Photoluminescence and composition of amorphous As<Subscript>2</Subscript>Se<Subscript>3</Subscript> films modified with Er(<Emphasis Type="Italic">thd</Emphasis>)<Subscript>3</Subscript> complex compound

The photoluminescence and composition of amorphous As₂Se₃ films modified with an Er(thd)₃ complex compound have been studied. A band centered at 1.54 μm, characteristic of photoluminescence from Er embedded in amorphous matrices, has been revealed at room temperature. The composition of thin amorphous As₂Se₃ films modified with an Er(thd)₃ complex compound has been examined by methods of nuclear microanalysis: Rutherford backscattering and nuclear resonant reactions. Dependences of the concentrations of Er ions, oxygen, and carbon on the growth conditions of the films are obtained. It is shown that the Er concentration in a thin film varies nonlinearly as the relative concentration of the starting complex compound increases. In addition, the increase in the Er content of a film is accompanied by a simultaneous rise in the content of such light elements as oxygen and carbon. Comparative analysis of the nuclear microanalysis data and IR spectra demonstrates that, in modification of As₂Se₃ with the Er(thd)₃ complex compound by the given method, the nearest environment of Er in the complex compound is partly preserved.     

Effect of thallium doping on the mobility of electrons in Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> and holes in Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>

The Shubnikov–de Haas effect and the Hall effect in n-Bi_2–xTl_xSe₃ (x = 0, 0.01, 0.02, 0.04) and p-Sb_2–xTl_xTe₃ (x = 0, 0.005, 0.015, 0.05) single crystals are studied. The carrier mobilities and their changes upon Tl doping are calculated by the Fourier spectra of oscillations. It is found shown that Tl doping decreases the electron concentration in n-Bi_2–xTl_xSe₃ and increases the electron mobility. In p-Sb_2–xTl_xTe₃, both the hole concentration and mobility decrease upon Tl doping. The change in the crystal defect concentration, which leads to these effects, is discussed.     

Anti-stokes luminescence of Zn<Subscript>0.75</Subscript>Cd<Subscript>0.25</Subscript>S microcrystals annealed in the presence of oxygen

The nature of anti-Stokes luminescence centers excited in the temperature range 77–300 K by light with wavelengths from 620 to 710 nm and intensities in the range 10¹⁵–10¹⁶ photons/cm² in Zn_0.75Cd_0.25S microcrystals annealed in the presence of oxygen has been investigated. It is shown that the centers of two-photon excitation of this luminescence are clusters of native metal oxides (ZnO) _n and (CdO) _n , whose energy levels in the Zn_0.75Cd_0.25S band gap are 1.70–1.95 eV below the bottom of the conduction band.     

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.     

Effect of copper doping on kinetic phenomena in <Emphasis Type="Italic">n</Emphasis>-Bi<Subscript>2</Subscript>Te<Subscript>2.85</Subscript>Se<Subscript>0.15</Subscript>

In single crystals of copper-doped and undoped Bi₂Te_2.85Se_0.15 solid solutions with an electron concentration close to 1 × 10¹⁹ cm^?3, the temperature dependences are investigated for the Hall (R ₁₂₃, R ₃₂₁) and Seebeck (S ₁₁) kinetic coefficients, the electrical-conductivity (σ ₁₁), Nernst-Ettingshausen (Q ₁₂₃), and thermalconductivity (k ₁₁) coefficients in the temperature range of 77–400 K. The absence of noticeable anomalies in the temperature dependences of the kinetic coefficients makes it possible to use the one-band model when analyzing the experimental results. Within the framework of the one-band model, the effective mass of density of states (m _d ≈ 0.8m ₀), the energy gap (ε_g ≈ 0.2 eV), and the effective scattering parameter (r _eff ≈ 0.2) are estimated. The obtained value of the parameter r _eff is indicative of the mixed electron-scattering mechanism with the dominant scattering by acoustic phonons. Data on the thermal conductivity and the lattice resistivity obtained by subtracting the electron contribution according to the Wiedemann-Franz law are presented.     

Fabrication and photosensitivity of heterojunctions based on CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> crystals

Heterojunctions based on p-CuIn₃Se₅ crystals are fabricated by magnetron sputtering of an n-ZnO:Al target and by putting naturally cleaved n-GaSe thin wafers onto polished surfaces of p-CuIn₃Se₅ wafers. The current-voltage characteristics and mechanisms of current flow in the diodes under study are analyzed. The photovoltaic effect revealed in the fabricated structures is discussed. It is shown that the fabricated photosensitive heterojunctions are promising for the development of selective analyzers of linearly polarized radiation.     

Structural transformations and optical properties of As<Subscript>2</Subscript>S<Subscript>3</Subscript> chalcogenide glasses

The effects of melt temperature T _i and quenching rate V _i on the structure and optical properties of As₂S₃ glasses is studied. It is found that the glass band gap increases with T _i and V _i , whereas a decrease is observed in the glass density, refractive index (from 2.71 to 2.48), and two-photon absorption coefficient (from 0.37 to 0.15 cm/MW), which is accompanied by an increase in the optical-breakdown damage threshold.     

Influence of Element Substitution on Corrosion Behavior of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Based Compounds

Atmospheric water may condense on the surface of Bi₂Te₃-based compounds constituting the Peltier module, depending on the operating environment used. In the stage of disposal, Bi₂Te₃-based compounds may come into contact with water in waste disposal sites. There are very few publications about the influence of condensed water on Peltier modules. Bi₂Te₃-Sb₂Te₃ or Bi₂Te₃-Bi₂Se₃ pseudo binary system compounds are used as p-type material or n-type material, respectively. The lattice distortion will be induced in the crystal of Bi₂Te₃-based compounds by element substitution due to the reduction in their thermal conductivity. However, the influence of element substitution on the corrosion behavior of Bi₂Te₃-based compounds remains unclear. In this study, the influence of element substitution on the corrosion behavior of Bi₂Te₃-based compounds with practical compositions has been investigated. Bi_0.5Sb_1.5Te₃ or Bi₂Te_2.85Se_0.15 was prepared by the vertical Bridgman method. The electrochemical properties at room temperature were evaluated by cyclic voltammetry in a standard three-electrode cell. The working electrolyte was a naturally aerated 0.6 or 3.0 mass% NaCl solution. From the tendency for corrosion potential for all the samples, the corrosion sensitivity of ternary compounds was slightly higher than that of binary compounds. From the trend of current density, it was found that Bi_0.5Sb_1.5Te₃ had a corrosion resistance intermediate between Bi₂Te₃ and Sb₂Te₃. On the other hand, corrosion resistance was affected despite a small amount of Se substitution, and the corrosion resistance of Bi₂Te_2.85Se_0.15 was close to or lower than that of Bi₂Se₃. From the observation results of the corrosion products, the trends of morphology and composition of corrosion products for Bi_0.5Sb_1.5Te₃ or Bi₂Te_2.85Se_0.15 were consistent with those of Sb₂Te₃ or Bi₂Se₃, respectively. From the results of x-ray photoelectron spectroscopy for the electrolyte after testing, the possibility that a corrosion product diffuses to the environment including the salt was suggested in Bi_0.5Sb_1.5Te₃. However, the amount of dissolved corrosion product was very low, and the chemical stability of the corrosion product was not changed or improved by element substitution.     

Special features of charge transport in PbGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals

The current-voltage (I-V) characteristics of PbGa₂Se₄ single crystals grown by the Bridgman-Stockbarger method with a resistivity of 10¹⁰–10¹² Ω cm were measured. The value of the majority carrier mobility μ=14 cm² V^?1 s^?1, calculated by the differential method of analysis of I-V characteristics, makes it possible to evaluate a number of parameters: the carrier concentration at the cathode (n_c0=2.48 cm^?3), the width of the contact barrier d_c=5.4×10^?8 cm, the cathode transparency D _c ^* =10^?5–10^?4 eV, and the quasi-Fermi level E_F=0.38 eV. It is found that a high electric field provides the charge transport through PbGa₂Se₄ crystals in accordance with the Pool-Frenkel effect. The value of the dielectric constant calculated from the Frenkel factor is found to be equal to 8.4.     

Properties of CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> crystals and In/CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> structures

Using the method of planar crystallization from the melt with deviations from the stoichiometric composition, p-CuIn₃Se₅ single crystals are grown. The electrical properties of the homogeneous crystals are studied. It is found that the resistivity of the p-CuIn₃Se₅ crystals depends on the excess Se content in the melt. It is established that the voltaic photosensitivity of the In/CuIn₃Se₅ structures is enhanced with an increasing excess of Se content in the melt. The energy spectrum and the character of interband transitions in the CuIn₃Se₅ crystals are discussed. It is concluded that the CuIn₃Se₅ ternary compound can be used in high efficiency photoelectric converters of solar radiation.     

Specific thermoelectric properties of lightly doped Bi<Subscript>2</Subscript>(TeSe)<Subscript>3</Subscript> solid solutions

Electrical and thermoelectric properties of a lightly doped n-Bi₂Te_2.7Se_0.3 solid solution have been studied in the temperature range 77–300 K. The results are compared with data for the compound PbTe_0.9Se_0.1 with a similar magnitude of the Seebeck coefficient S at 84 K. Along with lower thermal conductivity, Bi₂Te_2.7Se_0.3 has a higher electrical conductivity σ and a much weaker temperature dependence. As a result, the power coefficient S ²σ in optimal samples begins to decrease only when the density of minority carriers becomes significant. In this case, |S| considerably exceeds the standard value of 200 μV/K. The reduction of the electron density reduces the thermoelectric figure of merit Z at its maximum and slightly lowers the temperature of the maximum; therefore, the expected effect on the average value of Z in the range 77–300 K is absent. Similar behavior is observed in Bi₂Te_2.88Se_0.12, although the effect is less pronounced. The experimental results are discussed taking into account possible changes in the dominant scattering mechanisms, carrier density, and electron energy spectrum. __________ Translated from Fizika i Tekhnika Poluprovodnikov, Vol. 38, No. 7, 2004, pp. 811–815. Original Russian Text Copyright ? 2004 by Konstantinov, Prokof’eva, Ravich, Fedorov, Kompaniets.     

Effects of Nb Content on the Ferroelectric and Dielectric Properties of Nb/Nd-Co-doped Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> Thin Films

Nd/Nb-co-substituted Bi_3.15Nd_0.85Ti_3?x Nb _x O₁₂ (BNTN _x , x = 0.01, 0.03, 0.05 and 0.07) thin films were grown on Pt/Ti/SiO₂/Si (100) substrates by chemical solution deposition. The effects of Nb content on the micro-structural, dielectric, ferroelectric, leakage current and capacitive properties of the BNTN _x thin films were investigated. A low-concentration substitution with Nb ions in BNTN _x can greatly enhance its remanent polarization (2P _r) and reduce the coercive field (2E _c) compared with those of Bi₄Ti₃O₁₂ (BIT) thin film. The highest 2P _r (71.4 μC/cm²) was observed in the BNTN_0.03 thin film when the 2E _c was 202 kV/cm. Leakage currents of all the films were on the order of 10^?6 to 10^?5 A/cm², and the BNTN_0.03 thin film has a minimum leakage current (2.1 × 10^?6 A/cm²) under the high electric field (267 kV/cm). Besides, the C–V curve of the BNTN_0.03 thin film is the most symmetrical, and the maximum tunability (21.0%) was also observed in this film. The BNTN_0.03 thin film shows the largest dielectric constant and the lowest dielectric loss and its maximum Curie temperature is 410 ± 5°C.     

An impurity band in Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript> crystals doped with silicon

The influence of silicon impurity on the energy-band spectrum in the Hg₃In₂Te₆ semiconductor compound, which incorporated a high concentration of stoichiometric vacancies, was studied on the basis of the results of electrical and optical measurements. It is shown that silicon impurity forms an impurity band of donor states whose density can be approximated by a Gaussian distribution with a peak at E_c-0.29 eV. The emergence of the impurity band is accompanied with the formation of a quasi-continuous spectrum of localized states in the band gap (E_g=0.74 eV); the density of these states is shown to increase as the doping level increases. All states merge into a continuous band if the impurity concentration N_Si>4.5×10¹⁷ cm^?3. Experimental data are explained on the basis of the effect of impurity self-compensation, in which case donor impurity states arise simultaneously with acceptor states of defects.     

Electrical and photoelectric properties of <Emphasis Type="Italic">n</Emphasis>-TiN/<Emphasis Type="Italic">p</Emphasis>-Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript> heterostructures

n-TiN/p-Hg₃In₂Te₆ heterostructures are fabricated by depositing a thin n-type titanium nitride (TiN) film onto prepared p-type Hg₃In₂Te₆ plates using reactive magnetron sputtering. Their electrical and photoelectric properties are studied. Dominant charge-transport mechanisms under forward bias are analyzed within tunneling-recombination and tunneling models. The fabricated n-TiN/p-Hg₃In₂Te₆ structures have the following photoelectric parameters at an illumination intensity of 80 mW/cm²: the open-circuit voltage is V_OC = 0.52 V, the short-circuit current is I_SC = 0.265 mA/cm², and the fill factor is FF = 0.39.     

Fabrication and photoelectric properties of oxide/CuIn<Subscript>5</Subscript>Se<Subscript>8</Subscript> heterojunctions

Single crystals of the n-CuIn₅Se₈ compound of hexagonal modification have been grown by direct crystallization from melt. On the basis of the experimental study of its thermal interaction with air oxygen, a method for fabricating new oxide/n-CuIn₅Se₈ heterojunctions is proposed. Electrical and photoelectric properties of the structures obtained have been investigated. It is shown that the interaction of n-CuIn₅Se₈ of hexagonal modification with air oxygen makes it possible to obtain heterojunctions with high photosensitivity. The new technology can be used in the design of broadband optical radiation converters based on n-CuIn₅Se₈ crystals.     

Structural and Electrical Properties of Ag/<Emphasis Type="Italic">n</Emphasis>-TiO<Subscript>2</Subscript>/<Emphasis Type="Italic">p</Emphasis>-Si/Al Heterostructure Fabricated by Pulsed Laser Deposition Technique

We have investigated the structural and electrical characteristics of the Ag/n-TiO₂/p-Si/Al heterostructure. Thin films of pure TiO₂ were deposited on p-type silicon (100) by optimized pulsed laser ablation with a KrF-excimer laser in an oxygen-controlled environment. X-ray diffraction analysis showed the formation of crystalline TiO₂ film having a tetragonal texture with a strong (210) plane as the preferred direction. High purity aluminium and silver metals were deposited to obtain ohmic contacts on p-Si and n-TiO₂, respectively. The current–voltage (I–V) characteristics of the fabricated heterostructure were studied by using thermionic emission diffusion mechanism over the temperature range of 80–300 K. Parameters such as barrier height and ideality factor were derived from the measured I–V data of the heterostructure. The detailed analysis of I–V measurements revealed good rectifying behavior in the inhomogeneous Ag/n-TiO₂/p-Si(100)/Al heterostructure. The variations of barrier height and ideality factor with temperature and the non-linearity of the activation energy plot confirmed that barrier heights at the interface follow Gaussian distributions. The value of Richardson’s constant was found to be 6.73 × 10⁵ Am^?2 K^?2, which is of the order of the theoretical value 3.2 × 10⁵ Am^?2 K^?2. The capacitance–voltage (C–V) measurements of the heterostructure were investigated as a function of temperature. The frequency dependence (Mott–Schottky plot) of the C–V characteristics was also studied. These measurements indicate the occurrence of a built-in barrier and impurity concentration in TiO₂ film. The optical studies were also performed using a UV–Vis spectrophotometer. The optical band gap energy of TiO₂ films was found to be 3.60 eV.     

Influence of the Thermal Conditions of Fabrication and Treatment on the Optical Properties of In<Subscript>2</Subscript>O<Subscript>3</Subscript> Films

In₂O₃ films on Al₂O₃ (012) substrates are fabricated by dc magnetron sputtering at various temperatures (20–600°C). The effect of annealing and the substrate temperature on the film properties are studied by the ellipsometric method and the optical transmission method. Refractive-index profiles are constructed and band gaps for direct and indirect transitions are found. It is established that annealing leads to densification of the film material and unifies the refractive index. Annealing also decreases and unifies the energies of band-to-band transitions, which can be explained by lowering the influence of barriers in annealed films. However, the band gap for direct transitions varies greater than for indirect transitions. This fact can be associated with the mechanism of indirect transitions, notably, the participation of phonons facilitates interband transitions even if they are hindered by extra barriers caused by grain boundaries. The latter can be indirect evidence of the actuality of indirect transitions in indium oxide.     

Effect of the magnetic phase transition on the charge transport in layered semiconductor ferromagnets TlCrS<Subscript>2</Subscript> and TlCrSe<Subscript>2</Subscript>

TlCrS₂ and TlCrSe₂ crystals were synthesized by solid-state reaction. X-ray diffraction analysis showed that TlCrS₂ and TlCrSe₂ compounds crystallize in the hexagonal crystal system with lattice parameters a = 3.538 Å, c = 21.962 Å, c/a ≈ 6.207, z = 3; a = 3.6999 Å, c = 22.6901 Å, c/a ≈ 6.133, z = 3; and X-ray densities ρ _x = 6.705 and 6.209 g/cm³, respectively. Magnetic and electric studies in a temperature range of 77–400 K showed that TlCrS₂ and TlCrSe₂ are semiconductor ferromagnets. Rather large deviations of the experimental effective magnetic moment of TlCrS₂ (3.26 μ_B) and TlCrSe₂ (3.05 μ_B) from the theoretical one (3.85 μ_B) are attributed to two-dimensional magnetic ordering in the paramagnetic region of strongly layered ferromagnets TlCrS₂ and TlCrSe₂. The effect of the magnetic phase’s transition on the charge transport in TlCrS₂ and TlCrSe₂ is detected.     

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.     

Magnetic susceptibility of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> alloys

The magnetic susceptibility of Czochralski-grown single crystals of Bi₂Te₃-Sb₂Te₃ alloys containing 0, 10, 25, 40, 50, 60, 65, 70, 80, 90, 99.5, or 100 mol % Sb₂Te₃ has been investigated. The magnetic susceptibility of these crystals was determined at the temperature T = 291 K and the magnetic field H oriented parallel (χ_‖) and perpendicularly (χ_⊥) to the trigonal crystallographic axis C ₃. A complicated concentration dependence of the anisotropy of magnetic susceptibility χ_‖/χ_⊥ has been revealed. The crystals with the free carrier concentration p ≈ 5 × 10¹⁹ cm^?3 do not exhibit anisotropy of magnetic susceptibility. The transition to the isotropic magnetic state occurs for the compositions characterized by a significantly increased (from 200 to 300 meV) optical bandgap.