Optical Properties of Nonstoichiometric Tantalum Oxide TaO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> (<Emphasis Type="Italic">x</Emphasis> &lt; 5/2) According to Spectral-Ellipsometry and Raman-Scattering Data

Optical properties of amorphous nonstoichiometric tantalum-oxide films of variable composition (TaO_x, x = 1.94–2.51) in the spectral range of 1.12–4.96 eV, obtained by ion-beam sputtering-deposition of metallic tantalum at different partial oxygen pressures (0.53–9.09 × 10^–3 Pa), have been investigated. It is shown by spectral ellipsometry that the character of dispersion of the absorption coefficient and refractive index in TaO_x of variable composition suggests that light-absorbing films with dispersion similar to that in metals are formed at oxygen pressures in the growth chamber below 2.21 × 10^–3 Pa, whereas transparent films with dielectric dispersion are formed at pressures above 2.81 × 10^–3 Pa. According to the data of quantumchemical simulation, the absorption peak at a photon energy of 4.6 eV in TaO_x observed in the absorptioncoefficient dispersion spectrum is due to oxygen vacancy. The peak in the Raman-scattering spectra of TaO_x films with metallic dispersion at frequencies of 200–230 cm^–1 is presumably related to tantalum nanoclusters.     

Atomic and Electronic Structures of Metal-Rich Noncentrosymmetric ZrO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

The atomic and electronic structures of metal-rich noncentrosymmetric zirconium oxide synthesized by the ion beam sputtering of a metallic target in an oxygen atmosphere has been studied by X-ray photoelectron spectroscopy, Raman scattering, spectral ellipsometry, and quantum-chemical simulation. It has been established that ZrO_{x < 2} consists of ZrO₂, metallic Zr, and zirconium suboxides ZrO_y. The stoichiometry parameter of ZrO_y has been estimated. It has been shown that the optical properties of ZrO_{x < 2} are determined by metallic Zr. A model of fluctuation of the width of the band gap and a potential for electrons and holes in ZrO_{x < 2} based on spatial fluctuations of the chemical composition has been proposed.     

Oxygen isotope effect in chromium-doped Pr<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganites

The effect of oxygen isotope substitution on the properties of Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x O₃ manganites (x = 0, 0.02, 0.05) have been studied. The introduction of chromium favors (i) the decomposition of a charge-ordered state and (ii) the appearance of a ferromagnetic metallic phase in Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x ^16–18O₃. The isotope substitution ¹⁶O → ¹⁸O leads to a decrease in the content of the ferromagnetic phase, an increase in the charge-ordering transition temperature (T _CO), and a decrease in the ferromagnetic transition temperature (T _FM). The isotope mass exponent is evaluated.     

Comparative study of solid-state reaction and sol-gel process for synthesis of Zr-doped Li<Subscript>0.5</Subscript>La<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> solid electrolytes

We investigated the synergistic influences of synthesis methods (solid-state reaction vs. sol-gel process) and Zr⁴⁺ doping on the structure and ionic conductivity of perovskite-structured Li_0.5La_0.5TiO₃ (LLTO) solid electrolytes. The lithium-ion conductivity of Li_0.5La_0.5Ti_1???x Zr _x O₃ ceramic specimens was evaluated as a function of x value and compared carefully between those two synthesis methods. Regarding the conductivity, sol-gel process is better for the synthesis of LLTO than solid-state reaction. As a result, the highest grain conductivity is obtained in the sol-gel-derived pure LLTO sample with x?=?0, reaching 1.10?×?10^?3 S?·?cm^?1. Partial substitution of Zr⁴⁺ enlarges the LLTO’s grain aggregate size and increases the total superficial area of aggregates. Consequently, Zr⁴⁺ substitution not only affects the grain (bulk) conductivity, but more importantly, also improves the grain boundary conductivity and the total conductivity. The highest total conductivity is 5.84?×?10^?5 S?·?cm^?1 with x?=?0.04 by sol-gel process.     

Study of the anisotropy of the dielectric response of Na<Subscript>1/2</Subscript>Bi<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> relaxor ferroelectric

The dielectric response, conductivity, and domain structure of (Na_1/2Bi_1/2)TiO₃ single crystals are studied in the temperature range of 290–750 K for the [100], [110], and [111] crystallographic directions. It is shown that the region of optical isotropization is observed in polarized light in the temperature range of 570–620 K. In this case, the birefringence (Δn) decreases and disappears (together with the image of the domain structure) for the [100] directions. The region of optical isotropization in the [111] directions is characterized by the disappearance of the image of the domain structure and by the existence of individual regions with partial quenching. The domain structure in the [110] directions remains distinguished against the background of a significant decrease in Δn in the indicated temperature range. The region of isotropization is also manifested in the temperature dependence of the imaginary part of the dielectric response and is determined by the isotropic character of the conductivity in the range of 570–620 K. The bulk conductivity has a thermally activated character with activation energies E _a = 50?60 meV at T < 500 K and E _a = 700?900 meV for T > 620 K. The low-frequency dispersion of the dielectric response is determined by the Maxwell–Wagner mechanism and is due to an increase in the ionic conductivity at temperatures above 620 K. The anisotropy of the susceptibility holds in the entire studied ranges of frequencies (25 Hz–1 MHz) and temperatures.     

Divalent rare-earth ions in LaF<Subscript>3</Subscript> crystals

The optical spectra and electric conductivity of LaF₃ crystals doped with 0.01, 0.1, and 0.3 mol % YbF₃, where Yb was partly or completely recharged to the divalent state, are studied. The long-wavelength absorption band of 370 nm is caused by electrons transitioning from state 4f ¹⁴ to the level of anion vacancies. The remaining bands at 300–190 nm are caused by 4f ¹⁴–5d ¹4f ¹³ transitions in Yb²⁺. The bulk electric conductivity and peaks of the dielectric losses of LaF₃–Yb²⁺ crystals are caused by Yb²⁺–anion vacancy dipoles. The activation energy of the reorientation of Yb dipoles is 0.58 eV. The optical and dielectric properties of Yb²⁺ centers are compared to those of Sm²⁺ and Eu²⁺ centers studied earlier in LaF₃ crystals.     

Conductivity and spectroscopic studies of Li<Subscript>2</Subscript>O-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

Lithium vanadium-borate glasses with the composition of 0.3Li₂O–(0.7-x)B₂O₃–xV₂O₅ (x?=?0.3, 0.325, 0.35, 0.375, 0.4, 0.425, 0.45, and 0.475) were prepared by melt-quenching method. According to differential scanning calorimetry data, vanadium oxide acts as both glass former and glass modifier, since the thermal stability of glasses decreases with an increase in V₂O₅ concentration. Fourier transform infrared spectroscopy data show that the vibrations of [VO₄] structural units occur at V₂O₅ concentration of 45 mol%. It is established that the concentration of V⁴⁺ ions increases exponentially with the growth of vanadium oxide concentration. Direct and alternative current measurements are carried out to estimate the contribution both electronic and ionic conductivities to the value of total conductivity. It is shown that the electronic conductivity is predominant in the total one. The glass having the composition of 0.3Li₂O-0.275B₂O₃-0.475V₂O₅ shows the highest electrical conductivity that has the value of 7.4?×?10^?5 S cm^?1 at room temperature.     

CeAlO<Subscript>3</Subscript> crystals: Preparation and study of their electrical and optical characteristics

Crystals of cerium aluminate with perovskite structure were obtained using the cold-crucible technique. The electrical and optical properties of cerium aluminate were studied in air in the range 300–1300 K. The main characteristics of CeAlO₃ at T=300 K are a follows: electrical conductivity σ=10^?7 S/cm, dielectric permittivity ?=3000–10000 (both measured at a frequency of 1000 Hz), thermal band-gap width ΔE=2.3±0.5 eV, and optical width δE=2.65±0.25 eV, which decreases at a rate of ?0.62×10^?3 eV/K with increasing temperature in the 300-to 1500-K interval.     

Optical properties and mechanisms of current flow in Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> films prepared by spray pyrolysis

Thin films Cu₂ZnSnS₄ (up to 0.9 μm thick) with p-type conductivity and band gap E_g = 1.54 eV have been prepared by the spray pyrolysis of 0.1 M aqueous solutions of the salts CuCl₂ · 2H₂O, ZnCl₂ · 2H₂O, SnCl₄ · 5H₂O, and (NH₂)₂CS at a temperature T_S = 290°C. The electrophysical properties of the films have been analyzed using the model for polycrystalline materials with electrically active grain boundaries. The energy and geometric parameters of the grain boundaries have been determined as follows: the height of the barriers is E_b ≈ 0.045–0.048 eV, and the thickness of the depletion region is δ ≈ 3.25 nm. The effective concentrations of charge carriers p₀ = 3.16 × 10¹⁸ cm^–3 and their mobilities in crystallites μ_p = 85 cm²/(V s) have been found using the technique for determining the kinetic parameters from the absorption spectra of thin films at a photon energy hν ≈ E_g. The density of states at grain boundaries N_t = 9.57 × 10¹¹ cm^–2 has been estimated.     

Nonstoichiometric high-pressure phase of Tm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript>

Tm _x Cu₃V₄O₁₂, a perovskite-like oxide (space group, Im-3; Z = 2; a = 7.279–7.293 Å) containing vacancies in its cationic sublattice, was obtained barothermally (P = 7.0–9.0 GPa, t = 1000–1100°C) for the first time. The temperature dependences on the electrical resistivity (10–300 K) and the magnetic susceptibility (0–300 K) were investigated. It was shown that the oxide Tm _x Cu₃V₄O₁₂ is characterized by metal-type conductivity and paramagnetic properties.     

Raman scattering spectroscopy of inclusions of carbon in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> films and its solid solutions with HfO<Subscript>2</Subscript>

We apply Raman scattering spectroscopy to study the nature of carbon inclusions in Al₂O₃ and (HfO₂) _x (Al₂O₃)_{1 ? x} films deposited using volatile complex compounds. Raman spectra of the films under investigation contain D and G vibrational modes, which indicate that carbon clusters of the sp ² configuration tend to form in the films. We estimate the size of clusters from the integrated intensity ratio I _D /I _G and find it to be in the range of 14–20 Å. The content of hydrogen in carbon clusters is calculated from the height of the photoluminescence pedestal and is found to vary from 14 to 30 at % depending on the regime of the film’s synthesis.     

Electrical instability of LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> crystals

The temperature behavior of I-U curves and the field and temperature dependences of the electrical resistivity and dielectric permittivity of crystals of the LiCu₂O₂ phase have been studied. It was established that the crystals belong to p-type semiconductors and that their static resistivity in the range 80–260 K follows the Mott law ρ=Aexp(T₀/T)^1/4 describing variable-range hopping over localized states. At comparatively low electric fields, the crystals exhibit threshold switching and characteristic S-shaped I-U curves containing a region of negative differential resistivity. In the critical voltage region, jumps in the conductivity and dielectric permittivity are observed. Possible mechanisms of the disorder and electrical instability in these crystals are discussed.     

Annealing study of electrodeposited CuInSe<Subscript>2</Subscript> and CuInS<Subscript>2</Subscript> thin films

In this study CuInSe₂ and CuInS₂ thin films were prepared onto ITO glass substrate using the electrodeposition technique in aqueous solution. The electrodeposited films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis. The annealing effects on electrodeposited precursors were investigated. The chalcopyrite structure of CuInSe₂/CuInS₂ showed an enhancement of crystallinity after subsequent selenization/sulfurization treatment in Se/S atmosphere, respectively. XRD and SEM studies revealed a dramatic improvement of the crystalline quality of CIS films after annealing treatments. Mott–Schottky measurements were used to assess the conductivity type of the films and their carrier concentration. The prepared samples underwent an etching process to remove the binary accumulated Cu_2?x(Se,S) phases shown in FESEM pictures. This etching process has shown a noticeable decrease in both, the flat band potential, V_fb (V), and the number of acceptors, N_A (cm^?3) in selenized CuInSe₂ and sulfurized CuInS₂ samples.     

UV absorption spectra of thin films of Cs<Subscript>2</Subscript>CdI<Subscript>4</Subscript> and Rb<Subscript>2</Subscript>CdI<Subscript>4</Subscript> ferroelectrics

Thin films of M₂CdI₄ ferroelectrics (M=Cs, Rb) of orthorhombic structure were synthesized, and their electronic optical spectrum was studied. It was established that both compounds belong to direct-gap dielectrics and that their low-frequency excitons are localized on a sublattice made up of (CdI₄)^2? tetrahedra. The temperature dependence of the exciton band parameters was studied for Cs₂CdI₄ within the temperature interval 90–420 K. The phase transitions occurring in this interval manifest themselves as breaks in the temperature behavior of the band spectral positions and weak peaks in the halfwidth and oscillator strength.     

Linear and nonlinear optical spectroscopy of gadolinium iron borate GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

The optical spectra and the second-harmonic generation (SHG) are studied in a noncentrosymmetric GdFe₃(BO₃)₄ magnet. In the region of weak absorption (α～20–400 cm^?1) below ～3 eV, three absorption bands are distinguished, which can be unambiguously assigned to forbidden electronic transitions from the ground ⁶A₁ state of the Fe³⁺ ion to its excited states ⁴T₁(～1.4 eV), ⁴T₂(～2 eV), and ⁴A₁, ⁴E(～2.8 eV). Intense absorption begins in the region above 3 eV (α～2–4×10⁵ cm^?1), where two bands at ～4.0 and 4.8 eV are observed, which are caused by allowed electric dipole charge-transfer transitions. The spectral features of SHG in the 1.2–3.0-eV region are explained by a change in the SHG efficiency caused by a change in the phase mismatch. It is shown that in the weak absorption region, phase matching can be achieved for SHG.     

Absorption spectra of some radiation-doped A<Subscript>3</Subscript>B<Subscript>5</Subscript> compounds

Temperature dependences of the absorption coefficient in A₃B₅ crystals before and after irradiation by electrons with an energy of 6 MeV and a dose of Ф = 2 × 10¹⁷ electron/cm² are studied. A low-lying E_v + 0.4 eV center of a nonimpurity origin is found in both undoped GaAs crystals and those doped with various impurities (Te, Zn, Sn, Ga_1–xIn_xAs, InP, and InP〈Fe〉).     

Electrophysical parameters of <Emphasis Type="Italic">c</Emphasis>-oriented Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> films with a low concentration of antistructural defects

Epitaxial c-oriented Bi₂Te₃ films 1.2 μm in thickness are grown by the hot wall method for a low supersaturation of the vapor phase over the surface of mica substrates. The hexagonal unit cell parameters a = 4.386 Å and c = 30.452 Å of the grown films almost coincide with the corresponding parameters of stoichiometric bulk Bi₂Te₃ crystals. At T = 100 K, the Hall concentration of electrons in the films is on the order of 8 × 10¹⁸ cm^?3, while the highest values of the thermoelectric coefficient (α ≈ 280 μV K^?1) are observed at temperatures on the order of 260 K. Under impurity conduction conditions, conductivity σ of the films increases upon cooling in inverse proportion to the squared temperature. In the temperature range 100–200 K, thermoelectric power parameter α²σ of Bi₂Te₃ films has values of 80–90 μW cm^?1 K^?2.     

Optical spectroscopy of intermetallic compounds TbNi<Subscript>2</Subscript>Mn<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript> (<Emphasis Type="Italic">x</Emphasis> = 0, 0.5, 1)

The optical properties of intermetallic compounds TbNi₂Mn_x (x = 0, 0.5, 1) have been investigated using the ellipsometric method in the spectral range from 0.22 to 16 μm. The specific features of the modification of the dispersions of spectral characteristics with a variation in the manganese concentration have been determined. The behavior of the frequency dependences of the optical conductivity in the interband absorption region has been discussed in terms of the available data on the electronic structure of these compounds. The concentration dependences of a number of electronic parameters have been calculated.     

Dielectric response of doped Bi<Subscript>12</Subscript>TiO<Subscript>20</Subscript>: Ru crystals in an alternating electric field

The results of examination of AC dependences of capacitance and dielectric loss tangent of sillenite Bi₁₂TiO₂₀ crystals doped with ruthenium on frequency are presented. Non-Debye dispersion of dielectric coefficients is found in the frequency interval of 5 × 10²–10⁵ Hz, and a resonance phenomenon is observed. Polarization processes in the studied samples are attributed to relaxators associated with metal–oxygen vacancies and structural elements incorporating 6s² lone-pair electrons.     

Investigation on lithium ion conductivity and structural stability of yttrium-substituted Li<Subscript>7</Subscript>La<Subscript>3</Subscript>Zr<Subscript>2</Subscript>O<Subscript>12</Subscript>

Advanced Li-air battery architecture demands a high Li⁺ conductive solid electrolyte membrane that is electrochemically stable against metallic lithium and aqueous electrolyte. In this work, an investigation has been carried out on the microstructure, Li⁺ conduction behaviour and structural stability of Li₇La_3-x Y _x Zr₂O₁₂ (x = 0.125, 0.25 and 0.50) prepared by conventional solid-state reaction technique. The phase analysis of Li₇La_3-x Y _x Zr₂O₁₂ (x = 0.125, 0.25 and 0.50) sintered at 1200 °C by powder X-ray diffraction (PXRD) and Raman confirms the formation of high Li⁺ conductive cubic phase (\( Ia\overline{3}d \)) lithium garnets. Among the investigated lithium garnets, Li₇La_2.75Y_0.25Zr₂O₁₂ sintered at 1200 °C exhibits a maximized room temperature total (bulk + grain boundary) Li⁺ conductivity of 3.21 × 10^?4 S cm^?1 along with improved relative density of 96 %. The preliminary investigation on the structural stability of Li₇La_2.75Y_0.25Zr₂O₁₂ in the solutions of 1 M LiCl, dist. H₂O and 1 M LiOH at 30 °C/50 °C indicates that the Li₇La_2.75Y_0.25Zr₂O₁₂ is relatively stable against 1 M LiCl and dist. H₂O. Further electrochemical investigation is essential for practical application of Li₇La_2.75Y_0.25Zr₂O₁₂ as protective solid electrolyte membrane in aqueous Li-air battery.