退火条件对磁控溅射MgO-Ag3Sb-Sb2O4柔性薄膜热电性能的影响

doi:10.15541/jim20220107

无机材料学报 ›› 2022, Vol. 37 ›› Issue (12): 1302-1310.DOI: 10.15541/jim20220107

退火条件对磁控溅射MgO-Ag₃Sb-Sb₂O₄柔性薄膜热电性能的影响

刘丹¹(), 赵亚欣¹, 郭锐¹, 刘艳涛², 张志东¹, 张增星¹, 薛晨阳¹

1.中北大学仪器科学与动态测试教育部重点实验室, 太原030051
2.西安理工大学电子工程系, 西安710048

收稿日期:2022-03-02 修回日期:2022-04-17 出版日期:2022-12-20 网络出版日期:2022-04-26
作者简介:刘丹(1988-), 男, 博士, 副教授. E-mail: liudan235@nuc.edu.cn
基金资助:
国家自然科学基金青年项目(62001428);国家重点研发计划(2019YFB2004800);山西省高等学校科技创新项目(2020L0309)

Effect of Annealing Conditions on Thermoelectric Properties of Magnetron Sputtered MgO-Ag₃Sb-Sb₂O₄ Flexible Films

LIU Dan¹(), ZHAO Yaxin¹, GUO Rui¹, LIU Yantao², ZHANG Zhidong¹, ZHANG Zengxing¹, XUE Chenyang¹

1. Key Laboratory of Instrumentation Science & Dynamic Measurement, Ministry of Education, North University of China, Taiyuan 030051, China
2. Department of Electronic Engineering, Xi’an University of Technology, Xi’an 710048, China

Received:2022-03-02 Revised:2022-04-17 Published:2022-12-20 Online:2022-04-26
About author:LIU Dan (1988-), male, PhD, associate professor. E-mail: liudan235@nuc.edu.cn
Supported by:
National Natural Science Foundation of China(62001428);National Key Research and Development Program of China(2019YFB2004800);Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2020L0309)

摘要/Abstract

摘要：

MgAgSb是一种具有潜力且元素储量相对丰富的室温热电材料, 有望用于构建高性能可穿戴温差电池。本研究尝试在聚酰亚胺(PI)基底上磁控溅射制备MgAgSb薄膜, 并系统研究退火条件对其热电性能的影响。结果表明样品未形成纯相的MgAgSb柔性热电薄膜, 而是形成了由Ag₃Sb、MgO及Sb₂O₄多相组成的柔性薄膜, 其中Ag₃Sb起主要热电功能。不同气氛退火可以显著提升MgO-Ag₃Sb-Sb₂O₄(Mg-Ag-Sb)柔性薄膜的热电性能, 其中真空处理性能最佳。在真空条件下, 随着退火温度升高, 柔性薄膜的热电性能呈现先增加后减少的趋势, 当退火温度为573 K时热电性能最佳, 室温附近功率因子达到74.16 μW∙m^-1∙K^-2。并且, 薄膜表现出较好的柔性, 弯曲900次后, 电导率仅变化了14%。本研究为MgAgSb柔性热电薄膜的制备及可穿戴应用提供了参考。

关键词: MgAgSb, 退火处理, 热电性能, 柔性薄膜

Abstract:

MgAgSb is a promising room temperature thermoelectric material with relatively abundant element reserves for the construction of high-performance wearable thermoelectric batteries. In this study, Mg-Ag-Sb thin films were prepared on polyimide (PI) substrates by using magnetron sputtering, and the effects of annealing conditions on their thermoelectric properties were systematically investigated. The results showed that the MgAgSb flexible thermoelectric film composed of MgO, Ag₃Sb and Sb₂O₄ multiphases instead of pure phase, in which Ag₃Sb played main role of thermoelectric function. Different annealing atmospheres significantly improved the thermoelectric properties of MgO-Ag₃Sb-Sb₂O₄ (Mg-Ag-Sb) flexible thin films, among which the vacuum treatment appeared the best performance. Under vacuum conditions, the thermoelectric properties firstly increased and then decreased with the annealing temperature increasing, and the best thermoelectric property was achieved when the annealing temperature was 573 K, with a power factor of 74.16 μW∙m^-1∙K^-2 near room temperature. Moreover, the film exhibited good flexibility, and the conductivity changed by only 14% after 900 bending times. This study provides a reference for the preparation of MgAgSb flexible thermoelectric films and their wearable applications.

Key words: MgAgSb, annealing treatment, thermoelectric property, flexible film

中图分类号:

O472

刘丹, 赵亚欣, 郭锐, 刘艳涛, 张志东, 张增星, 薛晨阳. 退火条件对磁控溅射MgO-Ag₃Sb-Sb₂O₄柔性薄膜热电性能的影响[J]. 无机材料学报, 2022, 37(12): 1302-1310.

LIU Dan, ZHAO Yaxin, GUO Rui, LIU Yantao, ZHANG Zhidong, ZHANG Zengxing, XUE Chenyang. Effect of Annealing Conditions on Thermoelectric Properties of Magnetron Sputtered MgO-Ag₃Sb-Sb₂O₄ Flexible Films[J]. Journal of Inorganic Materials, 2022, 37(12): 1302-1310.

图/表 13

图1 VAC523、H2/N2523和N2523的XRD图谱

Fig. 1 XRD patterns of VAC523, H2/N2523 and N2523

图2 MAS-0(a)、VAC523(b)、H2/N2523(c)和N2523(d)的SEM照片

Fig. 2 Surface SEM images of MAS-0 (a), VAC523 (b), H2/N2523 (c), and N2523 (d)

图3 VAC523表面颗粒EDS图谱

Fig. 3 EDS spectrum of surface particles on VAC523

图4 MAS-0(a)、VAC523(b)、H2/N2523(c)和N2523(d)的SEM截面照片

Fig. 4 Cross-sectional SEM images of MAS-0 (a), VAC523 (b), H2/N2523 (c), and N2523 (d)

图5 VAC523、H2/N2523和N2523的塞贝克系数(a)、电导率(b)、功率因子(c)和MAS-0的热电参数(d)随测试温度的变化曲线

Fig. 5 Testing temperature dependent Seebeck coefficient (a), electrical conductivity (b), power factor(c) of VAC523, H2/N2523 and N2523, and thermoelectric parameters (d) of MAS-0

图6 VAC523(a)、H2/N2523(b)和N2523(c)的载流子浓度和迁移率随测试温度的变化曲线

Fig. 6 Testing temperature dependent carrier concentration and mobility of VAC523(a), H2/N2523(b) and N2523(c)

图7 VACx薄膜的XRD图谱

Fig. 7 XRD patterns of VACx films

图8 VACx (x=548 (a), 573 (b), 598 (c), 623 (d))薄膜的表面SEM照片, VAC573薄膜的表面高倍SEM照片(e)

Fig. 8 Surface SEM images of VACx (x=548 (a), 573 (b), 598 (c), 623 (d)) films, and high magnification surface SEM image of VAC573 film (e)

图9 VACx(x=548 (a), 573 (b), 598 (c), 623 (d))薄膜的SEM截面照片

Fig. 9 Cross-sectional SEM images of VACx (x=548 (a), 573 (b), 598 (c), 623 (d)) films

图10 VACx(x=523, 548, 573, 598)薄膜的塞贝克系数(a)、电导率(b)和功率因子(c) 随测试温度的变化曲线

Fig. 10 Testing temperature dependent Seebeck coefficient (a), electrical conductivity (b) and power factor (c) of VACx (x=523, 548, 573, 598)

图11 VACx(x=523 (a), 548 (b), 573 (c), 598 (d))的载流子浓度和迁移率随测试温度的变化曲线

Fig. 11 Testing temperature dependent carrier concentration and mobility of VACx(x=523 (a), 548 (b), 573 (c), 598 (d))

图12 VAC573薄膜的电导率随弯曲次数的变化情况

Fig. 12 Electrical conductivity of VAC573 film varied with bending times

图13 不同弯曲次数VAC573薄膜表面的SEM照片

Fig. 13 Surface SEM images of VAC573 film with different bending times (a) 400; (b) 600; (c) 900; (d) 1500

参考文献 30

[1]	SIDDIQUE A R M, MAHMUD S, HEYST B V. A review of the state of the science on wearable thermoelectric power generators (TEGs) and their existing challenges. Renewable and Sustainable Energy Reviews, 2017, 73: 730-744. DOI URL
[2]	HASAN M A M, WU H, YANG Y. Redox-induced electricity for energy scavenging and self-powered sensors. Journal of Materials Chemistry A, 2021, 9(35): 19116-19148. DOI URL
[3]	SHANG H, GU H, DING F, et al. Recent advances in flexible thermoelectrics. Applied Physics Letters, 2021, 118(17): 170503. DOI URL
[4]	KUMAR A, BANO S, GOVIND B, et al. A review on fundamentals, design and optimization to high ZT of thermoelectric materials for application to thermoelectric technology. Journal of Electronic Materials, 2021, 50(11): 6037-6059. DOI URL
[5]	FAN Z, ZHANG Y, PAN L, et al. Recent developments in flexible thermoelectrics: from materials to devices. Renewable and Sustainable Energy Reviews, 2021, 137: 110448. DOI URL
[6]	JAZIRI N, BOUGHAMOURA A, MÜLLER J, et al. A comprehensive review of thermoelectric generators: technologies and common applications. Energy Reports, 2020, 6: 264-287.
[7]	ZHANG Q H, HUANG X Y, BAI S Q, et al. Thermoelectric devices for power generation: recent progress and future challenges. Advanced Engineering Materials, 2016, 18(2): 194-213. DOI URL
[8]	RIMOLDI M, CECCHINI R, WIEMER C, et al. Effect of substrates and thermal treatments on metalorganic chemical vapor deposition-grown Sb₂Te₃ thin films. Crystal Growth & Design, 2021, 21(9): 5135-5144. DOI URL
[9]	CHEN B, KRUSE M, XU B, et al. Flexible thermoelectric generators with inkjet-printed bismuth telluride nanowires and liquid metal contacts. Nanoscale, 2019, 11(12): 5222-5230. DOI PMID
[10]	HAN C, TAN G, VARGHESE T, et al. High-performance PbTe thermoelectric films by scalable and low-cost printing. ACS Energy Letters, 2018, 3(4): 818-822. DOI URL
[11]	WEN D L, LIU X, BAO J F, et al. Flexible hybrid photo- thermoelectric generator based on single thermoelectric effect for simultaneously harvesting thermal and radiation energies. ACS Applied Materials & Interfaces, 2021, 13(18): 21401-21410.
[12]	GOTO M, SASAKI M, XU Y, et al. Control of p-type and n-type thermoelectric properties of bismuth telluride thin films by combinatorial sputter coating technology. Applied Surface Science, 2017, 407: 405-411. DOI URL
[13]	KOBAYASHI A, KONAGAYA R, TANAKA S, et al. Optimized structure of tubular thermoelectric generators using n-type Bi₂Te₃ and p-type Sb₂Te₃ thin films on flexible substrate for energy harvesting. Sensors and Actuators A: Physical, 2020, 313: 112199. DOI URL
[14]	GHOSH A, AHMAD M, BISHT P, et al. Modifying the thermoelectric transport of Sb₂Te₃ thin films via the carrier filtering effect by incorporating size-selected gold nanoparticles. ACS Applied Materials & Interfaces, 2021, 13(11): 13226-13234.
[15]	KIRKHAM M J, SANTOS A M D, RAWN C J, et al. Ab initio determination of crystal structures of the thermoelectric material MgAgSb. Physical Review B, 2012, 85(14): 144120. DOI URL
[16]	ZHAO H, SUI J, TANG Z, et al. High thermoelectric performance of MgAgSb-based materials. Nano Energy, 2014, 7: 97-103. DOI URL
[17]	LIU Z, SHUAI J, MAO J, et al. Effects of antimony content in MgAg_0.97Sb_x on output power and energy conversion efficiency. Acta Materialia, 2016, 102: 17-23. DOI URL
[18]	LIU Z, GAO W, MENG X, et al. Mechanical properties of nanostructured thermoelectric materials α-MgAgSb. Scripta Materialia, 2017, 127: 72-75. DOI URL
[19]	LIU Z, WANG Y, GAO W, et al. The influence of doping sites on achieving higher thermoelectric performance for nanostructured α-MgAgSb. Nano Energy, 2017, 31: 194-200. DOI URL
[20]	LIU Z, ZHANG Y, MAO J, et al. The microscopic origin of low thermal conductivity for enhanced thermoelectric performance of Yb doped MgAgSb. Acta Materialia, 2017, 128: 227-234. DOI URL
[21]	GAO W, YI X, CUI B, et al. The critical role of boron doping in the thermoelectric and mechanical properties of nanostructured α-MgAgSb. Journal of Materials Chemistry C, 2018, 6(36): 9821-9827. DOI URL
[22]	OUELDNA N, PORTAVOCE A, BERTOGLIO M, et al. Seebeck coefficient in multiphase thin films. Materials Letters, 2020, 266: 127460. DOI URL
[23]	OUELDNA N, PORTAVOCE A, BERTOGLIO M, et al. Phase transitions in thermoelectric Mg-Ag-Sb thin films. Journal of Alloys and Compounds, 2022, 900: 163534. DOI URL
[24]	ZHAI J, WANG T, WANG H, et al. Strategies for optimizing the thermoelectricity of PbTe alloys. Chinese Physics B, 2018, 27(4): 047306. DOI URL
[25]	HINES N J, YATES L, FOLEY B M, et al. Steady-state methods for measuring in-plane thermal conductivity of thin films for heat spreading applications. Review of Scientific Instruments, 2021, 92: 044907. DOI URL
[26]	ZHENG Z H, ZHANG D L, NIU J Y, et al. Achieving ultrahigh power factor in n-type Ag₂Se thin films by carrier engineering. Materials Today Energy, 2022, 24: 100933. DOI URL
[27]	ZENG X, REN L, XIE J, et al. Room-temperature welding of silver telluride nanowires for high-performance thermoelectric film. ACS Applied Materials & Interfaces, 2019, 11(41): 37892-37900.
[28]	LIU D, ZHAO Y, YAN Z, et al. Screen-printed flexible thermoelectric device based on hybrid silver selenide/PVP composite films. Nanomaterials, 2021, 11(8): 2042. DOI URL
[29]	DING Y, QIU Y, CAI K, et al. High performance n-type Ag₂Se film on Nylon membrane for flexible thermoelectric power generator. Nature Communications, 2019, 10(1): 841. DOI URL
[30]	JIANG C, DING Y, CAI K, et al. Ultrahigh performance of n-Type Ag₂Se films for flexible thermoelectric power generators. ACS Applied Materials & Interfaces, 2020, 12(8): 9646-9655.

退火条件对磁控溅射MgO-Ag₃Sb-Sb₂O₄柔性薄膜热电性能的影响

Effect of Annealing Conditions on Thermoelectric Properties of Magnetron Sputtered MgO-Ag₃Sb-Sb₂O₄ Flexible Films

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