High-Performance p-Type Bi2Te3-Based Thermoelectric Materials with a Wide Temperature Range Obtained by Direct Sb Doping

doi:10.1007/s40195-024-01794-x

Abstract

Abstract:

Doping modification is one of the most effective ways to optimize the thermoelectric properties of Bi₂Te₃-based alloys. P-type Bi₂₋_xSb_xTe₃ thermoelectric materials have been successfully prepared by direct Sb doping method. It can be found that doping Sb into Bi₂Te₃ lattice array for Bi-site replacement facilitates the generation of Sb′_Te anti-site defects. This anti-site defects can increase the hole concentration and optimize electrical transport properties of Bi₂₋_xSb_xTe₃ alloys. In addition, the point defects induced by mass and stress fluctuations and the Sb impurities produced during the sintering process can enhance the multi-scale phonon scattering and reduce the lattice thermal conductivity. As a result, the Bi_0.47Sb_1.63Te₃ sample has a maximum thermoelectric figure of merit ZT of 1.04 at 350 K. It is worth noting that the bipolar effect of Bi₂Te₃-based alloys can be weakened with the increase of Sb content. The Bi_0.44Sb_1.66Te₃ sample has a maximum average ZT value (0.93) in the temperature range of 300-500 K, indicating that direct doping of Sb can broaden the temperature range corresponding to the optimal ZT value. This work provides an idea for developing high-performance near room temperature thermoelectric materials with a wide temperature range.

Key words: Bi₂Te₃-based materials, Sb doping, Wide temperature range, Thermoelectric properties

Xicheng Guan, Zhiyuan Liu, Ni Ma, Zhou Li, Juan Liu, Huiyan Zhang, Hailing Li, Qian Ba, Junjie Ma, Chuangui Jin, Ailin Xia. High-Performance p-Type Bi₂Te₃-Based Thermoelectric Materials with a Wide Temperature Range Obtained by Direct Sb Doping[J]. Acta Metallurgica Sinica (English Letters), 2025, 38(5): 849-858.

Figures/Tables 7

Fig. 1 Structural characterization of Bi2−xSbxTe3 (x = 1.50-1.69) samples: a XRD patterns of Bi2−xSbxTe3 samples, b the enlarged XRD patterns of in the 2θ range of 26-31°, c-g rietveld refinement of XRD patterns of Bi2−xSbxTe3 samples, h Raman spectra of Bi2−xSbxTe3 samples

Fig. 2 Microstructural characterization of Bi2−xSbxTe3 (x = 1.50-1.69) samples. FESEM images of fractured Bi2−xSbxTe3 samples: a BST163, b BST166, c BST169. BEI images of polished Bi2−xSbxTe3 samples: d BST150, e BST160, f BST163, g BST166, h BST169. i EDS spectrum of yellow elliptical region in BST166 sample

Table 1 Nominal compositions, EDS compositions, lattice parameter (a, b, and c), room-temperature Hall coefficients (RH), carrier concentrations (n), carrier mobilities (μH), and effective masses (m*) of Bi2−xSbxTe3 samples

Nominal composition	Bi_0.50Sb_1.50Te₃	Bi_0.40Sb_1.60Te₃	Bi_0.37Sb_1.63Te₃	Bi_0.34Sb_1.66Te₃	Bi_0.31Sb_1.69Te₃
EDS composition	Bi_0.53Sb_1.47Te_2.85	Bi_0.40Sb_1.60Te₃	Bi_0.35Sb_1.65Te_2.88	Bi_0.32Sb_1.68Te_2.72	Bi_0.31Sb_1.69Te_2.74
a or b (Å)	4.3122	4.3005	4.2954	4.2911	4.2878
c (Å)	30.5564	30.5190	30.5086	30.4836	30.4780
R_H (cm³/C)	0.24171	0.22782	0.20878	0.18837	0.16513
n (× 10¹⁹ cm⁻³)	2.58252	2.73997	2.98984	3.3138	3.78017
μ_H (cm²·V⁻¹·s⁻¹)	116	113	108	104	98.9
m^⁎	1.95m_e	1.39m_e	1.35m_e	1.36m_e	1.32m_e

Fig. 3 Electrical transport properties of Bi2−xSbxTe3 (x = 1.50-1.69) samples: a Hall coefficients (RH), b carrier concentrations (n) and Hall mobilities (μH) as a function of Sb content at 300 K; c electrical conductivity and d Seebeck coefficient as a function of temperature for Bi2−xSbxTe3 samples in the temperature range of 300-500 K; e curves of |S| vs. n of Bi2−xSbxTe3 samples at 300 K obtained by Pisarenko relation with m* = 1.32me and m* = 1.95me; f power factor as a function of temperature for Bi2−xSbxTe3 samples in the temperature range of 300-500 K

Fig. 4 Temperature dependence of a total thermal conductivity, b carrier thermal conductivity, and c Lorentz number L of Bi2−xSbxTe3 (x = 1.50-1.69) samples; d the difference between the total thermal conductivity and carrier thermal conductivity as a function of temperature for Bi2−xSbxTe3 samples in the temperature range of 300-500 K; e the calculation process of bipolar thermal conductivity of Bi0.34Sb1.66Te3 sample in the temperature range of 300-500 K, and the blue dashed line is linearly fitting to the lattice thermal conductivity at low temperatures from 300 to 330 K; f temperature dependence of bipolar thermal conductivity for Bi2−xSbxTe3 samples in the range of 300-500 K

Fig. 5 Effect of the Sb doping on the band gap of the Bi2Te3 material: a UV-visible spectra of Bi2−xSbxTe3 (x = 1.50-1.69), b-e (αhv)2 versus hv for the direct bandgap of Bi2−xSbxTe3, f variation in the direct band gap for Bi2−xSbxTe3 with the Sb doping

Fig. 6 Temperature dependence of a ZT values of Bi2−xSbxTe3 samples in the temperature range of 300-500 K, b average ZT (300-500 K) values of Bi2−xSbxTe3 samples, c comparison of the average ZT (300-500 K) of the optimized Bi0.34Sb1.66Te3 in this study and other studies on Sb-doped Bi2Te3-based alloys [9,24,29,45]

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High-Performance p-Type Bi₂Te₃-Based Thermoelectric Materials with a Wide Temperature Range Obtained by Direct Sb Doping

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