柔性Cu0.005Bi0.5Sb1.495Te3薄膜的磁控溅射制备与热电性能研究

doi:10.15541/jim20250134

无机材料学报 ›› 2025, Vol. 40 ›› Issue (11): 1237-1244.DOI: 10.15541/jim20250134

柔性Cu_0.005Bi_0.5Sb_1.495Te₃薄膜的磁控溅射制备与热电性能研究

葛泽生¹(), 刘苗¹, 汤哲¹, 周岩²(), 万舜³, 宗鹏安¹()

1.南京工业大学材料科学与工程学院, 南京 211800
2.南京师范大学物理科学与技术学院, 南京 210023
3.乌镇实验室, 桐乡 314500

收稿日期:2025-03-30 修回日期:2025-05-26 出版日期:2025-06-03 网络出版日期:2025-06-03
通讯作者: 宗鹏安, 教授. E-mail: pazong@njtech.edu.cn;
周岩, 副教授. E-mail: yan.zhou@nnu.edu.cn
作者简介:葛泽生(1998-), 男, 硕士研究生. E-mail: zsge37@njtech.edu.cn
基金资助:
国家自然科学基金-NSAF联合基金(U2230131)

Flexible Cu_0.005Bi_0.5Sb_1.495Te₃ Thin Films: Magnetron Sputtering Preparation and Thermoelectric Properties

GE Zesheng¹(), LIU Miao¹, TANG Zhe¹, ZHOU Yan²(), WAN Shun³, ZONG Peng’an¹()

1. College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211800, China
2. School of Physics and Technology, Nanjing Normal University, Nanjing 210023, China
3. Wuzhen Laboratory, Tongxiang 314500, China

Received:2025-03-30 Revised:2025-05-26 Published:2025-06-03 Online:2025-06-03
Contact: ZONG Peng’an, professor. E-mail: pazong@njtech.edu.cn;
ZHOU Yan, associate professor. E-mail: yan.zhou@nnu.edu.cn
About author:GE Zesheng (1998-), male, Master candidate. E-mail: zsge37@njtech.edu.cn
Supported by:
Joint Fund of the National Natural Science Foundation of China and NSAF(U2230131)

摘要/Abstract

摘要：

碲化铋基材料因具有优异的室温热电性能而得到广泛研究。但碲化铋具有本征脆性, 如何制备柔性高热电性能碲化铋基材料成为热电领域的难点。本研究采用磁控溅射技术在聚酰亚胺(PI)衬底上沉积了Cu_0.005Bi_0.5Sb_1.495Te₃, 成功制备了非(00l)层状取向柔性p型热电薄膜, 并研究了磁控溅射工作气压对热电性能的影响。结果表明, 在0.7 Pa磁控溅射工作气压下, 由于晶粒尺寸大、结晶性高, 迁移率提升, 同时载流子浓度得到优化, 达到5.78×10¹⁹ cm⁻³, 室温功率因子(PF)达到1660 μW·m⁻¹·K⁻²。此外, 该薄膜具有优异的机械柔性, 在弯曲半径为5 mm时, 薄膜电阻率变化小于10%, 在循环弯曲600次后, 薄膜塞贝克系数变化小于5%。基于该柔性薄膜, 设计并集成了由四个p型热电臂(5 mm×25 mm×767 nm)组成的柔性热电器件。当温差为30 K时, 柔性热电器件的输出电压达到18.5 mV, 功率密度达到44.80 μW·cm⁻²。基于该热电器件的触碰传感语言输出设计有望用于语言辅助与人机交互应用。本研究为高性能柔性碲化铋基热电薄膜的磁控溅射制备与性能优化提供了重要参考。

关键词: Cu_0.005Bi_0.5Sb_1.495Te₃, 磁控溅射, 薄膜, 柔性热电器件

Abstract:

Bismuth telluride-based materials have been extensively studied due to their outstanding thermoelectric performance at room temperature. However, bismuth telluride is inherently brittle, which poses a significant challenge in developing flexible bismuth telluride-based materials with high thermoelectric performance remains in thermoelectric research. In this study, a non(00l) layered flexible p-type thermoelectric thin film was fabricated by depositing Cu_0.005Bi_0.5Sb_1.495Te₃onto polyimide (PI) substrates using magnetron sputtering technology, with a systematic investigation of the effect of sputtering pressure on thermoelectric properties. The results show that at 0.7 Pa sputtering pressure, its mobility is enhanced due to the large grain size and high crystallinity, its carrier concentration is optimized to 5.78×10¹⁹ cm⁻³, and its room-temperature power factor (PF) reaches 1660 μW·m⁻¹·K⁻². In addition, the film exhibits excellent mechanical flexibility, showing less than 10% variation in resistivity at a bending radius of 5 mm and less than 5% variation in Seebeck coefficient after 600 cycles of bending. Furthermore, a flexible thermoelectric device comprising four p-type thermoelectric legs (5 mm×25 mm×767 nm) was designed and fabricated based on this film. The device demonstrates promising performance, generating an output voltage of 18.5 mV, with a power density reaching 44.80 μW·cm⁻² under a temperature difference of 30 K. Touch-sensitive linguistic output design of the device demonstrates promising potential for language assistance applications. This work provides valuable insights into the magnetron sputtering preparation of high-performance flexible bismuth telluride-based thermoelectric materials and the optimization of their properties.

Key words: Cu_0.005Bi_0.5Sb_1.495Te₃, magnetron sputtering, thin film, flexible thermoelectric device

中图分类号:

TQ125

葛泽生, 刘苗, 汤哲, 周岩, 万舜, 宗鹏安. 柔性Cu_0.005Bi_0.5Sb_1.495Te₃薄膜的磁控溅射制备与热电性能研究[J]. 无机材料学报, 2025, 40(11): 1237-1244.

GE Zesheng, LIU Miao, TANG Zhe, ZHOU Yan, WAN Shun, ZONG Peng’an. Flexible Cu_0.005Bi_0.5Sb_1.495Te₃ Thin Films: Magnetron Sputtering Preparation and Thermoelectric Properties[J]. Journal of Inorganic Materials, 2025, 40(11): 1237-1244.

图/表 14

图1 CBST-x(x=0.5, 0.7, 1.0, 1.5)薄膜的XRD图谱

Fig. 1 XRD patterns of CBST-x (x=0.5, 0.7, 1.0, 1.5) thin films (a) XRD patterns; (b) Localized enlargements of (015) crystal plane diffraction peaks

图2 CBST-x(x=0.5, 0.7, 1.0, 1.5)薄膜的表面微观结构

Fig. 2 Surface microstructures of CBST-x (x=0.5, 0.7, 1.0, 1.5) thin films (a-d) Surface SEM images of (a) CBST-0.5, (b) CBST-0.7, (c) CBST-1.0, and (d) CBST-1.5; (e) TEM and (f) HRTEM images with SAED pattern of CBST-0.7

图3 CBST-x(x=0.5, 0.7, 1.0, 1.5)薄膜的截面微观结构

Fig. 3 Cross-sectional microstructures of CBST-x (x=0.5, 0.7, 1.0, 1.5) thin films (a) CBST-0.5; (b) CBST-0.7; (c) CBST-1.0; (d) CBST-1.5

图4 CBST-0.7薄膜的XPS谱图

Fig. 4 XPS spectra of CBST-0.7 thin film (a) Cu2p; (b) Bi4f; (c) Sb3d; (d) Te3d

图5 CBST薄膜的热电性能、柔性及集成器件输出性能

Fig. 5 Thermoelectric properties, flexibility and integrated device output properties of CBST thin films (a-c) Variation of (a) n and μ, (b) S and σ, (c) PF of CBST-x (x=0.5, 0.7, 1.0, 1.5) thin films; (d) S, (e) σ, and (f) PF of CBST-0.7 thin film (300-550 K); (g, h) Flexibility characterization of CBST-0.7 thin film: (g) Resistivity change under different bending radii (5-10 mm),(h) Seebeck coefficient changes with bending cycles (100-600 cycles); (i) Relationship between Voc, Poc and current of TEG composed of 4 single p-type thermoelectric legs with optimal performance at different temperatures (10-30 K)

图6 单p型热电器件及触碰传感语言输出设计

Fig. 6 Single p-type TEG and touch sensing language output design (a) Touching single-p-type TEG with different numbers of finger; (b) Voc generated by the TEG upon touching by one to four fingers; (c, d) TEG converts the resulting voltage signal into words (c) “RACE” and (d) “CARE”

表S1 不同工作压力(0.5~1.5 Pa)下制备的CBST薄膜的EDS元素原子百分比

Table S1 EDS detected atomic percentages of CBST films prepared at different working pressures (0.5-1.5 Pa)

Sample	Cu/%	Bi/%	Sb/%	Te/%	(Bi+Sb)/Te	Formula
CBST-0.5	0.14	10.53	31.25	58.08	41.78/58.08	Cu_0.0066Bi_0.50Sb_1.48Te_2.76
CBST-0.7	0.12	10.52	29.90	59.46	40.43/59.46	Cu_0.0057Bi_0.50Sb_1.42Te_2.83
CBST-1.0	0.11	9.73	29.87	60.29	39.60/60.29	Cu_0.0056Bi_0.50Sb_1.53Te_3.09
CBST-1.5	0.09	10.05	28.52	61.34	38.57/61.34	Cu_0.0045Bi_0.50Sb_1.42Te_3.05

图S1 CBST-x(x=0.5, 0.7, 1.0, 1.5)薄膜的不同晶面取向因子F

Fig. S1 Different crystal face orientation factor F of CBST- x(x=0.5, 0.7, 1.0, 1.5) thin films

图S2 CBST-0.7薄膜中各元素分布图

Fig. S2 Distributions of elements in CBST-0.7 thin film (a) Cu; (b) Bi; (c) Sb; (d) Te

表S2 不同工作气压下制备的CBST薄膜的XRD分析结果

Table S2 XRD analysis results of CBST thin films prepared at different working pressures

Sample	2θ/(°)	FWHM, β/rad	Grain size, D/nm	Dislocation density, δ/ (×10¹⁵, m⁻²)	Strain, ε/ (×10⁻³, line⁻²·m⁻⁴)
CBST-0.5	28.26	0.00435	32.511	0.946	1.054
CBST-0.7	28.18	0.00317	44.602	0.503	0.768
CBST-1.0	28.14	0.00332	42.556	0.552	0.805
CBST-1.5	27.98	0.00467	30.261	1.092	1.132

表S3 本工作制备的CBST薄膜的室温PF与文献报道数据的对比

Table S3 Comparison of room-temperature PF of the CBST film prepared in this work and literature

Material	Crystal orientation	PF/(μW·m⁻¹·K⁻²)
Bi₂Te₃^[16]	(00l)	3000
Bi_0.4Sb_1.6Te₃^[40]	(00l)	2000
Bi₂Te₃^[42]	(00l)	1610
Sb₂Te₃^[43]	(015)	1210
Sb₂Te₃^[44]	(015)	1220
W-Bi_0.5Sb_1.5Te₃^[19]	(015)	1375
Cu_0.005Bi_0.5Sb_1.495Te₃(This Work)	(015)	1660

表S4 本工作的热电器件与其它工作的输出性能对比

Table S4 Comparison of the output performance of the thermoelectric device in this work and literature

Material	Device type	N (leg numbers)	ΔT/K	V_oc/mV	P_max/nW	Average V_oc/mV	P_max density/(μW·cm⁻²)
Bi₂Te₃/CFF (carbon fiber fabric)^[27]	Single p-type	5	32	6.0	90.6	1.2	0.72
Bi₂Te₃/Ni Foam^[46]	Single n-type	5	30	3.7	22.7	0.8	0.71
Bi₂Te₃-Sb₂Te₃^[47]	π-type	26	24	48.9	693.5	1.9	−
Bi₂Te₃-Sb₂Te₃^[48]	π-type	200	40	430.0	32.0	2.2	94.81
Bi_0.5Sb_1.5Te₃-Bi₂Te_2.7Se_0.3^[49]	π-type	13	68	70.0	11000.0	5.4	140.00
This work	Single p-type	4	30	18.5	6.9	4.6	44.80

图S3 CBST-0.7薄膜的低倍率TEM照片和元素分布

Fig. S3 Low-magnification TEM image and element distributions of CBST-0.7 thin film

图S4 TEG结构示意、实物图以及发电回路图

Fig. S4 TEG structure diagram, physical diagram and power generation circuit diagram (a) Schematic and photograph of the single-p-type TEG composed of four thin-film legs with optimized performance; (b) Circuit schematic of the TEG integrated with an external load resistor

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柔性Cu_0.005Bi_0.5Sb_1.495Te₃薄膜的磁控溅射制备与热电性能研究

Flexible Cu_0.005Bi_0.5Sb_1.495Te₃ Thin Films: Magnetron Sputtering Preparation and Thermoelectric Properties

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