Donor-like Effect and Thermoelectric Performance in p-Type Bi0.5Sb1.5Te3 Alloy

doi:10.15541/jim20230121

Abstract

Abstract:

Grain refinement is an effective way to improve the mechanical properties of Bi_0.5Sb_1.5Te₃based alloys. However, the donor-like effect caused by the grain refinement during powder metallurgy severely degrades the thermoelectric properties of the material, which limits the application of Bi_0.5Sb_1.5Te₃-based alloys in micro thermoelectric devices. Therefore, in this study, focusing on p-type Bi_0.5Sb_1.5Te₃-base alloy, the impact of grinding and desorption atmosphere on donor-like effect and thermoelectric transport properties of sintered samples during powder metallurgy process were systematically studied through experiments combined with theoretical calculations. Surface defects $~\text{V}_{\text{Te}}^{\cdot \cdot }$ and ${{\text{{V}'''}}_{\text{Sb}}}$^， generated by the grinding process of Bi_0.5Sb_1.5Te₃-based alloy, reacts with the adsorbed O₂ during sintering process. This generates a large number of $\text{V}_{\text{Te}}^{\cdot \cdot }$ vacancies and free electrons, leading to a donor-like effect and a significant decrease in carrier concentration. The use of protective atmosphere (Ar atmosphere) during grinding to avoid exposure to air or O₂ desorption under protective atmosphere after grinding effectively suppresses the donor-like effect, maintaining high carrier concentration and electrical conductivity of the sample. Moreover, the performance is stable up to 473 K. The samples treated in air or sintered using powder placed in air exhibit a significant donor-like effect, and the carrier concentration decreases from 4.49×10¹⁹cm^–3 to 3.21×10¹⁹ cm^–3. The maximum thermoelectric ZT of 1.03 is obtained at 402 K for the samples sintered with the powders treated under protective atmosphere, and the overall average ZT_ave reaches 0.92. This study provides a new avenue to regulate the donor-like effect of p-type polycrystalline Bi₂Te₃-based compounds and to optimize their thermoelectric properties.

Key words: Bi_0.5Sb_1.5Te₃ alloy, donor-like effect, carrier concentration, thermoelectric property

CLC Number:

TQ174

LU Zhiqiang, LIU Keke, LI Qiang, HU Qin, FENG Liping, ZHANG Qingjie, WU Jinsong, SU Xianli, TANG Xinfeng. Donor-like Effect and Thermoelectric Performance in p-Type Bi_0.5Sb_1.5Te₃ Alloy[J]. Journal of Inorganic Materials, 2023, 38(11): 1331-1337.

Figures/Tables 7

Fig. 1 (a) Powder XRD patterns of sintered samples with powders treated in different atmospheres, and (b) XRD patterns of bulk samples measured perpendicular to the sintered pressing direction

Table 1 Orientation factor (F), conductivity (σ), Seebeck coefficient (S), carrier concentration (n), mobility (μ), total thermal conductivity(κ), effective mass (m*/m0), and thermoelectric value ZT of the samples treated with different atmospheres at room temperature and average thermoelectric value ZTave

Sample	F	σ/(×10⁴, S•m⁻¹)	S/(μV•K⁻¹)	n/(×10¹⁹, cm⁻³)	μ/(cm²•V⁻¹•s⁻¹)	κ/(W•m⁻¹•K⁻¹)	m^/m*₀	ZT	ZT_ave
In-Ar	0.076	17.50	150	4.49	243	1.49	0.93	0.78	0.92
Out-Ar	0.074	15.55	160	3.88	249	1.45	0.91	0.82	0.86
In-Air	0.078	12.92	172	3.31	243	1.28	0.89	0.90	0.81
Out-Air	0.072	12.36	177	3.21	240	1.23	0.89	0.94	0.87

Fig. 2 FESEM images for In-Ar sample along the direction (a) perpendicular and (b) parallel to sintering pressure

Fig. 3 (a) Backscattered electron images, (b) Bi, (c) Sb, and (d) Te elemental distribution mappings on the polished surface of In-Ar sample via EDS along the direction perpendicular to the sintering pressure

Fig. 4 Formation energy with complex defects presented in Bi0.5Sb1.5Te3 alloys at different Te chemical potentials

Fig. 5 Temperature dependence of (a) electrical conductivity, (b) Seebeck coefficient, (c) power factor for samples treated with different atmospheres along the direction perpendicular to the sintering pressure, (d) relationship between Seebeck coefficient and carrier concentration (Pisarenko curve) at room temperature for Bi-Sb-Te alloy

Fig. 6 Temperature dependence of (a) total thermal conductivity, (b) sum of lattice thermal conductivity and bipolar thermal conductivity, (c) thermoelectric merit ZT for samples treated with different atmospheres along the direction perpendicular to the sintering pressure

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Donor-like Effect and Thermoelectric Performance in p-Type Bi_0.5Sb_1.5Te₃ Alloy

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