Effect of constant-energy surface anisotropy on the thermoelectric figure-of-merit of the n-Bi2 (Te,Se,S)3 solid solutions

A study is reported of the thermoelectric and galvanomagnetic properties of n-Bi₂Te_3−x−y Se_xSe_y solid solutions for 0.12⩽x⩽0.36 and 0.12⩽y⩽0.21 within the 80–300 K temperature region. The thermoelectric figure-of-merit Z has been found to correlate with the parameters of the many-valley energy-band model including anisotropic carrier scattering. It is shown that a decrease in the constant-energy surface anisotropy and scattering anisotropy results in a growth of Z for optimum carrier concentrations in the solid solution. Fiz. Tverd. Tela (St. Petersburg) 41, 187–192 (February 1999)     

Galvanomagnetic and thermoelectric properties of p-Bi2?xSbxTe3?ySey solid solutions at low temperatures (<220 K)

The galvanomagnetic and thermoelectric properties of p-Bi_2−x Sb_xTe_3−y Se_y solid solutions (x≤1.2, y≤0.09) are studied for various carrier concentrations. The degeneracy parameter β_d governing the scattering processes in solid solutions was calculated in terms of the many-valley energy spectrum model. The data on the degeneracy parameter and the Seebeck coefficient α were used to calculate the effective scattering parameter r _eff and the reduced Fermi level η. The parameter r _eff was found to depend on the carrier concentration in the materials studied. The temperature dependences of the effective density-of-states mass m/m ₀ and mobility μ₀ in samples with various carrier concentrations were determined. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 8, 2004, pp. 13662–1371. Original Russian Text Copyright ? 2004 by Luk’yanova, Kutasov, Popov, Konstantinov.     

Anomalous increase of the thermopower and thermoelectric figure of merit in Ga-doped <Emphasis Type="Italic">p</Emphasis>-(Bi<Subscript>0.5</Subscript>Sb<Subscript>0.5</Subscript>)<Subscript>2</Subscript>Te<Subscript>3</Subscript> single crystals

The effect of Ga doping on the temperature dependences (5 K ≤ T ≤ 300 K) of the Seebeck coefficient α, electrical conductivity σ, thermal conductivity coefficient κ, and thermoelectric figure of merit Z of p-(Bi_0.5Sb_0.5)₂Te₃ single crystals has been investigated. It has been shown that, upon Ga doping, the hole concentration decreases, the Seebeck coefficient increases, the electrical conductivity decreases, and the thermoelectric figure of merit increases. The observed variations in the Seebeck coefficient cannot be completely explained by the decrease in the hole concentration and indicate a noticeable variation in the density of states due to the Ga doping.     

Thermoelectric properties of n-type Sr x M y Co4Sb12 (M=Yb, Ba) double-filled skutterudites

Alkaline-earth (AE) and rare-earth (RE) atoms are usually used as void fillers in the caged compound CoSb₃ to improve the thermoelectric performance of the filled system. Polycrystalline single-filled Sr_0.21Co₄Sb₁₂, double-filled Sr _x Yb _y Co₄Sb₁₂, and Sr _x Ba _y Co₄Sb₁₂ skutterudites have been synthesized. Rietveld structure refinement confirms that both Sr and Yb occupy the Sb-icosaedron voids in skutterudite frame work. In this paper, we report the high-temperature thermoelectric properties including electrical conductivity, Seebeck coefficient, and thermal conductivity. Double filling of the Sr–Yb combinations shows a stronger suppression on lattice thermal conductivity than that of Sr–Ba combination. Furthermore, the double-filled Sr _x Yb _y Co₄Sb₁₂ skutterudites exhibit a much higher power factor than the Sr-filled system. The maximum power factor for Sr_0.22Yb_0.03Co₄Sb_12.12 reaches 41 μW cm⁻¹ K⁻² at room temperature and 57.5 μW cm⁻¹ K⁻² at 850 K, respectively. The enhanced thermoelectric figures of merit are 1.32 for Sr _x Yb _y Co₄Sb₁₂ and 1.22 for Sr _x Ba _y Co₄Sb₁₂ at 850 K, respectively.     

Carrier mobility in nonstoichiometric n-Bi2Te3−x Sex solid solutions

A study has been made of the thermoelectric and galvanomagnetic properties of n-Bi₂Te_3−x Se_x solid solutions (x=0.3 and 0.36) in the temperature range 80–300 K. The lowest carrier concentrations, (0.8–1)×10¹⁸ cm⁻³, were obtained by displacing the solid solution from the stoichiometric to a Te-rich composition. At such carrier concentrations, the second subband in the conduction band of n-Bi₂Te_3−x Se_x is not filled, which results in a growth of mobility because of the absence of interband scattering, and brings about an increase of thermoelectric efficiency in the 80–120-K range. Fiz. Tverd. Tela (St. Petersburg) 39, 483–487 (March 1997)     

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.     

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.     

Effective mass and mobility of carriers in p-Bi2?xSbxTe3?ySey solid solutions at temperatures below 300 K

The temperature dependences of the Seebeck coefficient α and of the electrical conductivity σ of p-Bi_2−x Sb_xTe_3−y Se_y solid solutions were studied under atomic substitution on the cation (1 ≤ x ≤ 1.5) and anion (0.04 ≤ y ≤ 0.09) bismuth and antimony telluride sublattices within the temperature interval 80–340 K. The effect of variation in the solid-solution composition on the average effective density-of-states mass (m/m ₀) and carrier mobility (μ₀, calculated with due account of degeneracy) was studied under the assumption that carrier scattering is isotropic and that the relaxation time can be approximated by a power-law function , where r _eff is an effective scattering parameter. It is shown that variations in the pattern of the m/m ₀ and μ₀ temperature dependences produced in the temperature region under study by properly varying the number of substituted atoms in the solid solutions may favor an increase in thermoelectric efficiency. __________ Translated from Fizika Tverdogo Tela, Vol. 47, No. 2, 2005, pp. 224–228. Original Russian Text Copyright ? 2005 by Luk’yanova, Kutasov, Konstantinov.     

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.     

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.     

Thermoelectric properties of indium-filled skutterudites prepared by combining solvothermal synthesis and melting

Indium-filled skutterudites with nominal compositions of In _x Co₄Sb₁₂ (x=0,0.1,0.2,0.3) were prepared by combining solvothermal synthesis and melting. The bulk samples were characterized by X-ray diffraction and scanning electron microscopy, respectively. The Seebeck coefficient, electrical conductivity, and thermal conductivity were measured from room temperature up to ∼773 K. Hall effect measurements were performed at room temperature. The thermoelectric properties of the samples were significantly influenced by filling In into CoSb₃. The dimensionless thermoelectric figure of merit, ZT, increased with increasing temperature and reached a maximum value of ∼0.79 for In_0.1Co₄Sb₁₂ at 573 K.     

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.     

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.     

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.     

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.     

Giant magnetoresistance in Hg<Subscript>1−x−y</Subscript>Mn<Subscript>x</Subscript>Fe<Subscript>y</Subscript>Te crystals

Giant magnetoresistance in Hg _1−x−y Mn _x Fe _y Te crystals is caused by clusters with “antiferromagnetic” (Mn-Te-Mn-Te, Mn-Te-Fe-Te) and “ferromagnetic” (Fe-Fe-Fe) ordering. The effect is due to the fact that the charge carriers taking part in electric current interact with the “ferromagnetic” cluster subsystem (Fe-Fe-Fe) magnetized to saturation and become spin-polarized. These spin-polarized charge carriers are strongly scattered by the “antiferromagnetic” Mn-Te-Mn-Te and Mn-Te-Fe-Te clusters, because the magnetic moments inside the clusters and resultant moments of clusters have chaotic orientations. Investigations of kinetic coefficients of Hg _1−x−y Mn _x Fe _y Te crystals before and after thermal treatment show that there is no marked correlation between the giant magnetoresistance and charge-carrier concentration, mobility, and band parameters of crystals. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 28–33, October, 2007.     

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.     

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.     

Fundamental band edge optical absorption in Bi<Subscript>0.5</Subscript>Sb<Subscript>1.5</Subscript>Te<Subscript>3</Subscript>

Spectra of optical absorption in Bi_0.5Sb_1.5Te₃ films grown on mica and KBr substrates have been investigated for T = 145 and 300 K. The data obtained have been analyzed together with the data of investigations on the fundamental absorption edge for Bi₂Te₃ available in the scientific literature. It has been revealed that the interband absorption spectra for both Bi_0.5Sb_1.5Te₃ and Bi₂Te₃ represent a superposition of two components corresponding to direct and indirect allowed optical transitions. In this case, the least energy gap separating the valence band and the conduction band is direct for Bi_2−xSb_xTe₃ (x ≤ 1.5, T = 300 K). For Bi_0.5Sb_1.5Te₃ the temperature variation rates have been estimated for the thresholds of direct and indirect interband transitions. It has been shown that this solid solution is direct gap solution at T ≥ 145 K. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 50–52, July, 2008.     

Spectral features of Ge50−ySbxTe50−x+y alloys where 0x15 and 0y30 in thin film state

Optical spectral features of Ge_50−ySb_xTe_50−x+y alloys where 0x15 and 0y30 in the thin film state were measured. The transmittance and reflectance have been measured at normal incidence at room temperature in the spectral range 190–2500 nm for all compositions with different thicknesses. Refractive index and extinction coefficient have been evaluated in the above spectral range. Band tail width and the band edge parameter were almost constant for all samples with different compositions. Absorption band spectrum on the basis of the imaginary parts of the dielectric constant, ε₂, was applied in evaluating the optical band gap.