Bi2Te3基热电材料的单带和双带传输特性转变

doi:10.15541/jim20240165

无机材料学报 ›› 2024, Vol. 39 ›› Issue (11): 1283-1291.DOI: 10.15541/jim20240165 CSTR: 32189.14.10.15541/jim20240165

所属专题：【能源环境】热电材料(202409)

Bi₂Te₃基热电材料的单带和双带传输特性转变

孟雨婷(), 王雪梅, 章淑娴, 陈志炜(), 裴艳中()

同济大学材料科学与工程学院, 跨学科材料研究中心, 上海 201804

收稿日期:2024-04-02 修回日期:2024-05-20 出版日期:2024-11-20 网络出版日期:2024-06-13
通讯作者: 裴艳中, 教授. E-mail: yanzhong@tongji.edu.cn;
陈志炜, 副教授. E-mail: 14czw@tongji.edu.cn
作者简介:孟雨婷(1999-), 女, 硕士研究生. E-mail: 2130605@tongji.edu.cn

Single- and Two-band Transport Properties Crossover in Bi₂Te₃ Based Thermoelectrics

MENG Yuting(), WANG Xuemei, ZHANG Shuxian, CHEN Zhiwei(), PEI Yanzhong()

Interdisciplinary Materials Research Center, School of Materials Science and Engineering, Tongji University, Shanghai 201804, China

Received:2024-04-02 Revised:2024-05-20 Published:2024-11-20 Online:2024-06-13
Contact: PEI Yanzhong, professor. E-mail: yanzhong@tongji.edu.cn;
CHEN Zhiwei, associate professor. E-mail: 14czw@tongji.edu.cn
About author:MENG Yuting (1999-), female, Master candidate. E-mail: 2130605@tongji.edu.cn
Supported by:
National Natural Science Foundation of China(T2125008);National Natural Science Foundation of China(92263108);National Natural Science Foundation of China(92163203);National Natural Science Foundation of China(52102292);National Natural Science Foundation of China(52003198);Shanghai Rising-Star Program(23QA1409300);Innovation Program of Shanghai Municipal Education Commission(2021-01-07-00-07-E00096)

摘要/Abstract

摘要：

基于Peltier效应, Bi₂Te₃基合金被广泛应用于室温商用固态制冷。提高Bi₂Te₃室温热电性能的主流策略聚焦于能带和微结构工程。然而, 少数载流子部分补偿了窄带隙半导体Bi₂Te₃在室温下的宏观输运特性(即双极效应), 这使得人们深入理解能带结构、散射机制仍具挑战。本工作搜集了大量文献中Bi₂Te₃基热电材料的热电性能数据, 通过同时考虑多数载流子和少数载流子贡献的双带模型模拟了Bi₂Te₃基热电材料在双极效应区域附近和远离双极效应区域的热电输运特性。在模拟过程中, 将费米能级从导带过渡到价带以预测热电各项输运参数的变化情况, 并且量化了Bi₂Te₃基热电材料的各项基本参数, 如态密度有效质量、形变势系数等。该分析方法有助于找出提高Bi₂Te₃基合金热电性能的重要影响因素(如导带迁移率因子与价带迁移率因子的比值)。本工作为分析和预测材料在双极效应下的输运性能提供了一个方便的工具, 为窄带隙热电半导体的发展提供了有利的条件。

关键词: 热电材料, Bi₂Te₃基合金, 双带模型, 窄带隙热电半导体

Abstract:

Based on Peltier effect, Bi₂Te₃-based alloy is widely used in commercial solid-state refrigeration at room temperature. The mainstream strategies for enhancing room-temperature thermoelectric performance in Bi₂Te₃focus on band and microstructure engineering. However, a clear understanding of the modulation of band structure and scattering through such engineering remains still challenging, because the minority carriers compensate partially the overall transport properties for the narrow-gap Bi₂Te₃ at room temperature (known as the bipolar effect). The purpose of this work is to model the transport properties near and far away from the bipolar effect region for Bi₂Te₃-based thermoelectric material by a two-band model taking contributions of both majority and minority carriers into account. This is endowed by shifting the Fermi level from the conduction band to the valence band during the modeling. A large amount of data of Bi₂Te₃-based materials is collected from various studies for the comparison between experimental and predicted properties. The fundamental parameters, such as the density of states effective masses and deformation potential coefficients, of Bi₂Te₃-based materials are quantified. The analysis can help find out the impact factors (e.g. the mobility ratio between conduction and valence bands) for the improvement of thermoelectric properties for Bi₂Te₃-based alloys. This work provides a convenient tool for analyzing and predicting the transport performance even in the presence of bipolar effect, which can facilitate the development of the narrow-gap thermoelectric semiconductors.

Key words: thermoelectric material, Bi₂Te₃-based alloy, two-band model, narrow-gap thermoelectric semiconductor

中图分类号:

TB64

孟雨婷, 王雪梅, 章淑娴, 陈志炜, 裴艳中. Bi₂Te₃基热电材料的单带和双带传输特性转变[J]. 无机材料学报, 2024, 39(11): 1283-1291.

MENG Yuting, WANG Xuemei, ZHANG Shuxian, CHEN Zhiwei, PEI Yanzhong. Single- and Two-band Transport Properties Crossover in Bi₂Te₃ Based Thermoelectrics[J]. Journal of Inorganic Materials, 2024, 39(11): 1283-1291.

图/表 6

Table 1 Parameters used in the two-band model for Bi2Te3 and Bi2Te2.7Se0.3

Parameter	Bi₂Te₃	Bi₂Te_2.7Se_0.3
E_g/eV	0.14^[24]	0.21^[24]
μ_{0,VB,300 K}/(cm²·V^-1·s^-1)	369	265
μ_{0,CB,300 K}/(cm²·V^-1·s^-1)	487	214
Ξ_VB/eV	11.5	12.5
Ξ_CB/eV	10	13.8
N_v,VB	6	6
N_v,CB	6	6
m_d*_,VB/m_e	1.06^{[24,40 -41]}	1.4^[42]
m_d*_,CB/m_e	1.06^[24,41]	1.4^{[43⇓⇓⇓⇓⇓-49]}
κ_{L,300 K}/(W·m^-1·K^-1)	-	0.9

Fig. 1 Crystal structure of Bi2Te2.7Se0.3

Fig. 2 XRD patterns of powder (a) and single crystal (b) specimens for Bi1.99Ag0.01Te3, Bi2Te2.7Se0.3 and Bi2Te2.697Se0.3I0.003

Fig. 3 Two-band model for n- and p-type Bi2Te3[24,40 -41] at room temperature Seebeck coefficient (a, c) and Hall mobility (b, d) along the in-plane direction with respect to the Hall coefficient and Hall carrier concentration; Colorful figures are available on website

Fig. 4 Two-band model for n- and p-type Bi2Te2.7Se0.3 at room temperature with different mobility ratios Seebeck coefficient (a, c) and Hall mobility (b, d) along the in-plane direction[42⇓⇓⇓⇓⇓⇓-49] (circles) and random-orientation[50⇓⇓-53] (stars) with respect to the Hall coefficient and Hall carrier concentration, respectively; Varying thicknesses of the lines represents two-band curves simulated with different ratios of mobility for conduction and valence bands; Colorful figures are available on website

Fig. 5 Room-temperature Seebeck coefficient (a), total thermal conductivity (b), power factor (c), and zT (d) for n- and p-type Bi2Te2.7Se0.3 (along the in-plane direction[42⇓⇓⇓⇓⇓⇓-49] and random-orientation[50⇓⇓-53]) as a function of electrical conductivity, along with the estimation by single-band (dashed lines) and two-band (solid lines) models Colorful figures are available on website

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Bi₂Te₃基热电材料的单带和双带传输特性转变

Single- and Two-band Transport Properties Crossover in Bi₂Te₃ Based Thermoelectrics

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