能带优化和载流子调控改善SnTe的热电性能

doi:10.15541/jim20230316

无机材料学报 ›› 2024, Vol. 39 ›› Issue (3): 306-312.DOI: 10.15541/jim20230316 CSTR: 32189.14.10.15541/jim20230316

所属专题：【能源环境】热电材料(202409)

能带优化和载流子调控改善SnTe的热电性能

陈浩¹(), 樊文浩², 安德成³, 陈少平¹()

1.太原理工大学材料科学与工程学院, 太原 030024
2.太原理工大学物理学院, 太原 030024
3.太原理工大学化学学院, 太原 030024

收稿日期:2023-07-13 修回日期:2023-09-14 出版日期:2024-03-20 网络出版日期:2023-10-07
通讯作者: 陈少平, 教授. E-mail: chenshaoping@tyut.edu.cn
作者简介:陈浩(1995-), 男, 硕士研究生. E-mail: chenha024@163.com
基金资助:
国家自然科学基金(52202277);山西省自然科学基金(202203021221071);山西省科技合作与交流专项项目(202104041101007);山西省回国留学人员科研资助项目(2023-083)

Improvement of Thermoelectric Performance of SnTe by Energy Band Optimization and Carrier Regulation

CHEN Hao¹(), FAN Wenhao², AN Decheng³, CHEN Shaoping¹()

1. College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2. College of Physics, Taiyuan University of Technology, Taiyuan 030024, China
3. College of Chemistry, Taiyuan University of Technology, Taiyuan 030024, China

Received:2023-07-13 Revised:2023-09-14 Published:2024-03-20 Online:2023-10-07
Contact: CHEN Shaoping, professor. E-mail: chenshaoping@tyut.edu.cn
About author:CHEN Hao (1995-), male, Master candidate. E-mail: chenha024@163.com
Supported by:
National Natural Science Foundation of China(52202277);Natural Science Foundation of Shanxi Province(202203021221071);Special Project of Scientific and Technological Cooperation and Exchange in Shanxi Province(202104041101007);Shanxi Scholarship Council of China(2023-083)

摘要/Abstract

摘要：

作为ⅣA族碲化物, SnTe具有与PbTe相同的晶体结构和相似的双价带结构, 是一种非常有前途的热电材料, 但高温软化和低温热电性能差等问题阻碍了其进一步推广应用。因此, 提升SnTe的平均热电优值, 拓宽服役区间, 有重要的研究意义。能带工程和晶格工程可同时优化功率因子和晶格热导率, 提升SnTe的热电性能。本研究采用MgSe合金化策略, 通过熔炼和放电等离子烧结(SPS)的方法制备了一系列Sn_1-_yPb_yTe-x%MgSe(0.01≤y≤0.05, 0≤x≤6)样品。研究发现, 合金化MgSe可增大能带带隙, 有效抑制本征SnTe在高温段的双极扩散, 使高温Seebeck系数得到提升, 同时声子散射降低了体系晶格热导率, 使高温热电性能(873 K)提升了100%; 掺杂Pb元素可有效调制载流子浓度抑制电子热导率, 从而提升SnTe平均热电性能。其中, Sn_0.96Pb_0.04Te-4%MgSe样品在873 K的ZT为1.5, 423~873 K的平均ZT达到0.8, 得到了比文献更优异的结果。

关键词: 热电材料, 载流子调制, 合金化, 能带工程, SnTe

Abstract:

As group ⅣA tellurides, SnTe has the same crystal structure and similar bivalent band structure as PbTe, making it a promising thermoelectric material. However, the main concern of softening at elevated temperature and lower ZT at low temperatures has been hindering its application. Therefore, it is significant to expand the service temperature range of SnTe by improving its average ZT. It has been reported that the thermoelectric performance of SnTe is improved by regulating the power factor and lattice thermal conductivity based on band and lattice engineering. In this study, MgSe alloying strategy was used to prepare a series of Sn_1-_yPb_yTe-x%MgSe(0.01≤y≤0.05, 0≤x≤6) samples by combining melting and Spark Plasma Sintering (SPS) techniques. The results show that alloying MgSe leads to an increase in the band gap, effectively suppressing the bipolar effect of intrinsic SnTe, improving the Seebeck coefficient in the high-temperature range, and reducing lattice thermal conductivity through phonon scattering as well. As a result, ZT at 873 K is improved by 100%. The incorporation of Pb effectively modulates the carrier concentration, successfully suppressing electronic thermal conductivity, and thereby improving average thermoelectric performance of SnTe. Among them, Sn_0.96Pb_0.04Te-4%MgSe possesses a ZT value of 1.5 at 873 K and an average ZT value of 0.8 at 423-873 K, displaying superior performance compared to literature.

Key words: thermoelectric material, carrier modulation, alloying, band engineering, SnTe

中图分类号:

TB34

陈浩, 樊文浩, 安德成, 陈少平. 能带优化和载流子调控改善SnTe的热电性能[J]. 无机材料学报, 2024, 39(3): 306-312.

CHEN Hao, FAN Wenhao, AN Decheng, CHEN Shaoping. Improvement of Thermoelectric Performance of SnTe by Energy Band Optimization and Carrier Regulation[J]. Journal of Inorganic Materials, 2024, 39(3): 306-312.

图/表 8

图1 SnTe-x%MgSe (0≤x≤6)样品的(a)XRD图谱和(b)晶格常数

Fig. 1 (a) XRD patterns and (b) lattice parameter for SnTe-x%MgSe (0≤x≤6) samples

图2 SnTe-x%MgSe (0≤x≤6)样品的(a)电导率随温度变化曲线和(b)霍尔载流子浓度及迁移率测试

Fig. 2 (a) Temperature dependent electrical conductivity, and (b) Houle carrier concentration and mobility for SnTe-x%MgSe (0≤x≤6) samples

图3 (a)SnTe和(b)SnTe-4%MgSe的能带结构及(c)SnTe-x%MgSe (0≤x≤6)样品的Seebeck系数随温度变化曲线

Fig. 3 Band structures of (a) SnTe and (b) SnTe-4%MgSe, and (c) temperature dependent Seebeck coefficients of SnTe-x%MgSe (0≤x≤6) samples

图4 SnTe-x%MgSe (0≤x≤6)的热电性能随温度变化曲线

Fig. 4 Temperature dependent thermoelectric properties of SnTe-x%MgSe (0≤x≤6) (a) Power factor; (b) Thermal conductivity and lattice thermal conductivity; (c) Thermoelectric figure of merit (ZT)

图5 Sn1-yPbyTe-4%MgSe (0.01≤y≤0.05)样品的(a)XRD图谱和(b)晶格常数, 以及(c)Sn0.95Pb0.05Te-4%MgSe样品的EDS图谱

Fig. 5 (a) XRD patterns and (b) lattice parameter for Sn1-yPbyTe-4%MgSe (0.01≤y≤0.05) samples, and (c) EDS mappings for the sample Sn0.95Pb0.05Te-4%MgSe

图6 Sn1-yPbyTe-4%MgSe (0.01≤y≤0.05)样品的热电性能

Fig. 6 Thermoelectric properties of Sn1-yPbyTe-4%MgSe samples (0.01≤y≤0.05) (a) Houle carrier concentration and mobility; (b) Electrical conductivity; (c) Seebeck coefficient; (d) Power factor; (e) Average power factor; (f) Electronic thermal conductivity; (g) Total thermal conductivity; (h) Average ZT

表1 本研究中所有样品的室温热电性能参数

Table 1 Thermoelectric properties of Sn1-yPbyTe-x%MgSe (0.01≤y≤0.05, 0≤x≤6) at room temperature in this study

Sn_1-_yPb_yTe-x%MgSe	S/(μV·K^-1)	σ/(×10³, S·cm^-1)	PF/(μW·cm^-1·K^-2)	n_H/(×10²⁰, cm^-3)	κ_tot/(W·m^-1·K^-1)	ZT
x=0, y=0	24	7.28	4.2	4.3	8.62	0.015
x=2, y=0	15	6.75	1.52	4.21	8.06	0.006
x=4, y=0	17	6.2	1.79	4.31	7.68	0.007
x=6, y=0	18	6.03	1.95	4.02	7.67	0.008
x=4, y=0.01	18	6.87	2.23	3.84	3.74	0.018
x=4, y=0.02	23	5.89	3.12	3.56	3.44	0.027
x=4, y=0.03	30	5.4	4.86	3.42	3.36	0.043
x=4, y=0.04	32	5.2	5.32	3.2	3.27	0.049
x=4, y=0.05	39	4.45	6.77	2.8	3.25	0.062

图7 本研究中Sn0.96Pb0.04Te-4%MgSe与文献报导的SnTe热电性能比较[3,10,12,17,26,32,35⇓⇓⇓ -39]

Fig. 7 Thermoelectric property comparison of Sn0.96Pb0.04Te- 4%MgSe in this work with corresponding materials in literature[3,10,12,17,26,32,35⇓⇓⇓ -39]

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能带优化和载流子调控改善SnTe的热电性能

Improvement of Thermoelectric Performance of SnTe by Energy Band Optimization and Carrier Regulation

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