Anomalous thermoelectric power in Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript> crystals

Based on data on the Hall coefficient, it is shown that the existence of potential barriers in the region of impurity conductivity of highly compensated Hg₃In₂Te₆ crystals is possible. The role of barriers in the anomalous behavior of transport phenomena is discussed qualitatively. Extremely large values of the thermoelectric power are related to the combination of thermoelectric powers of contact potentials for regions with different concentrations of electrons.     

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.     

Conductivity of Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript> crystals in high electric fields

The effect of electric field and temperature on the conductivity of bulk Hg₃In₂Te₆ crystals is investigated. It is shown that the I–V characteristics in high electric fields are of the S type with the effect of switching into a low-resistance state. The critical voltage of transition from the Ohm law to the exponential dependence of the current (I) on the voltage (U) and the threshold voltage of transition into the region of negative differential resistance dU/dI = s< 0 linearly depend on the sample thickness. The activation energies of conductivity in low and high electric fields are determined. It is established that the superlinear portion of the I–V characteristic with dU/dI > 0 is described by the dependence of the type I = I ₀ exp(U/U ₀) and caused by the electron transitions from the local centers with the energy level E _t = 0.19 eV.     

Effect of gadolinium impurity on transmittance and reflectance of Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript> crystals

The results of measuring the optical transmission and reflection spectra in the transparency region of Hg₃In₂Te₆:Gd semiconducting crystals are reported. It is shown that, in the entire wavelength range under investigation (2–25 µm), doping with Gd results in an increase in the continuous structureless absorption by impurities and defects, which introduce a quasi-continuous spectrum of localized states within the band gap. A decrease in transmittivity is accompanied by a decrease in the wavelength-independent reflectivity. Variation in the refractive index is attributed to changes in the bonding and electronic polarization of Hg₃In₂Te₆:Gd crystals. It is ascertained that polarization constants depend linearly on the strength of internal electric fields which exist in the vicinity of impurity defects.     

Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> Superlattices Grown by Nanoalloying

In this work, Bi₂Te₃-Sb₂Te₃ superlattices were prepared by the nanoalloying approach. Very thin layers of Bi, Sb, and Te were deposited on cold substrates, rebuilding the crystal structure of V₂VI₃ compounds. Nanoalloyed super- lattices consisting of alternating Bi₂Te₃ and Sb₂Te₃ layers were grown with a thickness of 9 nm for the individual layers. The as-grown layers were annealed under different conditions to optimize the thermoelectric parameters. The obtained layers were investigated in their as-grown and annealed states using x-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive x-ray (EDX) spectroscopy, transmission electron microscopy (TEM), and electrical measurements. A lower limit of the elemental layer thickness was found to have c-orientation. Pure nanoalloyed Sb₂Te₃ layers were p-type as expected; however, it was impossible to synthesize p-type Bi₂Te₃ layers. Hence the Bi₂Te₃-Sb₂Te₃ superlattices consisting of alternating n- and p-type layers showed poor thermoelectric properties.     

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.     

Thermoelectric Properties of Spark Plasma-Sintered In<Subscript>4</Subscript>Se<Subscript>3</Subscript>-In<Subscript>4</Subscript>Te<Subscript>3</Subscript>

We report the thermoelectric properties of spark plasma-sintered In₄Se₃-In₄Te₃ materials. For comparison, pure In₄Se₃ and In₄Se₃ (80 wt.%)/In₄Te₃ (20 wt.%) mixture samples were prepared. In₄Se₃ and In₄Te₃ powders were synthesized by a conventional melting process in evacuated quartz ampoules, and a spark plasma method was used for the sintering of the pure In₄Se₃ and mixture samples. Thermoelectric and structural characterizations were carried out, and the mixing effect of In₄Se₃ and In₄Te₃ on the thermoelectric properties was investigated.     

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.     

Electrodeposition and Thermoelectric Characteristics of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> and Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> Films for Thermopile Sensor Applications

A thermopile sensor was processed on a glass substrate by electrodeposition of n-type bismuth telluride (Bi-Te) and p-type antimony telluride (Sb-Te) films. The n-type Bi-Te film electrodeposited at −50 mV in a 50 mM electrolyte with a Bi/(Bi + Te) mole ratio of 0.5 exhibited a Seebeck coefficient of −51.6 μV/K and a power factor of 7.1 × 10⁻⁴ W/K² · m. The p-type Sb-Te film electroplated at 20 mV in a 70 mM solution with an Sb/(Sb + Te) mole ratio of 0.9 exhibited a Seebeck coefficient of 52.1 μV/K and a power factor of 1.7 × 10⁻⁴ W/K² · m. A thermopile sensor composed of 196 pairs of the p-type Sb-Te and the n-type Bi-Te thin-film legs exhibited sensitivity of 7.3 mV/K.     

Photosensitive structures based on In<Subscript>2</Subscript>S<Subscript>3</Subscript> crystals

Crystals of the compound In₂S₃ were grown by planar crystallization of the melt. The composition, structure, and electrical characteristics of the crystals obtained were determined. Photosensitive structures based on the grown In₂S₃ crystals were fabricated for the first time; spectral dependences of photoconversion quantum efficiency for H₂O/In₂S₃ cells were measured. The features of the band-to-band absorption are discussed; energies of the direct and indirect optical transitions for In₂S₃ crystals are estimated. It is stated that In₂S₃ crystals can be used in wide-range (1.5–3.5 eV) photoconverters of nonpolarized radiation (in particular, in solar cells).     

Electrical properties of In<Subscript>2</Subscript>Se<Subscript>3</Subscript> single crystals and photosensitivity of Al/In<Subscript>2</Subscript>Se<Subscript>3</Subscript> Schottky barriers

In₂Se₃ single crystals ∼40 mm long and 14 mm in diameter were grown by the Bridgman method. The composition of grown single crystals and their crystal structure were determined. The conductivity (σ) and Hall constant (R) of grown single crystals were measured and the first Schottky barriers Al/n-In₂Se₃ were fabricated. Rectification and photovoltaic effect were detected in the new structures. Based on the study of the photosensitivity spectra of Al/n-In₂Se₃ structures, the nature of the interband transitions and band gap of In₂Se₃ crystals were determined. It was concluded that the new structures can be applied to develop broadband photoconverters of optical radiation.     

Optical properties of imperfect In<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Spectra of complete sets of optical functions for α-and β-In₂Se₃ in the range of 0–20 eV were calculated using experimental reflection spectra and the Kramers-Kronig relation. Special features in the spectra of optical functions for both In₂Se₃ phases were analyzed. The spectra of both permittivity and characteristic electron energy losses were decomposed into elementary transverse and longitudinal components using the combined Argand diagrams. The main parameters of the electron transitions for these components were determined. The structure of the components was compared with the structure of the expected spectrum of interband transitions.     

Optical properties of In<Subscript>2</Subscript>Se<Subscript>3</Subscript> thin films

In₂Se₃ films are produced by ion-beam evaporation at substrate temperatures of 313 and 623 K. As the target, In₂Se₃ single crystals grown by the vertical Bridgman method are used. The composition and structure of the crystals and films are determined by the X-ray spectral analysis and X-ray diffraction techniques, respectively. It is established that the crystals and films crystallize with the formation of a hexagonal structure. The band gap and refractive index of the In₂Se₃ films are determined from the transmittance and reflectance spectra. It is found that, as the substrate temperature is increased, the band gap increases.     

Features of reflection spectra of single crystals of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> solid solutions in the region of plasma effects

Reflectance spectra of single crystals of Bi₂Te₃-Sb₂Te₃ solid solutions containing 0, 10, 25, 40, 50, 60, 65, 70, 80, 90, 99.5, and 100 mol % of Sb₂Te₃ have been studied in the range of 400–4000 cm⁻¹ at the temperature T = 291 K and with orientation of the vector of the electric-field strength E perpendicular to the trigonal axis of the crystal C ₃ (E ⊥ C ₃). The shape of the spectra is characteristic of plasma reflection; the spectra include the features in the range 1250–3000 cm⁻¹ corresponding to the optical band gap E _{g opt}. The features become more pronounced as the content of Bi₂Te₃ is increased to 80 mol % in the composition of the Bi₂Te₃-Sb₂Te₃ solid solution. A further increase in the content of Sb₂Te₃ is accompanied by discontinuities in the functional dependences of the parameters characterizing the plasma oscillations of free charge carriers on the solid-solution composition and also by a sharp increase in E _{g opt}.     

Nernst-ettingshausen tensor in Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> single crystal

On one Sb₂Te₃ single crystal, the temperature dependences of all three independent components of the Nernst-Ettingshausen tensor (Q _ikl ) are measured in the temperature range of 85–450 K, all three components being negative. Alongside with the Nernst-Ettingshausen effect, the anisotropy of the Hall (R _ikl ) and Seebeck (S _ij ) coefficients and the conductivity (σ _ii ) is also investigated. The carried-out analysis of the experimental data on the Nernst-Ettingshausen and Seebeck effects indicates that there is the mixed scattering mechanism with the participation of acoustic phonons and impurity ions, the relative contributions of these mechanisms varying with temperature. In the relaxation-time-tensor approximation, the values of the effective scattering parameter (r) are determined. The obtained values point to the dominant scattering at acoustic phonons in the cleavage plane and to the substantial contribution of charged ions to the scattering along the trigonal axis c ₃. It is shown that it is possible to explain the major features of experimental data on the Nernst-Ettingshausen effect within the two-valence-band model with the participation of several groups of holes in the transport phenomena.     

Photoelectric properties of In/In<Subscript>2</Subscript>Se<Subscript>3</Subscript> structures

The hexagonal modification of In₂Se₃ single crystal is grown by planar crystallization from nearly stoichiometric melt and by the vapor-phase method. For the first time, the Schottky barriers In/n-In₂Se₃, which are photosensitive in a wide incident-photon energy range of 1–3.8 eV at 300 K, are obtained. The nature of the interband photoactive absorption is studied. The energy-barrier height and interband optical-transition energy are estimated. It is concluded that the grown crystals can be used in broadband optical-radiation converters.     

Effect of Vacancy Distribution on the Thermal Conductivity of Ga<Subscript>2</Subscript>Te<Subscript>3</Subscript> and Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Our group has focused attention on Ga₂Te₃ as a natural nanostructured thermoelectric material. Ga₂Te₃ has basically a zincblende structure, but one-third of the Ga sites are structural vacancies due to the valence mismatch between Ga and Te. It has been confirmed that (1) vacancies in Ga₂Te₃ exist as two-dimensional (2D) vacancy planes, and (2) Ga₂Te₃ exhibits an unexpectedly low thermal conductivity (κ), most likely due to highly effective phonon scattering by the 2D vacancy planes. However, the effect of the size and periodicity of the 2D vacancy planes on κ has been unclear. In addition, it has also been unclear whether only the 2D vacancy planes reduce κ or if point-type vacancies can also reduce κ. In the present study, we tried to prepare Ga₂Te₃ and Ga₂Se₃ with various vacancy distributions by controlling annealing conditions. The atomic structures of the samples were characterized by means of transmission electron microscopy, and κ was evaluated from the thermal diffusivity measured by the laser flash method. The effects of vacancy distributions on κ of Ga₂Te₃ and Ga₂Se₃ are discussed.     

Thermoelectric Properties of Mo<Subscript>3</Subscript>Sb<Subscript>5.4</Subscript>Te<Subscript>1.6</Subscript> and Ni<Subscript>0.06</Subscript>Mo<Subscript>3</Subscript>Sb<Subscript>5.4</Subscript>Te<Subscript>1.6</Subscript>

Mo₃Sb₇, crystallizing in the Ir₃Ge₇ type structure, has poor thermoelectric (TE) properties due to its metallic behavior. However, by a partial Sb-Te exchange, it becomes semiconducting without noticeable structure changes and so achieves a significant enhancement in the thermopower with the composition of Mo₃Sb₅Te₂. Meanwhile, large cubic voids in the Mo₃Sb₅Te₂ crystal structure provide the possibility of filling the voids with small cations to decrease the thermal conductivity by the so-called rattling effect. As part of the effort to verify this idea, we report herein the growth as well as measurements of the thermal and electrical transport properties of Mo₃Sb_5.4Te_1.6 and Ni_0.06Mo₃Sb_5.4Te_1.6.     

Segmented Generator Modules Using Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Based Materials

Previously, the Institute of Thermoelectricity has created Bi₂Te₃-based modules with an efficiency of ~7% in the temperature range of 30°C to 300°C, with legs that employed homogeneous thermoelectric materials. Herein, we present the results of development of such modules with legs made of inhomogeneous materials. Based on the theory of optimal control and object-oriented computer technology, programs to determine the requirements for material properties in the inhomogeneous legs were created. It was established that introduction of inhomogeneity in the form of continuous and step changes in three-segment n- and p-type legs yields almost identical efficiency increases of about 15%. Use of two segments reduces this value of 10% to 12%. Modules with two-segment legs encapsulated in thin-walled metal cases filled with inert gas have been built, yielding improved efficiency of 7.8% to 8%.