at 900 nm. Angular acceptance measurements of these three types of compositions present very large values, compared to pure GdCOB or YCOB oriented in critical phase matching configurations.     

The effect of excess titanium and crystal symmetry on electronic properties of Pb(Zr1−xTix)O3 compounds

In this paper the structural and electronic properties including band structure, energy gap and density of states have been studied for different phases of Pb(Zr_1−xTi_x)O₃ compounds with a wide range of Ti/Zr ratio (i.e. from x = 0 to x = 1). The calculations were performed in the framework of density functional theory (DFT), using the full potential-linearized augmented plane wave (FP-LAPW) method with the generalized gradient approximation (GGA). In general, our results show that for all cases (x = 0, 0.33, 0.5, 0.66 and 1) by increasing the amount of Ti atoms the band gap decreases, because of the strong hybridization between Ti-3d and O-2p orbital. But, in other hand, decreasing the crystal symmetry results in widening the band gap. For the monoclinic phase (x = 0.5) the effect of excess Ti on the band gap is less than the effect of crystal symmetry, so there is an increase in the band gap.     

The structural properties of Pb1−xHgxS films of variable optical gap

Electron diffraction and differential thermal analysis studies of solution-grown films of Pb_1?xHg_xS suggest that PbS will alloy with both phases (α and β) of HgS over a wide (up to about 33 at.% Hg) concentration range to form two different types of Pb_1?xHg_xS (semiconducting systems of variable band gap) with f.c.c. symmetry. The two alloy phases can be stabilized by choosing appropriate growth conditions. The lattice parameter and the optical band gap of the f.c.c. alloy of PbS with α-HgS increases with increasing Hg concentration in the films. The alloy of PbS with β-HgS also has an f.c.c. structure, but its lattice parameter and the optical gap decrease with increasing Hg concentration. By changing the composition up to 33 at.% Hg, the optical gap can be varied over a wide range from 0.2 to 1.2 eV.     

Structural and electronic properties of BiOX (X = F, Cl, Br, I) considering Bi 5f states

Density functional theory (DFT) calculations have been performed to investigate the structural and electronic properties of BiOX (X = F, Cl, Br, I) photocatalysts, considering the Bi 5f states. Comparing with our previous results without Bi 5f states, the present work conveys similar gap features and comparable gap widths for the unrelaxed species, but the relaxation here causes opposite directions of atomic displacements and different trends for band and gap widths. The unrelaxed BiOF exhibits a direct band gap of 3.25 eV, while the other three species present the indirect gaps of 2.62, 2.16 and 1.51, respectively. Atomic relaxation expands the above gaps to 3.41, 2.69, 2.21 and 1.62 eV correspondingly. Analyses based on wavefunction isosurfaces and decomposed orbitals reveal that at the valence-band tops, O 2p_z and F 2p_z states prevail in BiOF, O 2p_y and X np_y dominate in BiOCl and BiOBr, and the I 5p_x state governs in BiOI. The conduction-band bottoms are composed mainly of the Bi 6p_z orbital.