Ce0.9Fe3CoSb12薄膜的磁控溅射制备及其热电与传感性能研究

doi:10.15541/jim20250137

无机材料学报 ›› 2026, Vol. 41 ›› Issue (1): 55-62.DOI: 10.15541/jim20250137 CSTR: 32189.14.10.15541/jim20250137

Ce_0.9Fe₃CoSb₁₂薄膜的磁控溅射制备及其热电与传感性能研究

葛烨明¹(), 汤哲¹, 刘苗¹, 娄四泽¹, 刘振国², 周岩³, 万舜⁴(), 宗鹏安¹()

1.南京工业大学材料科学与工程学院, 南京 211800
2.西北工业大学宁波研究院浙江省柔性电子重点实验室, 宁波 315103
3.南京师范大学物理科学与技术学院, 南京 211046
4.乌镇实验室, 桐乡 314500

收稿日期:2025-04-01 修回日期:2025-06-05 出版日期:2026-01-20 网络出版日期:2025-06-27
通讯作者: 宗鹏安, 副教授. E-mail: pazong@njtech.edu.cn;
万舜, 副研究员. E-mail: wans@wuzhenlab.com
作者简介:葛烨明(2000-), 男, 硕士研究生. E-mail: 202261103011@njtech.edu.cn
基金资助:
国家自然科学基金NSAF联合基金(U2230131)

Fabrication and Thermoelectric Performance of Ce_0.9Fe₃CoSb₁₂ Thin Films via Magnetron Sputtering for Flexible Thermoelectric and Sensing Applications

GE Yeming¹(), TANG Zhe¹, LIU Miao¹, LOU Size¹, LIU Zhenguo², ZHOU Yan³, WAN Shun⁴(), ZONG Peng'an¹()

1. College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211800, China
2. Key laboratory of Flexible Electronics of Zhejiang Province, Ningbo Institute of Northwestern Polytechnical University, Ningbo 315103, China
3. School of Physics and Technology, Nanjing Normal University, Nanjing 211046, China
4. Wuzhen Laboratory, Tongxiang 314500, China

Received:2025-04-01 Revised:2025-06-05 Published:2026-01-20 Online:2025-06-27
Contact: ZONG Peng'an, associate professor. E-mail: pazong@njtech.edu.cn;
WAN Shun, associate professor. E-mail:wans@wuzhenlab.com
About author:GE Yeming (2000-), male, Master candidate. E-mail: 202261103011@njtech.edu.cn
Supported by:
Joint Funds of the National Natural Science Foundation of China NSAF(U2230131)

摘要/Abstract

摘要：

CoSb₃基方钴矿材料因其生态友好性、热稳定性及优异的热电性能, 被广泛应用于热电器件。相比于n型方钴矿热电薄膜, 目前对于高热电性能的p型填充方钴矿柔性热电薄膜的研究尚不充分, 尤其是在柔性器件方面。本研究基于磁控溅射技术在玻璃基底上制备了p型Ce_0.9Fe₃CoSb₁₂薄膜, 研究了不同溅射功率对薄膜成分、微观结构及热电性能的影响。研究结果表明, 随着溅射功率(100~120 W)的增加, Ce/Fe元素含量比逐渐下降, 空穴浓度随之提升, 导致薄膜电导率σ上升, 泽贝克系数S下降。其中110 W溅射功率制备的薄膜表现出最优的热电性能, 其室温功率因子(PF)达到76.7 μW∙m^-1∙K^-2, 随着温度的升高, 在500 K下其PF提升到103.5 μW∙m^-1∙K^-2。基于此, 本研究进一步利用柔性聚酰亚胺(PI)作为基底, 溅射时采用基板加热增强薄膜与基底之间的界面结合, 制备了柔性p型方钴矿薄膜, 并集成了薄膜热电发电器, 探究了其在温度传感器领域的应用。测试表明, 该器件在温度传感等领域具有良好的应用前景。

关键词: 热电, CoSb₃, 薄膜, 磁控溅射, 热电传感器

Abstract:

Skutterudite-based CoSb₃ materials have attracted significant attention in thermoelectric applications due to their environmental friendliness, thermal stability and excellent thermoelectric properties. While considerable progress has been made in the development of n-type skutterudite thermoelectric thin films, research on high-performance p-type filled skutterudite flexible thin films remains limited, particularly in the context of flexible device integration. In this work, p-type Ce_0.9Fe₃CoSb₁₂ thin films were deposited on glass substrates via radio frequency magnetron sputtering, and influence of sputtering power (100-120 W) on the film composition, microstructure, and thermoelectric properties was systematically investigated. The results reveal that increasing the sputtering power leads to a gradual decrease in the Ce/Fe atomic ratio and a corresponding increase in the hole concentration, which enhances the electrical conductivity (σ) but reduces the Seebeck coefficient (S). The film deposited at 110 W exhibits the highest thermoelectric performance, achieving a power factor (PF) of 76.7 μW·m^-1∙K^-2 at room temperature and 103.5 μW·m^-1∙K^-2 at 500 K. Building upon these findings, flexible Ce_0.9Fe₃CoSb₁₂ films were further fabricated on polyimide (PI) substrates with substrate heating applied during deposition to improve interfacial adhesion. A flexible thin-film thermoelectric generator was successfully integrated, and its potential application in temperature sensing was evaluated. The device demonstrates excellent mechanical flexibility and reliable thermal sensing performance, highlighting its promise for use in flexible thermoelectric sensor technologies.

Key words: thermoelectric, CoSb₃, thin film, magnetron sputtering, thermoelectric sensor

中图分类号:

TB34

葛烨明, 汤哲, 刘苗, 娄四泽, 刘振国, 周岩, 万舜, 宗鹏安. Ce_0.9Fe₃CoSb₁₂薄膜的磁控溅射制备及其热电与传感性能研究[J]. 无机材料学报, 2026, 41(1): 55-62.

GE Yeming, TANG Zhe, LIU Miao, LOU Size, LIU Zhenguo, ZHOU Yan, WAN Shun, ZONG Peng'an. Fabrication and Thermoelectric Performance of Ce_0.9Fe₃CoSb₁₂ Thin Films via Magnetron Sputtering for Flexible Thermoelectric and Sensing Applications[J]. Journal of Inorganic Materials, 2026, 41(1): 55-62.

图/表 8

图1 薄膜与热电器件制备示意图

Fig. 1 Diagrams of thin film and thermoelectric device fabrication (a) Schematic diagram of fabrication of Ce0.9Fe3CoSb12 thin film by magnetron sputtering; (b) Schematic diagram of thermoelectric device

图2 不同溅射功率沉积的Ce0.9Fe3CoSb12薄膜样品的XRD图谱

Fig. 2 XRD patterns of Ce0.9Fe3CoSb12 thin films deposited at different sputtering powers (a) XRD patterns; (b) Localized enlargements of (013) crystal plane diffraction peak

图3 Ce0.9Fe3CoSb12薄膜样品的微观表征

Fig. 3 Microstructure analyses of Ce0.9Fe3CoSb12 thin films (a-d) SEM images of Ce0.9Fe3CoSb12 thin films deposited at different sputtering powers; (e) EDS elemental mappings and (f) HRTEM image of Ce0.9Fe3CoSb12 thin film deposited at 110 W

图4 不同溅射功率制备的Ce0.9Fe3CoSb12薄膜的热电性能

Fig. 4 Thermoelectric performance of Ce0.9Fe3CoSb12 thin films prepared at various sputtering powers (a-e) p, μ, σ, S, and PF of Ce0.9Fe3CoSb12 thin films prepared under different sputtering powers; (f) Comparison of PF of CoSb3-based films at room temperature[20-22,24,30 -31]; (g-i) Relationship between σ, S, and PF of the 110 W Ce0.9Fe3CoSb12 sample as a function of temperature

图5 Ce0.9Fe3CoSb12柔性热电器件的柔性、发电性能以及触碰测试

Fig. 5 Characterization of mechanical flexibility, thermoelectric output and touch sensing capability of the Ce0.9Fe3CoSb12 flexible thermoelectric device (a) Schematic diagram of Ce0.9Fe3CoSb12 flexible thin film placed on a bent tube during the bending test; (b) σ/σ0 varied with different curvature radii after 200 bending cycles on tubes; (c) σ/σ0 varied with bending cycles on a tube with a curvature radius of 6 mm; (d) Schematic diagram of the voltage-current circuit for device output performance testing; (e) Relationship between output voltage and output current under different ΔT; (f) Relationship between output power and output current under different ΔT; (g, h) Output voltage corresponding to different numbers of legs touched on the touch sensor; (i) Voltage signals converted into words by touch sensor, using "FISH" as an example

图6 呼吸传感输出测试

Fig. 6 Respiratory sensing output test (a) Integration of the respiratory sensor into a mask, with the backside positioned near the breathing inlet and the front side exposed to the ambient air; (b) Voltage signals detected by the sensor while worn in a resting state; (c-e) Voltage signals recorded during the transition from jumping to sitting while wearing the sensor

表S1 不同溅射功率薄膜的各元素质量分数和以Co摩尔比为基准计算的薄膜化学式

Table S1 Mass fractions of various elements in thin films deposited at different sputtering powers and chemical formulas of films calculated with Co molar ratio as the base

Sputtering power/W	Ce/%	Fe/%	Co/%	Sb/%	Formula
100	7.23	8.91	3.24	80.62	Ce_0.938Fe_2.9CoSb_12.04
110	6.88	9.21	3.14	80.77	Ce_0.92Fe_3.09CoSb_12.43
120	6.82	9.98	3.38	79.81	Ce_0.85Fe_3.14CoSb_11.43
130	6.83	9.03	3.04	81.09	Ce_0.942Fe_3.13CoSb_12.9

图S1 开启与关闭基板加热的Ce0.9Fe3CoSb12薄膜在多次弯折后的电导率变化

Fig. S1 Changes in conductivities of Ce0.9Fe3CoSb12 thin films on multiple bending cycles with substrate heating on and off

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Ce_0.9Fe₃CoSb₁₂薄膜的磁控溅射制备及其热电与传感性能研究

Fabrication and Thermoelectric Performance of Ce_0.9Fe₃CoSb₁₂ Thin Films via Magnetron Sputtering for Flexible Thermoelectric and Sensing Applications

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