An analysis of the thermoelectric efficiency of n-(Bi,Sb)2(Te,Se,S)3 solid solutions within an isotropic scattering model

A study is reported on the thermoelectric properties of n-type solid solutions Bi₂Te_3?y Se_y (y=0.12, 0.3, 0.36), Bi_2?x Sb_xTe_3?y Se_y (x=0.08, 0.12; y=0.24, 0.36), and Bi₂Te_3?z S_z (z=0.12, 0.21) as functions of carrier concentration within the 80-to 300-K range. It has been established that the highest thermoelectric efficiency Z is observed in the Bi₂Te_3?y Se_y (y=0.3) solid solution containing excess Te at optimum carrier concentrations (0.35×10¹⁹ cm^?3) and at temperatures from 80 to 250 K. The increase in Z in the Bi₂Te_3?y Se_y solid solution compared with Bi_2?x Sb_xTe_3?y Se_y and Bi₂Te_3?z S_z is accounted for by the high mobility μ₀, an increase in the effective mass m/m ₀ with decreasing temperature, the low lattice heat conductivity κ_L, and the weak anisotropy of the constant-energy surface in a model assuming isotropic carrier scattering.     

Specific features in the behavior of the effective mass and mobility in n-(Bi, Sb)2(Te, Se, S)3 solid solutions

The thermoelectric properties of the multicomponent solid solutions Bi_2?x Sb_xTe_3?y?z Se_yS_z with substitutions of atoms in both sublattices of Bi₂Te₃ were studied. The data obtained in studies of the galvanomagnetic effects in weak magnetic fields were used to properly take into account the change in the carrier scattering mechanisms due to the substitutions Sb → Bi, Se, and S → Te in the solid solutions. The mobility μ₀ with inclusion of the degeneracy, the effective density-of-states mass m/m ₀, and the lattice thermal conductivity κ_L were calculated. An analysis was carried out for the quantities μ₀, m/m ₀, and κ_L in the solid solutions under study as functions of the composition, carrier concentration, and temperature.     

Band gap and type of optical transitions at the interband absorption edge in solid solutions based on bismuth telluride

The spectra of optical absorption in multicomponent n- and p-type solid solutions based on bismuth and antimony chalcogenides with substitutions in both sublattices of Bi₂Te₃ have been investigated. It has been found that, in all the solid solutions studied, just as in the parent compound Bi₂Te₃, direct allowed transitions occur at the interband absorption edge at T = 300 K. The band gap E _g in the n-Bi_{2 ? x} Sb _x Te_{3 ? y ? z} Se _y S _z solid solutions weakly increases with increasing number of substituted atoms in the Bi and Te sublattices. These atomic substitutions do not leads to an increase in E _g as compared to that of the n-Bi₂Te_2.7Se_0.3 composition. An analysis of the optical absorption spectra suggests that the solid solutions under consideration are weakly degenerate, a conclusion supported by the earlier studies of the thermoelectric and galvanomagnetic properties. It has been established that, in the conduction band of the Bi_1.8Sb_0.2Te_2.7Se_0.15S_0.15 solid solution, there is an additional extremum lying above the main extremum at a distance no more than 0.1 eV.     

Thermoelectric properties of n-Bi2Te3 − x − y Se x S y solid solutions under high pressure

The thermoelectric properties of n-Bi₂Te_{3 ? x ? y} Se _x S _y solid solutions with atomic substitutions in the tellurium sublattice (x = 0.27, 0.3, y = 0, and x = y = 0.09) have been studied under a pressure to 8 GPa. It has been found that the Seebeck coefficient and the resistance decrease with increasing P, and power factor χ increases in all compositions and becomes maximal at pressures of 2–4 GPa. It has been shown that the power factor χ, which is proportional to the product of the effective mass of the density of states m/m m/m ₀ and the charge carrier mobility μ₀ in the form (m/m ₀)^3/2μ₀, increases with increasing pressure mainly due to the increase in the mobility and also depends on the solid solution composition. In the composition with substitution Te → Se + S (x = y = 0.09), the peculiarity of the dependence of m/m ₀ on P in the pressure range corresponding to maximal values of the power factor can be explained by the existence of an electronic topological transition. The increase in the power factor under pressure in n-type Bi₂Te_{3 ? x ? y} Se _x S _y solid solutions combined with similar data for p-type Bi_{2 ? x} Sb _x Te₃ solid solutions obtained earlier, including the estimations of possible changes in the thermal conductivity with increasing pressure, give grounds to design thermoelements with improved value of the thermoelectric figure-of-merit, which can be 50–70% at pressures of 2–4 GPa.     

Galvanomagnetic and thermoelectric properties of multicomponent n-type solid solutions based on Bi and Sb chalcogenides

The galvanomagnetic and thermoelectric properties of n-Bi_2-x Sb_xTe_3-y-z Se_yS_z multicomponent solid solutions with atomic substitutions (Sb → Bi; Se, S → Te) are studied. The principal components of the effective mass tensor (m ₁, m ₂, m ₃) for the isotropic mechanism of charge carrier scattering are determined within a many-valley model of the energy spectrum for compositions 0.08 ≤ x ≤ 0.4 and 0.06 ≤ y = z ≤ 0.15. The effect of a variation in the parameters of the constant-energy surface on the thermoelectric efficiency is analyzed for different compositions and carrier concentrations in solid solutions.     

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.     

Electrodeposition of BixSb2−xTey thermoelectric thin films from nitric acid and hydrochloric acid systems

The electrochemical behaviors of Bi^III, Te^IV and Sb^III single ions and their mixtures were investigated in nitric acid and hydrochloric acid system separately. Based on which, Bi_xSb_2−xTe_y thermoelectric films were prepared by potentiostatic electrodeposition from the solutions with different concentrations of Bi^III, Te^IV and Sb^III in the two acid systems. The morphologies, compositions, structures, Seebeck coefficients and resistivities of the deposited thin films were characterized and compared by ESEM (or FESEM), EDS, XRD, Seebeck coefficient measurement system and four-probe resistivity measuring device respectively. The results show that although Bi_xSb_2−xTe_y thermoelectric thin film which structure is consistent with the standard pattern of Bi_0.5Sb_1.5Te₃ can be gained in both of the two acid solutions by adjusting the deposition potential, their morphologies and thermoelectric properties have big differences in different acid solutions.     

Effect of heat treatment on the structure and the thermoelectric properties of Sb<Subscript>0.9</Subscript>Bi<Subscript>1.1</Subscript>Te<Subscript>2.9</Subscript>Se<Subscript>0.1</Subscript> thin films and composites based on them

This work considers the effect of vacuum annealing on the thermoelectric properties of Sb_0.9Bi_1.1Te_2.9Se_0.1 thin film and Sb_0.9Bi_1.1Te_2.9Se_0.1–C composites with various carbon contents produced by ion-beam deposition in an argon atmosphere. The electrical resistivity and the thermopower of Sb_0.9Bi_1.1Te_2.9Se_0.1–C nanocomposites are found to be dependent on not only the carbon concentration but also the type and the concentration of intrinsic point defects of the Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution, which determine the type of conductivity of Sb_0.9Bi_1.1Te_2.9Se_0.1 granules. The power factors are estimated for films of Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution and films of Sb_0.9Bi_1.1Te_2.9Se_0.1–C composites and found to have values comparable with the values for nanostructured materials on the basis of (Bi,Sb)₂(Te,Se)₃ solid solutions.     

Influence of silver on the galvanomagnetic properties and energy spectrum of mixed (Bi1− x Sbx)2Te3 crystals

An investigation is made of the temperature dependences of the resistivity in the range 4.2–300 K, the Hall effect, and the Shubnikov-de Haas effect in magnetic fields up to 40 T in (Bi_{1? x} Sb_x)₂Te₃Ag_y single crystals (0 ≤ x ≤ 0.75). Doping (Bi_{1? x} Sb_x)₂Te₃ crystals with silver showed that in Sb₂Te₃ and (Bi_{1? x} Sb_x)₂Te₃ crystals unlike Bi₂Te₃ silver exhibits acceptor properties. The angular and concentration dependences of the Shubnikov-de Haas effect were studied in (Bi_{1? x} Sb_x)₂Te₃Ag_y. It was established that the anisotropy of the ellipsoids of the upper valence band in Bi_0.5Sb_1.5Te₃ remains unchanged as a result of silver doping.     

Fermi surface and thermoelectric power of (Bi1−x Sbx)2Te3<Ag, Sn> mixed crystals

The Fermi surface anisotropy of (Bi_1?x Sb_x)₂Te₃ single crystals (0.25 ≤ x ≤ 1) was studied by analyzing the angular dependence of the frequency of Shubnikov-de Haas oscillations and the effect of tin and silver doping on the thermoelectric power in these crystals in the temperature range 77 ≤ T ≤ 300 K. It was shown that silver doping of (Bi_1?x Sb_x)₂Te₃ mixed crystals produces acceptors, while silver in Bi₂Te₃ acts as a donor. Tin also exhibits acceptor properties. Both tin and silver doping of p-(Bi_1?x Sb_x)₂Te₃ mixed crystals decrease the thermoelectric power due to an increase in the hole concentration.     

Structural, electrical, and thermoelectrical properties of (Bi1 − x Sb x )2Se3 alloys prepared by a conventional melting technique

Polycrystalline solid solutions of (Bi_{1 ? x} Sb _x )₂Se₃ (x = 0, 0.025, 0.050, 0.075, 0.100) were prepared using a facile method based on the conventional melting technique followed by annealing process. X-ray analysis and Raman spectroscopical measurements revealed formation of Bi₂Se₃ in single phase. The electrical and thermoelectric properties have been studied on the bulk samples in the temperature range 100–420 K. The electrical conductivity measurements show that the activation energy and room-temperature electrical conductivity dependences on the Sb content respectively exhibit minimum and maximum values at x = 0.05. The thermoelectric power exhibited a maximum value near the room temperature suggesting promising materials for room-temperature applications. The highest power factor value was found to be 13.53 μW K^?2 cm^?1 and recorded for the x = 0.05 compound.     

熔体旋甩法合成n型(Bi_(0.85)Sb_(0.15))_2(Te_(1-x)Se_x)_3化合物的微结构及热电性能

采用熔体旋甩结合放电等离子烧结(MS-SPS)技术制备了单相n型四元(Bi0.85Sb0.15)2(Te1-xSex)3(x=0.15,0.17,0.19,0.21)化合物,并对所得样品的微结构和热电传输性能进行了系统研究.样品自由断裂面的场发射扫描电子显微镜及抛光面的背散射电子成分分析表明:块体材料晶粒细小,晶粒排列紧密,成分分布均匀且相结构单一,样品中存在大量10—100nm的层状结构.随着Se含量x的增加,样品的电导率和热导率逐渐增加,而Seebeck系数逐渐降低.相比商业应用的区熔材料,MS-SPS方法合成的高Se组成的样品均在425K后表现出更高的ZT值,其中(Bi0.85Sb0.15)2(Te0.83Se0.17)3样品具有最高的ZT值,在360K可达到0.96,并在320—500K均保持较高的ZT值,500K时其ZT值相比区熔材料提高了48%.此外,通过调节Se的含量,可以有效地调控材料的ZT峰值出现的温度段,这对多级或梯度热电器件的制备具有重要意义.     

Electrical conduction and thermoelectric properties of perovskite-type BaBi1−xSbxO3

To elucidate the thermoelectric properties at high temperatures, the electrical conductivity and Seebeck coefficient were measured at temperatures between 423 K and 973 K for perovskite-type ceramics of BaBi_1?xSb_xO₃ solid solutions with x=0.0–0.5. All the ceramics exhibit p-type semiconducting behaviors and electrical conduction is attributed to hopping of small polaronic holes localized on the pentavalent cations. Substitution of Bi with Sb causes the electrical conductivity σ and cell volume to decrease, but the Seebeck coefficient S to increase, suggesting that the Sb atoms are doped as Sb⁵⁺ and replace Bi⁵⁺, reducing 6s holes conduction from Bi⁵⁺(6s⁰) to Bi³⁺ (6s²). The thermoelectric power factor S ²σ has values of 6×10^?8–3×10^?5 W m^?1 K^?2 in the measured temperature range, and is maximized for an Sb-undoped BaBiO_3?δ, but decreases upon Sb doping due to the decreased σ values.     

Effect of chromium and tellurium impurities on the thermoelectric parameters of galena

Concentration dependences of the Seebeck coefficient, resistivity, and thermal conductivity of thermoelectric PbS crystals with chromium (0 < x ≤ 0.01) and tellurium (0 < y ≤ 0.03) impurities are examined in the temperature region of 300–800 K. It is shown that the introduction of chromium increases the number of free electrons in PbCr _x S _1–x crystals and reduces the Seebeck coefficient. However, an increase in the concentration of tellurium in PbCr _x S _1–x–y Te _y alloys raises the Seebeck coefficient while simultaneously reducing the thermal conductivity. As a result, the thermoelectric efficiency of PbCr _x S _1–x–y Te _y crystals increases. The reasons for the observed effects are discussed.     

Effect of bond polarity in Sb2Te3−x Se x single crystals

Sb₂Te_3?x Se _x (x=0·00?1·25) single crystals were prepared from 5N purity elements using a modified Bridgman method. Measurements of the reflectivity spectra in the plasma resonance frequency range, Hall constantR _H(B∥c) and electrical conductivityσ _⊥C were carried out on these samples at room temperature. With increasing selenium content a shift of the reflectivity minimum towards longer wavelengths was observed as well as an increase of the Hall constant and a decrease of the electrical conductivity — the incorporation of Se atoms into the Sb₂Te₃ crystal lattice results obviously in a decrease in the concentration of free carriers. This effect is accounted for by a change in the polarity of bonds in the Sb₂Te₃ crystal lattice, due to the formation of Se _Te ^x substitutional defects.     

Thermoelectric properties of Bi2Se3/Bi2Te3/Bi2Se3 and Sb2Te3/Bi2Te3/Sb2Te3 quantum well systems

In this work, we develop a theory of thermoelectric transport properties in two-dimensional semiconducting quantum well structures. Calculations are performed for n-type 0.1 wt.% CuBr-doped Bi₂Se₃/Bi₂Te₃/Bi₂Se₃ and p-type 3 wt.% Te-doped Sb₂Te₃/Bi₂Te₃/Sb₂Te₃ quantum well systems in the temperature range 50–600 K. It is found that reducing the well thickness has a pronounced effect on enhancing the thermoelectric figure of merit (ZT). For the n-type Bi₂Se₃/Bi₂Te₃/Bi₂Se₃ with 7 nm well width, the maximum value of ZT is estimated to be 0.97 at 350 K and for the p-type Sb₂Te₃/Bi₂Te₃/Sb₂Te₃ with well width 10 nm the highest value of the ZT is found to be 1.945 at 440 K. An explanation is provided for the resulting higher ZT value of the p-type system compared to the n-type system.     

Inversion of conductivity type in Bi2Te3−xSx crystals

Transport parameters and optical properties of Bi₂Te_3?xS_x single-crystals with x=0–0.18 were studied. With increasing sulphur content the concentration of free current carriers decreases up to x=0.12, due to the interaction of S^x_Te defects with antisite defects Bi^′_Te, and then the p-type conductivity changes to the n-type. The optical gap of Bi₂Te_3?xS_x crystals increases with increasing S content. The obtained results led to the preparation of Bi₂Te₃-Bi₂Te_3?xS_xp–n junction by the heat treatment of p-type Bi₂Te₃ in S vapours.     

Effects of double filling of Pb and Ba on thermoelectric properties of PbxBayCo4Sb11.5Te0.5 compounds by HPHT

Skutterudite compounds Pb_xBa_yCo₄Sb_11.5Te_0.5 (x≤0.23,y≤0.27) with bcc crystal structure have been prepared by the high pressure and high temperature (HPHT) method. The study explored a chemical method for filling Pb and Ba atoms into the voids of CoSb₃ to optimize the thermoelectric figure of merit ZT in the system of Pb_yBa_xCo₄Sb_11.5Te_0.5. The structure of Pb_xBa_yCo₄Sb_11.5Te_0.5 skutterudites was evaluated by means of X-ray diffraction. The Seebeck coefficient, electrical resistivity and power factor were performed from room temperature to 710 K. Compared with Co₄Sb_11.5Te_0.5, the thermal conductivity of Pb and Ba double-filled samples was reduced evidently. Among all filled samples, Pb_0.03Ba_0.27Co₄Sb_11.5Te_0.5 showed the highest power factor of 31.64 μW cm⁻¹ K⁻² at 663 K. Pb_0.05Ba_0.25Co₄Sb_11.5Te_0.5 showed the lowest thermal conductivity of 2.73 W m⁻¹ K⁻¹ at 663 K, and its maximum ZT value reached 0.63 at 673 K.     

Effect of thermal treatment on the thermoelectric properties of Sb<Subscript>0.9</Subscript>Bi<Subscript>1.1</Subscript>Te<Subscript>2.9</Subscript>Se<Subscript>0.1</Subscript> solid solution thin films

The effect thermal treatment in a vacuum has on the thermoelectric properties of Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution thin films obtained via ion-beam sputtering in an argon atmosphere is considered. It is established that the specific resistance and thermopower are determined by the type and concentration of intrinsic point defects of the Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution. The power factor values are found to be comparable to those of nanostructured materials based on (Bi,Sb)₂(Te,Se)₃ solid solutions.     

Thermoelectric figure-of-merit in <Emphasis Type="Italic">p</Emphasis>-type bismuth- and antimony-chalcogenide-based solid solutions above room temperature

The specific features of the variation in the thermoelectric figure-of merit Z for p-type bismuth- and antimony-chalcogenide-based solid solutions p-(Bi,Sb)₂(Te,Se)₃ have been analyzed with allowance made for the data amassed in the investigation of thermoelectric and galvanomagnetic properties. It has been shown that, in the samples with optimum carrier concentrations, the increase in Z in the multicomponent p-Bi_{2 − x} Sb _x Te_{3 − y} Se _y composition (x = 1.3, y = 0.06) in the temperature range 300–370 K is mediated by the high carrier mobility and the low lattice thermal conductivity. The higher effective mass of the density of states and the larger slope of the temperature dependence of the mobility as compared to the other compositions bring about an increase in Z in the p-Bi_{2 − x} Sb _x Te₃ solid solution for x = 1.6 in the temperature range 370–550 K. The increase in the figure-of merit reached in the compositions under study stems also from the increasing contraction of constant-energy ellipsoids along the binary and bisector directions and from the change in the angle θ between the principal axes of the ellipsoids and the crystallographic axes.