Multicomponent <Emphasis Type="Italic">n</Emphasis>-(Bi,Sb)<Subscript>2</Subscript>(Te,Se,S)<Subscript>3</Subscript> solid solutions with different atomic substitutions in the Bi and Te sublattices

The thermoelectric properties of n-Bi_{2 ? x} Sb _x Te_{3 ? y ? z} Se _y S _z solid solutions are studied in the temperature range 300–550 K. It is shown that an increase in the parameter β determining the figure-of-merit Z of the material is observed in compositions with the optimally related effective mass of the density of states m/m ₀, the carrier mobility μ₀, and the lattice thermal conductivity κ _L . Within the temperature range 300–350 K, the parameter β and the figure-of-merit Z are found to increase in solid solutions with substitutions in both bismuth telluride sublattices Bi → Sb and Te → Se, S (x = 0.16, y = z = 0.12) for optimum electron concentrations. An increase in the electron concentration and substitutions of atoms only in the tellurium sublattice bring about an increase in the β parameter and the value of Z at higher temperatures. Within the range 350–450 K, the parameters β and Z are observed to increase in a solid solution with a low content of substituted atoms in the tellurium sublattice Te → Se, S for y = z = 0.09 and, at higher temperatures up to 550 K, in compositions with tellurium substituted by selenium only, with increasing content of substituted atoms.     

Thermoelectric properties and ferromagnetism of diluted magnetic semiconductors Sb<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>Cr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript>3</Subscript>

Thermoelectric properties of single crystals of a new dilute magnetic semiconductor p-Sb_{2 ? x} Cr _x Te₃ are studied in the temperature interval 7–300 K. The temperature dependences of the thermal conductivity are measured. The Seebeck coefficient S is found to increase upon doping with Cr. At low temperatures, a ferromagnetic phase with Curie temperature T _C ≈ 5.8 K exists for a Cr concentration x = 0.0215, its easy magnetization axis being parallel to the crystallographic axis C ₃. At T = 4.2 K, a negative magnetoresistance and anomalous Hall effect are observed; in strong magnetic fields, the Shubnikov-de Haas effect is manifested.     

Low-Temperature Transport Properties of Lanthanum Hexaboride La<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Ce<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>B<Subscript>6</Subscript> Single Crystals

Resistivity (ρ), thermal conductivity (k) and Seebeck coefficient (S) of La_1–xCe_xB₆ single crystals with various concentrations of cerium Ce ions was measured in a wide temperature range 3?300 K. The obtained data were analyzed in the framework of the Coqblin–Shrieffer model. The contributions of scattering of carriers on magnetic ions Ce for all transport parameters ρ(T), k(T), S(T) are revealed. Strong dependence of the magnetic scattering on concentration of the cerium ions are identified. The anomalous behavior of the transport parameters ρ(T), k(T), S(T) in the region near 30 K is attributed to the Δ ~ 30 K splitting of Г₈ level.     

New promising bulk thermoelectrics: intermetallics,pnictides and chalcogenides

The need of alternative “green” energy sources has recently renewed the interest in thermoelectric (TE) materials, which can directly convert heat to electricity or, conversely, electric current to cooling. The thermoelectric performance of a material can be estimated by the so-called figure of merit, zT = σ α ² T/λ (α the Seebeck coefficient, σ α ² the power factor, σ and λ the electrical and thermal conductivity, respectively), that depends only on the material. In the middle 1990s the “phonon glass and electron crystal” concept was developed, which, together with a better understanding of the parameters that affect zT and the use of new synthesis methods and characterization techniques, has led to the discovery of improved bulk thermoelectric materials that start being implemented in applications. During last decades, special focus has been made on skutterudites, clathrates, half-Heusler alloys, Si_1?x Ge _x-, Bi₂Te_3- and PbTe-based materials. However, many other materials, in particular based on intermetallics, pnictides, chalcogenides, oxides, etc. are now emerging as potential advanced bulk thermoelectrics. Herein we discuss the current understanding in this field, with special emphasis on the strategies to reduce the lattice part of the thermal conductivity and maximize the power factor, and review those new potential thermoelectric bulk materials, in particular based on intermetallics, pnictides and chalcogenides. A final chapter, discussing different shaping techniques leading to bulk materials (eventually from nanostructured TE materials), is also included.     

The Nernst-Ettingshausen coefficient in the normal phase of doped HTSCs of the YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>y</Subscript> system

The temperature dependence of the Nernst-Ettingshausen coefficient Q(T) in the normal phase of doped HTSCs of the yttrium system was studied. The main features characterizing the behavior of this coefficient were revealed, and the character and mechanism of the effect that various nonisovalent substituents exert on the Q(T) dependence were analyzed. It is shown that the narrow-band model permits one not only to describe all the specific features observed in the Q(T) curves but also to perform a simultaneous quantitative analysis of the temperature dependences of four kinetic coefficients (the electrical resistivity and the Seebeck, Hall, and Nernst-Ettingshausen coefficients) with the use of a common set of model parameters characterizing the band structure and carrier system in the normal phase of an HTSC. This approach was employed to determine the carrier mobilities and the asymmetry of the dispersion curve in the systems studied (YBa₂Cu₃O_y, y = 6.37–6.91; YBa₂Cu_3?xCo_xO_y, x = 0–0.3; Y_1?xCa_xBa₂Cu₃O_y, x = 0–0.25; Y_1?xCa_xBa_2?xLa_xCu₃O_y, x = 0–0.5) and to analyze the effect of the substitutions involved on the variation of these parameters.     

Anomalous Hall effect and ferromagnetism in the new diluted magnetic semiconductor Sb<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Cr<Subscript>x</Subscript>Te<Subscript>3</Subscript>

The magnetic and galvanomagnetic properties of single crystals of the new diluted magnetic semiconductor p-Sb_2?xCr_xTe₃ (0 ≤ x ≤ 0.02) have been studied in the temperature range 1.7–300 K. A ferromagnetic phase with the Curie temperature T_c ≈ 5.8 K and the maximum Cr content x = 0.0215 has been revealed. The easy magnetization axis is parallel to the C₃ crystallographic axis. In the presence of strong magnetic fields, the Shubnikov-de Haas effect has been observed. Analysis of this effect shows that doping with chrome reduces the concentration of holes. Negative magnetoresistance and the anomalous Hall effect are observed at liquid helium temperature.     

Synthesis,structure, and optical and photocatalytic properties of quasi-one-dimensional ZnO doped with Со<Subscript>3</Subscript>O<Subscript>4</Subscript> and carbon

One-dimensional nanocomposites Zn_1–x Co _x O_1–y С _у :nCo₃O₄ and solid solutions Zn_1–x Co _x O_1–y С _у , which are promising photocatalysts for the oxidation of toxic organic compounds in visible light, are obtained via the thermolysis of Zn_1–x Co _x (HCOO)(OCH₂CH₂O)_1/2 (0.1 ≤ x ≤ 0.5) precursor in a controlled gaseous atmosphere.     

Suppression of superconductivity in layered Bi<Subscript>4</Subscript>O<Subscript>4</Subscript>S<Subscript>3</Subscript> by Ag doping

We report X-ray diffraction, magnetization and transport measurements for polycrystalline samples of the new layered superconductor Bi_4?x Ag _x O₄S₃(0 ≤ x ≤ 0.2). The superconducting transition temperature (T _C) decreases gradually and finally suppressed when x < 0.10. Accordingly, the resistivity changes from a metallic behavior for x < 0.1 to a semiconductor-like behavior for x > 0.1. The analysis of Seebeck coefficient shows there are two types of electron-like carriers dominate at different temperature regions, indicative of a multiband effect responsible for the transport properties. The suppression of superconductivity and the increased resistivity can be attributed to a shift of the Fermi level to the lower-energy side upon doping, which reduces the density of states at E _F. Further, our result indicates the superconductivity in Bi₄O₄S₃ is intrinsic and the dopant Ag prefers to enter the BiS₂ layers, which may essentially modify the electronic structure.     

Effect of electron irradiation on the galvanomagnetic properties of In<Subscript>x</Subscript>Bi<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript>3</Subscript> semiconductor single crystals

The effect of 5-MeV electron irradiation of p-In_xBi_2?xTe₃ single crystals (x=0, 0.04, 0.07), performed at 250 K, on the galvanomagnetic properties of the crystals was studied. The irradiation was shown to change the conduction from the p to the n type. Annealing at temperatures of 310–390 K restores the conduction to the p type. The reversal of the conduction type and variation of the carrier concentration can be accounted for by an increase in the concentration of charged point radiation defects produced in In_xBi_2?xTe₃ by irradiation. Electron irradiation of p-type Te single crystals reduces the electrical resistivity without reversing the conduction type. Annealing restores the original properties almost completely.     

Optical and electrical properties of β-Tl<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>x</Subscript>InS<Subscript>2</Subscript> (0 ≤ <Emphasis Type="Italic">x</Emphasis> ≤ 0.015) single crystals

The peculiarities of fundamental optical absorption, thermally stimulated conductivity, and depolarization currents in β-Tl_{1 ? x} Cu_xInS₂ (0 ≤ x ≤ 0.015) single crystals have been investigated in the temperature range 4.2–300 K. It is found that the temperature coefficient of the band gap E _g changes near the temperature of the structural phase transition.     

Spectroscopy of optical centers of Eu<Superscript>3+</Superscript> ions in partially stabilized and stabilized zirconium crystals

The structure of the optical centers of Eu³⁺ ions in tetragonal (ZrO₂)_1–x–y (Y₂O₃) _x (Eu₂O₃) _y (х = 2.7–3.6; y = 0.1) and cubic (ZrO₂)_1–x–y (Y₂O₃) _x (Eu₂O₃) _y (х = 8–38; y = 0.1–0.5) crystals of solid solutions on the basis of zirconium dioxide is studied using the methods of optical and Raman-scattering spectroscopy. Characteristic optical centers of Eu³⁺ ions with different crystalline environments are revealed in the above compounds.     

Transport phenomena in superionic Na<Subscript><Emphasis Type="Italic">х</Emphasis></Subscript>Cu<Subscript>2 − <Emphasis Type="Italic">х</Emphasis></Subscript>S (<Emphasis Type="Italic">х</Emphasis> = 0.05; 0.1; 0.15; 0.2) compounds

The electronic and ionic conductivity, the electronic and ionic Seebeck coefficients, and the thermal conductivity of Na _x Cu_2 ? x S (x = 0.05, 0.1, 0.15, 0.2) compounds were measured in the temperature range of 20–450 °С. The total cationic conductivity of Na_0.2Cu_1.8S is about 2 S/cm at 400 °С (the activation energy ≈ 0.21 eV). Over the studied compounds, the composition Na_0.2Cu_1.8S has the highest electronic conductivity (500–800 S/cm) in the temperature range from 20 to 300 °С, and the highest electronic Seebeck coefficient (about 0.2 mV/K) in the same temperature range is observed for Na_0.15Cu_1.85S composition; the electronic Seebeck coefficient increases abruptly above 300 °С for all compounds. The thermal conductivity of superionic Na_0.2Cu_1.8S is low, which causes high values of the dimensionless thermoelectric figure of merit ZT from 0.4 to 1 at temperatures from 150 to 340 °С.     

Thermodynamic study of compounds of the Nd-Ba-Cu-O system

Standard enthalpies of formation for solid solutions of composition Nd_{1 + x} Ba_{2 ? x} Cu₃O _y (x = 0–0.8, y = 6.65–7.24) from oxides were determined by solution calorimetry. The heat capacity of NdBa₂Cu₃O_6.87 phase was measured in the range 5–320 K by low-temperature adiabatic calorimetry. The absolute entropy S ^o(T), the difference of enthalpies H ^o(T)-H ^o(0 K), and the reduced Gibbs energy Φ^o(T) = S ^o(T)–[H ^o(T)–H ^o(0)]/T were calculated on the basis of smoothed dependence C _p (T) in the 0–320 K range. An assessment was made for the heat capacities and the absolute entropies of solid solutions Nd_1+x Ba_2?x Cu₃O _y . The obtained set of thermodynamic parameters can be used for the calculation of phase equilibria in the Nd-Ba-Cu-O system.     

Anomalous thermopower in heavy-fermion compounds CeB<Subscript>6</Subscript>, CeAl<Subscript>3</Subscript>, and CeCu<Subscript>6 − <Emphasis Type="Italic">x</Emphasis></Subscript>Au<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

High-precision measurements of thermopower have been performed in a wide temperature range (2–300 K) for a series of cerium-based heavy-fermion compounds, including CeB₆, CeAl₃, CeCu₆, and substitutional solid solutions of the CeCu_{6 ? x} Au _x system (x = 0.1, 0.2). All compounds exhibit an unusual (logarithmic) asymptotic behavior of the temperature dependence of the Seebeck coefficient: S ∝ ?lnT. In the case of cerium hexaboride, this anomalous behavior of S(T) is accompanied by the appearance of weak-carrier-localization-mode asymptotics in the conductivity (σ(T) ∝ T ^0.39), while the paramagnetic susceptibility χ(T) and the effective mass of charge carriers m _eff(T) vary according to a power law (χ(T), m _eff(T) ∝ T ^?0.8) in the temperature interval T = 10–80 K. This behavior corresponds to renormalization of the density of states at the Fermi level. The observed anomalous behavior of thermopower in CeB₆ and other cerium-based intermetallic compounds is attributed to the formation of heavy fermions (many-body states in the metal matrix) at low temperatures.     

Electrical conductivity and thermopower in Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript> S sulfides

This paper reports on the results of investigations into the structural, electrical, and thermoelectrical properties of sulfides Co _x Mn_{1 ? x} S (0 ≤ x ≤ 0.4) in the temperature range 80–950 K. It is established that the thermopower coefficient α decreases significantly with an increase in the cobalt concentration in the lattice of the α-MnS compound. The Co _x Mn_{1 ? x} S compounds with cobalt concentrations in the range 0 ≤ x ≤ 0.3 are semiconductors with hole conduction (α > 0), whereas the compound with x = 0.4 exhibits metallic conduction (α < 0). It is found that the band gap E _g of the compounds under investigation varies in the range from 1.46 eV for α-MnS (x = 0) to 0.26 eV for Co _x Mn_{1 ? x} S (x = 0.4).     

Energy spectrum of holes in Sb<Subscript>2</Subscript>Te<Subscript>2.9</Subscript>Se<Subscript>0.1</Subscript> solid solution according to the data on the transfer phenomena

The temperature dependence of the Hall coefficient of a single crystal of the p-Sb₂Te_2.9Se_0.1 solid solution grown by the Czochralski technique is studied in the temperature range 77–450 K. The data on the Hall coefficient of the p-Sb₂Te_2.9Se_0.1 are analyzed in combination with the data on the Seebeck and Nernst–Ettingshausen effects and the electrical conductivity with allowance for interband scattering. From an analysis of the temperature dependences of the four kinetic coefficients, it follows that, at T < 200 K, the experimental data are qualitatively and quantitatively described in terms of the one-band model. At higher temperatures, a complex structure of the valence band and the participation of the second-kind additional carriers (heavy holes) in the kinetic phenomena should be taken into account. It is shown that the calculations of the temperature dependences of the Seebeck and Hall coefficients performed in the two-band model agree with the experimental data with inclusion of the interband scattering when using the following parameters: effective masses of the density of states of light holes m_d1^*≈ 0.5m₀ (m₀ is the free electron mass) and heavy holes m_d2^*≈ 1.4m₀, the energy gap between the main and the additional extremes of the valence band ΔE_v ≈ 0.14 eV that is weakly dependent on temperature.     

Ion conductivity,structural features,and multifractal properties of grain boundaries in CuCr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>V<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>2</Subscript>

The ion conductivity, crystal structure, and multifractal parameters of the sections of grain boundaries in CuCr_1?x V _x S₂ superionic conductors with 0 ≤ x ≤ 0.3 have been investigated. It is established that an increase in the surface area of grain boundaries and complication of their shape in such compounds facilitate ion transport. The effect of crystal structure peculiarities on the grain structure of these compounds has been revealed.     

Dielectric properties of CuInP<Subscript>2</Subscript>(Se<Subscript>x</Subscript>S<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>6</Subscript> solid solutions

The dielectric properties of layered crystals of CuInP₂(Se_xS_1?x)₆ solid solutions are studied at x = 0.02, 0.05, 0.20, and 0.40. At a low selenium content (x ≤ 0.05), the solid solutions undergo a transition to the phase with short-range polar order. This transition manifests itself as a diffuse maximum in the temperature dependence of the permittivity ε′(T). Ferroelectric ordering in the solid solutions under investigation is suppressed at x > 1. It is assumed that the structural disordering initiated by the substitution of atoms in the anion sublattice of the solid solutions at 0.1 < x < 0.75 leads to the formation of the state of structured glass. The dielectric relaxation dispersion observed in the radio-frequency range at temperatures of 80–140 K is associated with the freezing of the relaxation dynamics of individual copper atoms.     

Ferromagnetism in a new dilute magnetic semiconductor Sb<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Cr<Subscript>x</Subscript>Te<Subscript>3</Subscript>

Magnetic and galvanomagnetic properties of single crystals of a new dilute magnetic semiconductor p-Sb_2?xCr_xTe₃ (x = 0, 0.0115, 0.0215) are investigated in a temperature range of 1.7–300 K. A ferromagnetic phase with a Curie temperature of T_C ≈ 5.8 (x = 0.0215) and 2.0 K (x = 0.0115) is detected. The easy magnetization axis is parallel to the C₃ crystallographic axis. Analysis of the Shubnikov-de Haas effect observed in these crystals in strong magnetic fields leads to the conclusion that the hole concentration decreases as a result of doping with Cr. Negative magnetoresistance and the anomalous Hall effect are observed in Cr-doped samples at liquid helium temperature.     

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.