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.     

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.     

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.     

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.     

Thermoelectric Properties of Cu-doped Bi<Subscript>0.4</Subscript>Sb<Subscript>1.6</Subscript>Te<Subscript>3</Subscript> Prepared by Hot Extrusion

Cu_0.003Bi_0.4Sb_1.6Te₃ alloys were prepared by using encapsulated melting and hot extrusion (HE). The hot-extruded specimens had the relative average density of 98%. The (00l) planes were preferentially oriented parallel to the extrusion direction, but the specimens showed low crystallographic anisotropy with low orientation factors. The specimens were hot-extruded at 698 K, and they showed excellent mechanical properties with a Vickers hardness of 76 Hv and a bending strength of 59 MPa. However, as the HE temperature increased, the mechanical properties degraded due to grain growth. The hot-extruded specimens showed positive Seebeck coefficients, indicating that the specimens have p-type conduction. These specimens exhibited negative temperature dependences of electrical conductivity, and thus behaved as degenerate semiconductors. The Seebeck coefficient reached the maximum value at 373 K and then decreased with increasing temperature due to intrinsic conduction. Cu-doped specimens exhibited high power factors due to relatively higher electrical conductivities and Seebeck coefficients than those of undoped specimens. A thermal conductivity of 1.00 Wm^?1 K^?1 was obtained at 373 K for Cu_0.003Bi_0.4Sb_1.6Te₃ hot-extruded at 723 K. A maximum dimensionless figure of merit, ZT _max = 1.05, and an average dimensionless figure of merit, ZT _ave = 0.98, were achieved at 373 K.     

Quasi-local states of Sn in Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> according to the studies of galvanomagnetic effects in classical and quantizing magnetic fields

The magnetic-field dependences of the Hall coefficient and transverse magnetoresistance are studied experimentally and theoretically in p-Bi₂Te₃ crystals doped heavily with Sn and grown by the Czochralski method in the case of both classical and quantizing magnetic fields as high as 12 T with the magnetic-field orientation along the C ₃ trigonal axis. The Shubnikov-de Haas effect and quantum oscillations of the Hall coefficient were measured at temperatures of 4.2 and 11 K. The six-ellipsoid Drabble-Wolfe model of the energy spectrum and the magnetic-field dependence of the Hall coefficient are used as the basis for the method for determining the Hall factor and Hall mobility. New evidence is obtained in support of the existence of the narrow band of impurity Sn states occupied partially with electrons against the background of the light-hole band spectrum. The parameters of impurity states are estimated including their energy (E _Sn ≈ 15 meV), the broadening (Γ « kT), and the radius of localization of the impurity state (R ≈ 30 Å).     

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.     

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 properties of the <Emphasis Type="Italic">p</Emphasis><Superscript>+</Superscript>-Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-<Emphasis Type="Italic">p</Emphasis>-GaSe isotype heterostructure

Electrical properties of a p⁺-Bi₂Te₃-p-GaSe isotype heterostructure fabricated for the first time are reported. A qualitative model is suggested which explains the emergence of negative differential conductivity for a forward-biased structure and for a reverse-biased structure, which is also illuminated.     

On the photoconductivity of TlInSe<Subscript>2</Subscript>

The current–voltage (I–V) and photocurrent–light intensity (I _pc –Φ) characteristics and the photoconductivity relaxation kinetics of TlInSe₂ single crystals are investigated. Anomalously long relaxation times (τ ≈ 10³ s) and some other specific features of the photoconductivity are observed, which are explained within the barrier theory of inhomogeneous semiconductors. The heights of the drift and recombination barriers are found to be, respectively, E _dr ≈ 0.1 eV and E _r ≈ 0.45 eV.     

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.     

Transport coefficients of <Emphasis Type="Italic">n</Emphasis>-Bi<Subscript>2</Subscript>Te<Subscript>2.7</Subscript>Se<Subscript>0.3</Subscript> in a two-band model of the electron spectrum

The Hall factor and thermoelectric properties of an n-Bi₂Te_2.7Se_0.3 solid solution with the roomtemperature Seebeck coefficient |S| = 212 μV/K have been studied in the temperature range 77–350 K. The observed temperature dependences demonstrate a number of specific features, which were earlier found in samples with a lower electron density N. The effect of these specific features on the thermoelectric figure of merit Z appears to be more favorable for the sample under study: this sample is most efficient in the temperature range 120–340 K, and the average value of ZT is 0.71. It is found that a rise in the density N enhances the factor responsible for the effective mass decreasing as the temperature increases. This effect appears when the analysis is carried out in terms of a single-band parabolic model with N = const(T). This finding suggests that the most probable reason for the unusual behavior of these properties is the complex structure of the electron spectrum. Temperature dependences obtained from calculations of the transport coefficients show good agreement with the experimental data for two samples of the mentioned composition with different electron densities. The calculations have been performed in terms of a two-band model and an acoustic scattering mechanism and take into account the anisotropy and nonparabolicity of the light-electron spectrum.     

Reflectance spectra of <Emphasis Type="Italic">p</Emphasis>-Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>:Sn crystals in a wide IR region

The reflectance spectra of a p-Bi₂Te₃:Sn crystal are recorded in the range 50–7900 cm^–1. The spectra possess features characteristic of charge-carrier plasma oscillations and a contribution of phonons. It is shown that the dielectric function that is used in the context of Drude–Lorentz theory and includes the contributions of hole plasma oscillations and two phonons adequately describes the experimental data obtained at room temperature and at a temperature of T = 78 K.     

Low-temperature instabilities of the electrical properties of Cd<Subscript>0.96</Subscript>Zn<Subscript>0.04</Subscript>Te:Cl semi-insulating crystals

The electrical properties in the temperature range 295–430 K and low-temperature (4.2 K) photoluminescence of Cd_1?xZn_xTe:Cl semi-insulating crystals grown from melts with a variable impurity content (C _Cl ⁰ = 5 × 10¹⁷–1 × 10¹⁹ cm^?3) are investigated. Nonequilibrium processes leading to a decrease in carrier concentration are observed in all the samples at low temperatures (T = 330–385 K). These changes are reversible. The activation energy of these processes E _a is found to be 0.88 eV. As with semi-insulating CdTe:Cl, the observed phenomena can be explained by a change in the charge state of background copper atoms: Cu_Cd ? Cu_i. The introduction of Zn changes the ratio of the concentrations of shallow-level donors Cu_i and Cl_Te from their levels in the initial material.     

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.     

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.     

On the density-of-states effective mass and charge-carrier mobility in heteroepitaxial films of bismuth telluride and Bi<Subscript>0.5</Subscript>Sb<Subscript>1.5</Subscript>Te<Subscript>3</Subscript> solid solution

It is shown that the Seebeck coefficient α, the power factor α²σ, and the density-of-states effective mass m/m ₀ in heteroepitaxial films of Bi0.5Sb1.5Te3 solid solution are higher than the corresponding characteristics of bulk thermoelectric materials. The elevated values and weak temperature dependences of these parameters lead to a rise in the parameter proportional to the effective mass, the charge-carrier mobility, and the figure of merit. The character of change in α, α²σ, and m/m ₀ is determined by the peculiarities of the mechanism of charge-carrier scattering, the anisotropy of the constant-energy surface, and the possible influence of topological surface states of Dirac fermions in the films.     

Thermoelectric Properties for a Suspended Microribbon of Quasi-One-Dimensional TiS<Subscript>3</Subscript>

Transition-metal trichalcogenides MX₃ (M = Ti, Zr, Nb, Ta; X = S, Se) are well-known inorganic quasi-one-dimensional conductors. Among them, we have investigated the thermoelectric properties of titanium trisulfide TiS₃ microribbon. The electrical resistivity ρ, thermal conductivity κ, and thermoelectric power S were measured using 3ω method. The weight mean values were found to be ρ = 5 mω m and κ = 10 W K^?1 m^?1 along the one-dimensional direction (b-axis) of the TiS₃ microribbon. Combined with the thermoelectric power S = ?530 μV K^?1, the figure of merit was calculated as ZT = 0.0023. This efficiency is the same as that of randomly oriented bulk TiS₃. We also estimated the anisotropy of σ and κ using the present results and those for randomly oriented bulk material. The obtained weak anisotropy for TiS₃ is attributable to strong coupling between triangular columns consisting of TiS₃ units. These experimental results are consistent with theoretical results obtained using density functional theory (DFT) calculations.     

Reflectance of a PbSb<Subscript>2</Subscript>Te<Subscript>4</Subscript> crystal in a wide spectral range

For the anisotropic PbSb₂Te₄ single crystal with a high hole concentration (p ≈ 3 × 10²⁰ cm^–3) and high conductivity (σ ≈ 2500 Ω^–1 cm^–1), the reflectance spectrum for a cleavage plane orthogonal to the trigonal axis C₃ is recorded in a wide spectral range from 50 to 50000 cm^–1. It is shown that, in the long-wavelength and mid-infrared regions, the reflectance can be described with consideration for the contribution of plasma vibrations and two crystal-lattice vibrations. The quantitative characteristics of these vibrations are determined. The characteristics are in satisfactory agreement with the electrical parameters. The discrepancies between the values of the hole effective mass calculated by different methods are attributed to the complex structure of the crystal’s valence band.