区熔n型Bi1.96Sb0.04Te2.70Se0.30热电材料均匀性研究

doi:10.15541/jim20250045

无机材料学报 ›› 2025, Vol. 40 ›› Issue (11): 1252-1260.DOI: 10.15541/jim20250045

区熔n型Bi_1.96Sb_0.04Te_2.70Se_0.30热电材料均匀性研究

吴明轩¹^,²(), 李珺杰¹^,²(), 陈硕¹^,², 鄢永高¹^,², 苏贤礼¹^,²(), 张清杰², 唐新峰¹^,²

1.武汉理工大学襄阳示范区湖北隆中实验室, 襄阳 441000
2.武汉理工大学材料复合新技术全国重点实验室, 武汉 430070

收稿日期:2025-02-07 修回日期:2025-05-14 出版日期:2025-11-20 网络出版日期:2025-06-05
通讯作者: 苏贤礼, 研究员. E-mail: suxianli@whut.edu.cn;
李珺杰, 实验师. E-mail: lijunjie2012@whut.edu.cn
作者简介:吴明轩(2000-), 男, 硕士研究生. E-mail: krenwu_u@whut.edu.cn
基金资助:
国家重点研发计划(2024YFF0505900);国家自然科学基金(W2412066)

Homogeneity of Zone-melted n-type Bi_1.96Sb_0.04Te_2.70Se_0.30 Thermoelectric Material

WU Mingxuan¹^,²(), LI Junjie¹^,²(), CHEN Shuo¹^,², YAN Yonggao¹^,², SU Xianli¹^,²(), ZHANG Qingjie², TANG Xinfeng¹^,²

1. Longzhong Laboratory in Hubei Province Xiangyang Demonstration Zone of Wuhan University of Technology, Xiangyang 441000, China
2. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China

Received:2025-02-07 Revised:2025-05-14 Published:2025-11-20 Online:2025-06-05
Contact: SU Xianli, professor. E-mail: suxianli@whut.edu.cn;
LI Junjie, lecturer. E-mail: lijunjie2012@whut.edu.cn
About author:WU Mingxuan (2000-), male, Master candidate. E-mail: krenwu_u@whut.edu.cn
Supported by:
National Key Research and Development Program(2024YFF0505900);National Natural Science Foundation of China(W2412066)

摘要/Abstract

摘要：

区熔制备技术是商业化制备Bi₂Te₃基热电材料的重要方法, 区熔纯化过程受材料分凝的影响, 但迄今为止, 区熔工艺对Bi₂Te₃基材料分凝机制影响的研究尚未形成统一认识, 特别是材料组元增加后会显著影响分凝过程和均匀性。本研究以n型Bi_1.96Sb_0.04Te_2.694Se_0.3Br_0.006材料为研究对象, 采用熔融-区熔-退火工艺, 系统探讨了区熔温度对材料组成和热电性能均匀性的影响规律, 发现区熔温度对棒材均匀性有很大影响, 轴向组成分凝是影响其均匀性的重要因素, 在高区熔温度(≥988 K)下, 棒材顶部出现了Bi₂Te₃富集相的分凝, 这种组成分凝现象导致材料热电性能的均匀性变差。区熔温度为988和1003 K样品的室温ZT在不同区域(中心顶部、边缘顶部(ET)、中心底部、边缘底部)最大差异达到了31.5%和28.6%。降低区熔温度至958 K显著抑制了Bi₂Te₃富集相分凝, 制备得到具有优异热电性能和均匀性的圆柱型锭体(内径16 mm, 高55 mm), 样品不同区域的室温ZT最大差异仅为14%, 并且958 K-ET样品在350 K下获得最大ZT为1.05。本研究揭示了区熔温度对多组元n型(Bi, Sb)₂(Te, Se)₃基材料组成成分及热电性能均匀性的调控机制, 为制备具有优异均匀性的高性能热电材料提供了重要指导。

关键词: n型碲化铋, 区熔工艺, 均匀性, 热电性能

Abstract:

Zone melting technique is an important method for commercial preparation of Bi₂Te₃-based thermoelectric materials. The zone melting purification process is affected by segregation of materials. However, so far, the effect of zone melting process on the segregation mechanism of Bi₂Te₃-based materials has not yet formed unified understanding. In particular, increase of material components significantly affects the segregation process and uniformity. In this study, n-type Bi_1.96Sb_0.04Te_2.694Se_0.3Br_0.006 material was used as the research object, and the melting-zone melting-annealing process was used to systematically explore the influence of zone melting temperature on the composition and uniformity of thermoelectric performance. It was found that the zone melting temperature had a great influence on uniformity of the ingot, and the axial composition segregation was an important factor affecting its uniformity. At high zone melting temperature (≥988 K), the segregation of Bi₂Te₃-rich phase appeared at the top of the ingot, which made the poor uniformity of thermoelectric properties of the material. The maximum difference of ZT at room temperature in different regions (center top, edge top (ET), center bottom, edge bottom) of samples with zone melting temperatures of 988 and 1003 K reached 31.5% and 28.6%, respectively. Reducing the zone melting temperature to 958 K significantly inhibited the segregation of Bi₂Te₃-enriched phase, and a cylindrical ingot (inner diameter of 16 mm, height of 55 mm) with excellent thermoelectric properties and uniformity was prepared. The maximum difference of ZT at room temperature in different regions was only 14%, and the maximum ZT of 958 K-ET sample was 1.05 at 350 K. This study reveals the regulation mechanism of zone melting temperature on the composition and thermoelectric performance uniformity of multi-component n-type (Bi, Sb)₂(Te, Se)₃-based materials, which provides important guidance for the preparation of high-performance thermoelectric materials with excellent uniformity.

Key words: n-type bismuth telluride, zone melting process, homogeneity, thermoelectric property

中图分类号:

TQ174

吴明轩, 李珺杰, 陈硕, 鄢永高, 苏贤礼, 张清杰, 唐新峰. 区熔n型Bi_1.96Sb_0.04Te_2.70Se_0.30热电材料均匀性研究[J]. 无机材料学报, 2025, 40(11): 1252-1260.

WU Mingxuan, LI Junjie, CHEN Shuo, YAN Yonggao, SU Xianli, ZHANG Qingjie, TANG Xinfeng. Homogeneity of Zone-melted n-type Bi_1.96Sb_0.04Te_2.70Se_0.30 Thermoelectric Material[J]. Journal of Inorganic Materials, 2025, 40(11): 1252-1260.

图/表 9

图1 测试样品在区熔棒材中的位置示意图

Fig. 1 Schematic diagram of positions of the test samples in the zone melting bar

图2 (a) 958、(b) 973、(c) 988和(d) 1003 K区熔温度制备的Bi1.96Sb0.04Te2.694Se0.3Br0.006不同区域样品的σ、S和PF

Fig. 2 σ, S and PF of different regions in Bi1.96Sb0.04Te2.694Se0.3Br0.006 with zone melting temperatures of (a) 958, (b) 973, (c) 988, and (d) 1003 K

图3 Bi1.96Sb0.04Te2.694Se0.3Br0.006样品的(a, d)热导率κ, (b, e) κL+κb和(c, f) ZT

Fig.3 (a, d) Thermal conductivities κ, (b, e) κL+κb and (c, f) ZT of Bi1.96Sb0.04Te2.694Se0.3Br0.006 samples

图4 Bi1.96Sb0.04Te2.694Se0.3Br0.006样品的XRD图谱

Fig. 4 XRD patterns of Bi1.96Sb0.04Te2.694Se0.3Br0.006 samples (a) 2θ=10°-70°; (b) 2θ=27.5°-28.5°

图5 不同区熔温度制备的Bi1.96Sb0.04Te2.694Se0.3Br0.006不同区域样品的Bi/Sb和Te/Se变化趋势

Fig. 5 Variation trends of Bi/Sb and Te/Se of different regions in Bi1.96Sb0.04Te2.694Se0.3Br0.006 samples prepared under different zone melting temperatures Colorful figures are available on website

图6 不同区熔温度制备的Bi1.96Sb0.04Te2.694Se0.3Br0.006不同区域样品的ne和μ

Fig. 6 ne and μ of different regions in Bi1.96Sb0.04Te2.694Se0.3Br0.006 samples prepared under different zone melting temperatures

图S1 (a) 1003 K-CB和(b) 1003 K-CT样品的自由断裂截面FESEM照片

Fig. S1 Cross-sectional FESEM images of the free fracture cross sections of (a) 1003 K-CB and (b) 1003 K-CT samples

图S2 (a) 958 K-Bottom和(b) 988 K-Top样品的抛光表面BSE图像及对应区域Bi、Sb、Se、Te和Br元素面分布图

Fig. S2 BSE images of polished surface and surface distributions of Bi, Sb, Se, Te and Br elements in the corresponding regions for (a) 958 K-Bottom and (b) 988 K-Top

表S1 Bi1.96Sb0.04Te2.694Se0.3Br0.006样品在室温下的σ、S、κ和ZT

Table S1 σ, S, κ and ZT of Bi1.96Sb0.04Te2.694Se0.3Br0.006 samples at room temperature

Sample	σ/(×10⁴, S·m⁻¹)	S/(μV·K^-1)	κ/(W·m^-1·K^-1)	ZT
958 K-CB	11.1	-186	1.37	0.86
958 K-CT	10.9	-195	1.43	0.89
958 K-EB	10.4	-195	1.38	0.88
958 K-ET	11.4	-199	1.42	0.98
973 K-CB	11.2	-197	1.50	0.89
973 K-CT	9.86	-201	1.48	0.82
973 K-EB	9.45	-196	1.50	0.74
973 K -ET	9.88	-204	1.48	0.85
988 K-CB	11.1	-205	1.47	0.96
988 K-CT	8.54	-202	1.44	0.73
988 K-EB	9.98	-200	1.48	0.76
988 K-ET	9.05	-201	1.43	0.86
1003 K-CB	9.00	-206	1.47	0.80
1003 K-CT	7.27	-216	1.39	0.74
1003 K-EB	7.34	-202	1.47	0.63
1003 K-ET	7.51	-214	1.39	0.76

参考文献 55

[1]	YANG D, XING Y, WANG J, et al. Multifactor roadmap for designing low-power-consumed micro thermoelectric thermostats in a closed-loop integrated 5G optical module. Interdisciplinary Materials, 2024, 3(2): 326. DOI URL
[2]	范人杰, 江先燕, 陶奇睿, 等. In₁₊_xTe化合物的结构及热电性能研究. 物理学报, 2021, 70(13): 393.
[3]	LIU Z, HONG T, XU L, et al. Lattice expansion enables interstitial doping to achieve a high average ZT in n-type PbS. Interdisciplinary Materials, 2023, 2(1): 161. DOI URL
[4]	QIU J, YAN Y, XIE H, et al. Achieving superior performance in thermoelectric Bi_0.4Sb_1.6Te_3.72 by enhancing texture and inducing high-density line defects. Science China Materials, 2021, 64: 1507. DOI
[5]	唐新峰, 柳伟, 谭刚健, 等. 热电材料物理化学. 北京: 科学出版社, 2024: 1-30.
[6]	陈立东, 刘睿恒, 史迅. 热电材料与器件. 北京: 科学出版社, 2018: 1-18.
[7]	张建中. 温差电技术. 电源技术, 2016(3): 754.
[8]	LIN L, ZHANG Y F, LIU H B, et al. A new configuration design of thermoelectric cooler driven by thermoelectric generator. Applied Thermal Engineering, 2019, 160: 114087. DOI URL
[9]	LIU W D, WANG D Z, LIU Q, et al. High-performance GeTe- based thermoelectrics: from materials to devices. Advanced Energy Materials, 2020, 10(19): 2000367. DOI URL
[10]	TAN G, ZHAO L D, KANATZIDIS M G. Rationally designing high-performance bulk thermoelectric materials. Chemical Reviews, 2016, 116(19): 12123. PMID
[11]	HE J, TRITT T M. Advances in thermoelectric materials research: looking back and moving forward. Science, 2017, 357(6358): eaak9997. DOI URL
[12]	ROWE D M. Thermoelectrics handbook:macro to nano. Boston: CRC press, 2018: 1008.
[13]	訾鹏, 白辉, 汪聪, 等. Ag_yIn_3.33-_y_/3Se₅化合物结构和热电性能. 物理学报, 2022, 71(11): 326.
[14]	XIE H, ZHAO L D, KANATZIDIS M G. Lattice dynamics and thermoelectric properties of diamondoid materials. Interdisciplinary Materials, 2024, 3(1): 5. DOI URL
[15]	HUANG Y, LYU T, ZENG M, et al. Manipulation of metavalent bonding to stabilize metastable phase: a strategy for enhancing ZT in GeSe. Interdisciplinary Materials, 2024: 3(4): 607. DOI URL
[16]	YANG D, LUO T, SU X, et al. Unveiling the intrinsic low thermal conductivity of BiAgSeS through entropy engineering in SHS kinetic process. Journal of Inorganic Materials, 2021, 36(9): 991. DOI
[17]	GONG H, SU X L, YAN Y G, et al. Ultra-fast synthesis of Cu₂S thermoelectric materials under pulsed electric field. Journal of Inorganic Materials, 2019, 34(12): 1295. DOI
[18]	PEIAN R, CONG W, PENG Z, et al. Effect of Te and In co-doping on thermoelectric properties of Cu₂SnSe₃ compounds. Journal of Inorganic Materials, 2022, 37(10): 1079. DOI URL
[19]	YANG J, CAILLAT T. Thermoelectric materials for space and automotive power generation. MRS Bulletin, 2006, 31(3): 224. DOI URL
[20]	WANG W C, CHANG Y L. Experimental investigation of thermal deformation in thermoelectric coolers. Strain, 2011, 47: 232. DOI URL
[21]	SNYDER G J, URSELL T S. Thermoelectric efficiency and compatibility. Physical Review Letters, 2003, 91(14): 148301. DOI URL
[22]	SNYDER G J, SNYDER A H. Figure of merit ZT of a thermoelectric device defined from materials properties. Energy & Environmental Science, 2017, 10(11): 2280.
[23]	郭凯, 骆军, 赵景泰. 热电材料的基本原理, 关键问题及研究进展. 自然杂志, 2015, 37(3): 175. DOI
[24]	唐昊, 白辉, 吕嘉南, 等. 表面修饰工程协同优化Bi₂Te₃基微型热电器件的界面性能. 物理学报, 2022, 71(16): 330.
[25]	YANG X, SU X L, YAN Y G, et al. Structures and thermoelectric properties of (GeTe)_(n)Bi₂Te₃. Journal of Inorganic Materials, 2021, 36(1): 75. DOI URL
[26]	CHEN Y, SHI Q, ZHONG Y, et al. Ga intercalation in van der Waals layers for advancing p-type Bi₂Te₃-based thermoelectrics. Chinese Physics B, 2023, 32(6): 067201. DOI
[27]	CHI H, LIU W, SUN K, et al. Low-temperature transport properties of Tl-doped Bi₂Te₃ single crystals. Physical Review B—Condensed Matter and Materials Physics, 2013, 88(4): 045202. DOI URL
[28]	LIU F, ZHANG M, NAN P, et al. Unraveling the origin of donor- like effect in bismuth-telluride-based thermoelectric materials. Small Science, 2023, 3(8): 2300082.
[29]	LIU D, BAI S, WEN Y, et al. Lattice plainification and band engineering lead to high thermoelectric cooling and power generation in n-type Bi₂Te₃ with mass production. National Science Review, 2025, 12(2): nwae448. DOI URL
[30]	ZHANG Z, SUN M, LIU J, et al. Ultra-fast fabrication of Bi₂Te₃ based thermoelectric materials by flash-sintering at room temperature combining with spark plasma sintering. Scientific Reports, 2022, 12: 10045. DOI
[31]	CHEN C, WANG B, YING P, et al. Microstructure engineered Bi₂Te₃-based materials with outstanding mechanical and thermoelectric properties. Journal of Alloys and Compounds, 2025, 1020: 179543. DOI URL
[32]	SHI Q, LI J, ZHAO X, et al. Comprehensive insight into p-type Bi₂Te₃-based thermoelectrics near room temperature. ACS Applied Materials & Interfaces, 2022, 14(44): 49425.
[33]	LU Z Q, LIU K K, LI Q, et al. Donor-like effect and thermoelectric performance in p-type Bi_0.5Sb_1.5Te₃ alloy. Journal of Inorganic Materials, 2023, 38(11): 1331. DOI URL
[34]	李强, 陈硕, 刘可可, 等. n型Bi₂Te₃基化合物的类施主效应和热电性能. 物理学报, 2023, 72(9): 135.
[35]	ZHANG Q, FANG T, LIU F, et al. Tuning optimum temperature range of Bi₂Te₃-based thermoelectric materials by defect engineering. Chemistry-An Asian Journal, 2020, 15(18): 2775. DOI URL
[36]	HUANG W, TAN X, CAI J, et al. Synergistic effects improve thermoelectric properties of zone-melted n-type Bi₂Te_2.7Se_0.3. Materials Today Physics, 2023, 32: 101022. DOI URL
[37]	田源, 汪波, 李存成, 等. 区熔n型碲化铋材料的制备及性能优化. 材料科学与工程学报, 2024, 42(2): 186.
[38]	LIU D, STÖTZEL J, SEYRING M, et al. Anisotropic n-type Bi₂Te₃-In₂Te₃ thermoelectric material produced by seeding zone melting and solid state transformation. Crystal Growth & Design, 2016, 16(2): 617. DOI URL
[39]	WANG T, ZHOU C, HUANG W, et al. Synergistic improvement of BiI₃ and In on thermoelectric properties of zone-melted n-type Bi₂Te_2.7Se_0.3. ACS Applied Materials & Interfaces, 2024, 16(31): 41080.
[40]	LIU D, LI X, BORLIDO P M D C, et al. Anisotropic layered Bi₂Te₃-In₂Te₃ composites: control of interface density for tuning of thermoelectric properties. Scientific Reports, 2017, 7: 43611. DOI
[41]	HA H P, HYUN D B, BYUN J Y, et al. Enhancement of the yield of high-quality ingots in the zone-melting growth of p-type bismuth telluride alloys. Journal of Materials Science, 2002, 37(21): 4691. DOI
[42]	KIM H S, HEINZ N A, GIBBS Z M, et al. High thermoelectric performance in (Bi_0.25Sb_0.75)₂Te₃ due to band convergence and improved by carrier concentration control. Materials Today, 2017, 20(8): 452. DOI URL
[43]	PERRIN D, CHITROUB M, SCHERRER S, et al. Study of the n-type Bi₂Te_2.7Se_0.3 doped with bromine impurity. Journal of Physics and Chemistry of Solids, 2000, 61(10): 1687. DOI URL
[44]	KAVEI G, KARAMI M. Thermoelectric crystals Bi₂Te_2.88Se_0.12 undoped and doped by CdCl₂ or CdBr₂ impurities, fabricated and characterized by XRD and Hall effect. Materials Research Bulletin, 2008, 43(2): 239. DOI URL
[45]	CHEN Y R, HWANG W S, HSIEH H L, et al. Thermal and microstructure simulation of thermoelectric material Bi₂Te₃ grown by zone- melting technique. Journal of Crystal Growth, 2014, 402: 273. DOI URL
[46]	KAVEI G, AHMADI K, KAVEI A. Electrical conductivity variation of (Bi₂Te₃)_0.25(Sb₂Te₃)_0.75 crystal grown using the zone melting method. International Journal of Materials Research, 2013, 104(3): 314. DOI URL
[47]	XIA H, LI X, XU Q. Macro-micro-coupling simulation and space experiment study on zone melting process of bismuth telluride-based crystal materials. Metals, 2022, 12(5): 886. DOI URL
[48]	GUO X, QIN J, JIA X, et al. Quaternary thermoelectric materials: synthesis, microstructure and thermoelectric properties of the (Bi,Sb)₂(Te,Se)₃ alloys. Journal of Alloys and Compounds, 2017, 705: 363. DOI URL
[49]	CHAUHAN N S, PYRLIN S V, LEBEDEV O I, et al. Compositional fluctuations mediated by excess tellurium in bismuth antimony telluride nanocomposites yield high thermoelectric performance. The Journal of Physical Chemistry C, 2021, 125(37): 20184. DOI URL
[50]	LIU Y, ZHANG Y, LIM K H, et al. High thermoelectric performance in crystallographically textured n-type Bi₂Te_3-_xSe_x produced from asymmetric colloidal nanocrystals. ACS Nano, 2018, 12(7): 7174. DOI URL
[51]	VASIL’EV A, IVANOV O, YAPRYNTSEV M, et al. Aspects of the microstructure and thermoelectric properties of a two-phase ceramic material based on the high-entropy system Bi-Sb-Te-Se-S. Glass and Ceramics, 2023, 80(1): 52. DOI
[52]	CHEN H W, CHEN B C, WU H J. Dilute Sb doping yields softer p-type Bi₂Te₃ thermoelectrics. Advanced Electronic Materials, 2024, 10(6): 2300793. DOI URL
[53]	GUAN X, LIU Z, MA N, et al. High-performance p-type Bi₂Te₃- based thermoelectric materials with a wide temperature range obtained by direct Sb doping. Acta Metallurgica Sinica (English Letters), 2025, 38: 849. DOI
[54]	WITTING I T, RICCI F, CHASAPIS T C, et al. The thermoelectric properties of n-type bismuth telluride: bismuth selenide alloys Bi₂Te_3-_xSe_x. Research, 2020, 2020: 4361703.
[55]	LI Y, BAI S, WEN Y, et al. Realizing high-efficiency thermoelectric module by suppressing donor-like effect and improving preferred orientation in n-type Bi₂(Te,Se)₃. Science Bulletin, 2024, 69(11): 1728. DOI URL

区熔n型Bi_1.96Sb_0.04Te_2.70Se_0.30热电材料均匀性研究

Homogeneity of Zone-melted n-type Bi_1.96Sb_0.04Te_2.70Se_0.30 Thermoelectric Material

RichHTML

PDF (PC)