Thermoelectric properties of p-Bi2 ? xSbxTe3 solid solutions under pressure

This paper reports on a study of the Seebeck coefficient and power factor κ of p-Bi_{2 − x} Sb _x Te₃ solid solutions with different contents of antimony atoms in the bismuth sublattice for x = 0, 1.4, 1.5, and 1.6 under variation of pressure of up to 15 GPa. The magnitude of κ has been found to grow nonmonotonically within the pressure region of 2–4 GPa. The effective mass of the density of states m/m ₀ and the mobility μ₀ have been calculated with due account of degeneracy within the parabolic model of the energy spectrum assuming isotropic charge carrier scattering. It has been shown that application of pressure brings about a decrease of the effective mass m/m ₀ and an increase of carrier mobility. The power factor κ of the p-Bi_0.6Sb_1.4Te₃ composition exhibits at the pressure P ≈ 4 GPa the largest increase of the power factor κ as a result of a weak decrease of the effective mass m/m ₀ and an increase of carrier mobility as compared to the other solid solution compositions. The specific feature of the variation of the power factor κ with a change of the pressure in bismuth telluride near P ≈ 3 GPa, which is accompanied by formation of a knee in the m/m ₀ vs. P dependence, can be assigned to an electronic topological transition.     

Thermal conductivity of single crystals of Ca1 ? xErxF2 + x and Ca1 ? xTmxF2 + x solid solutions

The thermal conductivity of single crystals of Ca_{1 − x} Er _x F_{2 + x} (x = 0.01, 0.05, 0.07, and 0.10) and Ca_{1 − x} Tm _x F_{2 + x} (x = 0.02, 0.04, and 0.06) solid solutions is studied in the temperature ranges 50–300 and 298–673 K. With increasing content of rare-earth elements, the behavior of thermal conductivity in these solid solutions changes from the characteristic of defect single crystals to glasslike. The concentration dependences of thermal conductivity for the two systems differ insignificantly.     

Effect of the spin and valence states of cobalt ions on the kinetic properties of Ho1 ? xSrxCoO3 ? δ and Er1 ? xSrxCoO3 ? δ compounds

The electrical conductivity and Seebeck effect in ceramics based on cobaltites Ho_{1 − x} Sr _x CoO_{3 − δ} (x = 0.65, 0.75, 0.85, 0.95) and Er_{1 − x} Sr _x CoO_{3 − δ} (x = 0.75, 0.85, 0.95) with a perovskite-like structure have been investigated in the temperature range T > 77 K. All the compounds under study are characterized by the variable-range-hopping conductivity with the temperature dependence of the electrical resistivity corresponding to the Mott law. It has been found that, in the Ho_0.35Sr_0.65CoO_{3 − δ} compound, thermally excited Co³⁺ ions contribute to the electrical conductivity with an increase in temperature to 250 K. The Seebeck coefficient of the systems studied decreases as the strontium concentration and temperature increase. It has been shown that, for an adequate explanation of this behavior, proper allowance must be made for the splitting of the 3d levels, as well as for the charge disproportionation of the cobalt ions.     

Ion-electron transfer in solid solutions Rb2 ? 2xFe2 ? xPxO4

The rubidium monoferrite RbFeO₂-based solid solutions with the composition Rb_{2 − 2x} Fe_{2 − x} P _x O₄ have been synthesized, and their crystal structure and the temperature and concentration dependences of the total and electron conductivities have been studied. The introduction of P⁵⁺ ions has been found to sharply decrease the electron conductivity that prevails in pure rubidium monoferrite and, at the same time, to increase the ionic conductivity. The latter becomes dominant as the phosphorus concentration increases. The maximum rubidium-cation conductivity of the materials under study is ∼3 × 10⁻² S/cm at 300°C and ∼3 × 10⁻¹ S/cm at 700°C. The results have been compared with the previously obtained data for similar solid solutions based on rubidium monogallate and monoaluminate.     

Structure and magnetism of semiconductor crystals of the (Ga1 ? xMnx)2Se3 (x = 0?0.04) compounds

Neutron diffraction and magnetic measurements have been used to study the effect of doping with Mn³⁺ ions on the fine crystal structure of the Ga₂Se₃ monoclinic compound. It has been established that the structural state of the crystals is changed even at a relatively low doping level (x = 0.04). Arguments in favor of the fact that local Jahn-Teller distortions are responsible for the formation of the fine structure and magnetism in compounds of this class are presented.     

Anomalous effect of magnetic field on the low-temperature thermal expansion of the Bi2Sr2?xLaxCuO6+δ and Nd2?xCexCuO4?δ HTSC systems in the non-superconducting phase

The thermal expansion of single crystals of the Bi₂Sr_2−x La _x CuO_6+δ high-temperature superconducting (HTSC) system in the insulating phase with compositions having no superconducting transition to a temperature of 1.8 K (x ≥ 0.8) is measured in an arbitrary direction in the (ab) plane in the temperature range of 7–50 K. Temperature regions of material compression upon heating are found. The study of anomalies in magnetic fields of 3 and 6 T, parallel and perpendicular to the c-axis revealed an anisotropic and nonmonotonic effect of the field on thermal expansion. Such anomalies for the n-type Nd_2−x Ce _x CuO_4−δ HTSC sample also having no superconducting transition are detected for the first time. The results show that the anomaly nature is caused by anisotropic electronic ordering, probably, by the charge density wave in the CuO₂ plane and superconductivity fluctuations in the insulating phase.     

Thermal expansion of (Ba1 ? xLax)Ti1 ? x/4O3 solid solutions

Deformation and the thermal expansion coefficient of ceramic samples of (Ba_{1 − x} La _x )Ti_{1 − x/4}O₃ solid solutions (x = 0, 0.026, 0.036, 0.054) were studied in the temperature range 120–700 K. Based on an analysis of the data obtained, the temperature-composition phase diagram is refined, and the temperature dependence of the polarization is calculated. The results are discussed in combination with the dielectric measurement data. Original Russian Text ? M.V. Gorev, I.N. Flerov, Ph. Sciau, S. Guillemet-Fritsch, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 4, pp. 746–752.     

Dielectric tunability and conduction mechanisms of?nanostructured (Pb1?xSrx)TiO3 thin films

The effect of nanosize grains to enhance dielectric tunability in chemically prepared (Pb_1−x Sr _x )TiO₃ (PST) (x=0.1 to 0.5) thin films has been observed. The grain size is evaluated from X-ray diffraction patterns and atomic force microscopy. The average grain size lies in the range of 80–23 nm with varying Sr content. The nanosize grains in the PST films control the dielectric behavior up to the higher frequency region and exhibit large tunability with low loss factor at room temperature. The current–voltage characteristics show a large tunability as electron transport takes place within a highly resistive Fermi gap.     

Mechanism of NdSr2 ? xCaxMn2O7 (0 ≤ x ≤ 2.0) solid solution formation

The mechanisms of formation of NdSr_{2− x} Ca _x Mn₂O₇ (0 ≤ x ≤ 2.0) solid solution have been studied. The dependence of its volume magnetic susceptibility on the calcium concentration is obtained. The stability of this solid solution is compared with that of similar solid solutions in lanthanum-containing systems.     

Dependences of the dielectric and pyroelectric properties of (1 ? x)PbFe1/2Nb1/2O3?xPbTiO3 ferroelectric ceramics solid solutions on the PbTiO3 content in a compositional range of 0 ≤ x ≤ 0.08

(1 − x)PbFe_1/2Nb_1/2O_3−x PbTiO₃ (PFN-xPT) ferroelectric ceramics with low dielectric loss and pronounced anomalies of dielectric and pyroelectric properties near the ferroelectric-ferroelectric phase transition was obtained by doping with lithium. The temperature dependence of the position of the morphotropic boundary between the rhombohedral (monoclinic) and tetragonal phases in the x-T phase diagram of the PFN-xPT system was determined for the first time.     

Mechanism of charge transfer in n-CdS/p-CdTe heterostructures with a thick layer of the CdTe1 ? xSx solid solution

The current-voltage and capacitance-voltage characteristics of the n-CdS/p-CdTe heterosystem are investigated. An analysis of the results obtained has demonstrated that a high-resistance i layer (the CdTe_{1 − x} S _x solid solution), which is inhomogeneous not only in the electrical conductivity but also in the composition, is formed at the n-CdS/p-CdTe heterointerface. The thicknesses of the solid-solution layers are estimated from the capacitance-voltage characteristics, and regions with different types of conduction are found to exist in the intermediate layer. It is shown that the ambipolar diffusion and drift in the high-resistance CdTe_{1 − x} S _x solid-solution layers are directed toward each other, thus resulting in the appearance of a sublinear portion in the current-voltage characteristics described by the dependence V = exp(Iaw). The observation of a sublinear portion in the current-voltage characteristics measured in both the forward and reverse electric current directions over a wide temperature range 77–323 K suggests that the diffusion-drift regime can occur in different parts of the i layer, depending on the electric current density and the ambient temperature. The changes observed in the electric current and capacitance, as well as in the current-voltage and capacitance-voltage characteristics, after ultrasonic irradiation indicate that, in the CdTe_{1 − x} S _x solid solutions, there exist metastable states, which most probably decay under ultrasonic irradiation and then again form solid solutions with more stable states. Original Russian Text ? Kh.Kh. Ismoilov, A.M. Abdugafurov, Sh.A. Mirsagatov, A.Yu. Leĭderman, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 11, pp. 1953–1957.     

Effect of chemical modification on the structure and dielectric and magnetic properties of multiferroic (1 – x)BiFeO3-xDyFeO3 solid solution

The solid solution of (1-x)BiFeO₃-xDyFeO₃ was prepared by solid state reactions in the form of ceramics. The effects of chemical modification by means of aliovalent ionic substitution of Ti⁴⁺ for Fe³⁺ on the structure and dielectric properties were investigated. A morphotropic phase boundary bridging the perovskite rhombohedral phase and the orthoferrite orthorhombic phase was identified at x around 0.1. The chemical modification was found to stabilize the perovsite phase. The dielectric performance of the solid solution was improved by the substitution of Ti⁴⁺ for Fe³⁺, which decreased the electric conductivity by reducing oxygen vacancies, as evidenced by the decrease in loss tangent values. Magnetic hysteresis and large saturated magnetization (0.5 μ_B/f.u.) were realized in 0.92BiFeO₃-0.08DyFeO₃ with 2% substitution of Ti⁴⁺ for Fe³⁺, which is believed to arise from the disruption of the spiral spin modulation after structural modification, and the interaction between the spins of the Dy³⁺ and Fe³⁺ at low temperatures which decouples the antiferromagnetic order between the Fe³⁺ ions.     

Low-field magnetization of ludwigites Co3O2BO3 and Co3 ? xFexO2BO3 (x ≈ 0.14)

Ludwigite single crystals of compositions Co₃O₂BO₃ and Co_{3 − x} Fe _x O₂BO₃ (x ≈ 0.14) have been synthesized. The crystal structure is investigated at room temperature, and the magnetization is studied in the temperature range T = 4.2–100 K in magnetic fields of up to 600 Oe. The orthorhombic symmetry is revealed, and the unit cell parameters are determined. A number of features are established for the temperature dependence of the magnetization. In unsubstituted Co₃O₂BO₃, two magnetic transitions are found at T _C1 = 43 K and T _C2 = 15 K. At temperatures below 40 K, spin-glass state is revealed. Substitution of iron ions for cobalt ions leads to a noticeable shift in the magnetic transitions toward the high-temperature range: T _C1 = 83 K and T _C2 = 74 K. A ferromagnetic ordering of the P type is found in the Co_{3 − x} Fe _x O₂BO₃ (x ≈ 0.14) compound. Original Russian Text ? N.V. Kazak, N.B. Ivanova, V.V. Rudenko, A.D. Vasil’ev, D.A. Velikanov, S.G. Ovchinnikov, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 5, pp. 916–919.     

Effect of biaxial strain on the band gap of wurtzite AlxGa1?xN

First-principles calculations are applied to investigate the effect of biaxial strain on the band gap of wurtzite Al _x Ga_1−x N. The band gap and band gap bowing parameter increase with compressive strain and decrease with tensile strain. The strain-induced changes in the band gap of Al _x Ga_1−x N are linear in the strain range of about −1% to 1% while the linearity is invalid out of the range. The linear coefficient B(x), characterizing the relationship between the band gap and the biaxial stress, with a quadratic form is obtained. The value of the band gap bowing parameter decreases from 1.0 eV for −2% strain to 0.91 eV for unstrained and to 0.67 eV for 2% strain.     

M?ssbauer study of compounds of Cu3 ? xFexSnS4 and Cu2Fe1 ?xZnxSnS4 systems

A M?ssbauer study of the structural and charge states of ⁵⁷Fe and ¹¹⁹Sn atoms in the compounds of Cu_{3 −x} Fe _x SnS₄ and Cu₂Fe_{1 − x} Zn _x SnS₄ systems was performed. It was shown that the iron atoms in the compounds of both systems were in the divalent and trivalent states occupying the tetrahedral positions of the structure. The character of the changes of the degree of covalency of the Fe²⁺-S, Fe³⁺-S and Sn⁴⁺-S bonds during the isomorphic substitution in the systems was established.     

Profile of the refractive index distribution over the depth of (HfO2)x(Al2O3)1 ? x films

Capabilities of the method of laser null ellipsometry for the study of optical parameters of thin films of multicomponent alloys are demonstrated. Films of alloys (HfO₂) _x (Al₂O₃)_{1 − x} on single-crystal silicon are obtained by the chemical vapor deposition with the use of the following volatile compounds: hafnium dipivaloylmethanate (IV) and aluminum acetylacetonate (III). The selection of initial sets for their optical parameters is justified. The selected model is shown to correspond to experimental data. In films deposited from the mixture of precursors, the refractive index increases from a substrate to a film surface. Due to the separation of sources, films described by a single-layer model were deposited. This fact is indicative of the homogeneous distribution of components over the film thickness.     

Anomalous enhancement of the thermoelectric power in gallium-doped p-(Bi1 ? xSbx)2Te3 single crystals

The effect of gallium on the temperature dependences (5 K ≤ T ≤ 300 K) of Seebeck coefficient α, electrical conductivity σ, thermal conductivity k, and thermoelectric efficiency Z of mixed p-(Bi_0.5Sb_0.5)₂Te₃ semiconductor single crystals is studied. The hole concentration decreases upon gallium doping; that is, gallium causes a donor effect. The Seebeck coefficient increases anomalously, i.e., much higher than it should be at the detected decrease in the hole concentration. This leads to an enhancement of the thermoelectric power. The observed changes in the Seebeck coefficient indicate a noticeable gallium-induced change in the density of states in the valence band.     

Anisotropy of plasma reflection of solid solutions (Bi2 ? xSbx)Te3 (0 < x < 1) in the Temperature Range 78–293 K

We study IR polarized reflection spectra of solid solutions (Bi_2−x Sb _x )Te₃ (0 < x < 1) in the temperature range 78–293 K and in the excitation range of plasma oscillations of free charge carriers. We reveal that, as the content of Sb₂Te₃ in the solid solution increases from 0 to 50%, the anisotropy of both plasma frequencies and magnetic susceptibility vary insignificantly. This indicates that, at 293 K, these crystals do not show significant changes in the composition of groups of free carriers near the chemical potential level. We have found that to describe the observed anisotropy of plasma frequencies, it is necessary to take into account the effect of heavy holes of the valence band. This is also confirmed by the results of the study of the temperature behavior of plasma reflection spectra, which exhibit regularities that are similar to anomalous temperature changes of the Hall coefficient. We show that a decrease in plasma frequencies with increasing temperature cannot be described by an increase in the effective mass of charge carriers in accordance with the expression m* ∼ T ^0.17, which was obtained upon interpretation of temperature dependences of a number of kinetic coefficients. We use the empirical Moss rule ɛ_∞² E _g to estimate the rate of decrease of the thermal band gap dE _g /dT = −1.6 × 10⁻⁴ eV/deg in a crystal that contains 25% Sb₂Te₃.     

Ferroelectric phase stabilization, phase transformations and?thermal properties in (1? x )PbZrO3– x Pb(Co1/3Nb2/3)O3 solid solution

The solid solution between the antiferroelectric PbZrO₃ (PZ) and relaxor ferroelectric Pb(Co_1/3Nb_2/3)O₃ (PCoN) was synthesized by the columbite method. The phase structure and thermal properties of (1−x)PZ–xPCoN, where x=0.0–0.3, were investigated. With these data, the ferroelectric phase diagram between PZ and PCoN has been established. The crystal structure data obtained from XRD indicates that the solid solution PZ–PCoN, where x=0.0–0.3, successively transforms from orthorhombic to rhombohedral symmetry with an increase in PCoN concentration. The AFE→FE phase transition was found in the compositions of 0.0≤x≤0.10. The AFE→FE phase transition shift to lower temperatures with higher compositions of x. The width of the temperature range of FE phase was increased with increasing amount of PCoN. It is apparent that the replacement of the Zr⁴⁺ ion by (Co_1/3Nb_2/3)⁴⁺ ions would decrease the driving force for antiparallel shift of Pb²⁺ ions, because they interrupt the translational symmetry. This interruption caused the appearance of a rhombohedral ferroelectric phase when the amount of PCoN was more than 10 mol%.