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Te基热电材料以其优异的热电性能得到科研工作者的广泛关注, 但该领域关于器件制备和连接界面方面的研究尚属空白. 本研究基于成分梯度、载流子浓度梯度构成的多元梯度势场对界面粒子传输过程的协同调控机制, 在热电材料Te和电极Fe之间引入β(FeTe)作为阻隔层, 设计制备了Te/β(FeTe)/Fe梯度连接结构, 并对界面新相、接触电阻和机械性能进行了研究. 研究结果表明, 中间合金层β(FeTe)与热电材料和电极材料的界面组织结构致密, 有效阻隔了界面元素间严重的交互扩散. 该β(FeTe)-Te间形成了约40 μm的反应层, β(FeTe)与Fe和Te间的接触电阻分别为4.1和7.54 μΩ·cm2, 剪切强度分别为16.11和15.63 MPa. 时效温度对梯度连接结构的服役寿命和性能影响显著, Te/β(FeTe)/Fe的界面组织在553 K温度下时效15 d, 界面性能保持稳定; 当时效温度升至573 K时, 由于高温下材料的不稳定性, 导致性能随着退火时间的延长急剧下降, 并在10 d之后完全破坏, 这表明其最佳工作温度不得高于553 K. 该梯度连接结构成功实现了抑制界面元素过度扩散、降低界面残余应力以及提升界面工作稳定性和服役寿命等目的, 其设计思路和研究结果对半导体领域器件的制备具有重要借鉴意义.Owing to their excellent performances, Te-based thermoelectric materials have been extensively concerned. However little attention has been paid to the bonding interfaces with electrodes, which play an important role in their practical applications. Excessive element mutual diffusion occurs across the bonding interfaces when Te is connected with metallic electrode, such as copper, aluminum, iron, etc, which will impair its transport performance and life especially when they serve in the higher temperature environments. Seeking proper barriers is the key to solving the interface problem. In this work, a gradient bonding structure of Te/FeTe/Fe is prepared in one step by the spark plasma sintering (SPS) method, in which a metallic layer of FeTe, referred to as β(FeTe) phase, is introduced as barrier. The interface microstructure, element distribution, and new phases are analyzed, and the joint properties including contact resistance and shearing strength after being aged are evaluated. The results show that the introduction of β(FeTe) phase can promote the boding of Fe/β(FeTe)/Te and thus inhibiting the excessive element diffusion across the interfaces, which is due to the formation of ε(FeTe2) phase between β(FeTe) phase and Te. The contact resistance of Fe/β(FeTe) and β(FeTe)/Te are 4.1 μΩ·cm2 and 7.54 μΩ·cm2, respectively, and the shearing strength are 16.11 MPa and 15.63 MPa, respectively. The annealing temperature has significant effect on the performance of the gradient bonding structure. It has been indicated that the whole joint still owns good performance after being annealed at 553 K for 15 days, while it decreases sharply when the temperature is increased to 573 K. Hence, the optimal service temperature of Te/β(FeTe)/Fe should not be higher than 553 K. The gradient bonding structure is successfully achieved, thus attaining the purposes of inhibiting interface elements from excessively diffuse, reducing interface residual stress, and improving interface working stability and service life. So the design ideas and research results in this work have great reference significance for the study on semiconductor devices.
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Keywords:
- Te /
- thermoelectric material /
- gradient bonding structure /
- thermal stability
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Google Scholar
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图 1 (a) 热电接头Te/Fe界面接触电阻测试示意图; (b) 梯度连接结构Te/β(FeTe)/Fe抗剪强度测试示意图
Fig. 1. Schematic diagram of (a) thermoelectric joint Te/Fe interface contact resistance test and (b) shear strength test of Te/β(FeTe)/Fe gradient structure.
图 2 (a)热电接头Te/Fe界面背散射电子图片; (b) Fe和(c) Te的元素分布; (d) 热电接头Te/Fe界面新相元素成分谱图
Fig. 2. (a) Back scattering image of the Te/Fe interface; elemental mappings of (b) Fe and (c) Te, respectively; (d) elemental composition spectrum of new phase at the Te/Fe interface.
图 3 Fe-Te二元合金相图(来源: 美国材料信息学会)
Fig. 3. Binary phase diagram of Fe-Te (Quoted from the materials information society, ASM Interantional).
图 4 β(FeTe), ε(FeTe2)的电性能测试结果 (a)电阻率; (b) Seebeck系数
Fig. 4. The electrical properties of β(FeTe) and ε(FeTe2): (a) Resistivity; (b) Seebeck coefficient.
图 5 (a)梯度连接结构Te/FeTe/Fe界面微观组织结构; (b), (c) 梯度连接结构Te/ε(FeTe2)/Fe界面微观组织结构; (d)梯度连接结构Te/β(FeTe)/Fe的EDS线扫
Fig. 5. Microstructure of gradient bonding structure: (a) Te/FeTe/Fe interface; (b), (c) Te/ε(FeTe2)/Fe interface; (d) EDS line scanning of Te/β(FeTe)/Fe.
图 6 梯度连接结构Te/β(FeTe)/Fe界面接触电阻测试示意图
Fig. 6. Schematic diagram of Te/β(FeTe)/Fe interface contact resistance test.
图 7 梯度连接结构Te/β(FeTe)/Fe的β(FeTe)-Te界面断口微观组织形貌和元素成分分布
Fig. 7. Microstructure morphology and elemental distribution of the β(FeTe)-Te fracture interface of Te/β(FeTe)/Fe.
图 8 梯度连接结构Te/β(FeTe)/Fe在553 K下退火不同时间后两界面组织结构图片 (a1), (a2) 0 d; (b1), (b2) 7 d; (c1), (c2) 10 d; (d1), (d2) 15 d
Fig. 8. Interface structure pictures of Te/β(FeTe)/Fe after annealing at 553 K for different time: (a1), (a2) 0 d; (b1), (b2) 7 d; (c1), (c2) 10 d; (d1), (d2) 15 d.
图 9 梯度连接结构Te/FeTe/Fe在573 K下退火10 d后的界面结构图片
Fig. 9. Interfacial structure picture of Te/β(FeTe)/Fe after annealing at 573 K for 10 d.
图 10 梯度连接结构Te/β(FeTe)/Fe在553 K下退火不同时间后界面性能的变化 (a) β(FeTe)-Fe界面; (b) β(FeTe)-Te界面
Fig. 10. Changes in interface properties of Te/β(FeTe)/Fe after annealing at 553 K for different time: (a) β(FeTe)-Fe interface; (b) β(FeTe)-Te interface.
图 11 梯度连接结构Te/β(FeTe)/Fe界面接触电阻率随老化时间和温度的变化曲线 (a), (c) β(FeTe)-Fe界面; (b), (d) β(FeTe)-Te界面
Fig. 11. Change of interface resistivity with aging time and temperature: (a), (c) β(FeTe)-Fe interface; (b), (d) β(FeTe)-Te interface
表 1 梯度连接结构Te/β(FeTe)/Fe和 Te/ε(FeTe2)/Fe区域成分扫描结果
Table 1. EDS point scanning results of Te/β(FeTe)/Fe and Fe/ε(FeTe2)/Fe.
Point number Fe /at.% Te /at.% b1 0 100.00 b2 29.92 70.08 b3 50.30 49.70 b4 100.00 0 b5 31.05 68.95 b6 17.10 82.90 
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表 2 β(FeTe)-Te界面断口特征点EDS成分扫描结果
Table 2. EDS scanning results of characteristic points of β(FeTe)-Te fracture interface.
Point number Fe/at.% Te/at.% 1 24.66 75.34 2 60.17 39.83 3 2.54 97.46
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[1] He W, Zhang G, Zhang X X, Ji J, Li G Q, Zhao X D 2015 Appl. Energy 143 1
Google Scholar
[2] Pothin R, Ayral R M, Berche A, Ziolkowski P, Oppitz G, Jund P 2018 Mater. Res. Bull. 101 90
Google Scholar
[3] Yang R Y, Chen S P, Fan W H, Gao X F, Long Y, Wang W X, Munir Z A 2017 J. Alloys Compd. 704 545
Google Scholar
[4] Kaszyca K, Schmidt M, Chmielewski M, Pietrzak K, Zybala R 2018 Mater. Today: Proc. 5 10277
Google Scholar
[5] Liu W S, Jie Q, Kim H S, Ren Z F 2015 Acta Mater. 87 357
Google Scholar
[6] Li F, Huang X Y, Jiang W, Chen L D 2013 J. Electron. Mater. 42 1219
Google Scholar
[7] Ferrario A, Battiston S, Boldrini S, Sakamoto T, Miorin E, Famengo A, Miozzo A, Fiameni S, Iida T, Fabrizio M 2015 Mater. Today: Proc. 2 573
Google Scholar
[8] Wang X, Wang H C, Su W B, Mehmood F, Zhai J Z, Wang T, Chen T T, Wang C L 2019 Renewable Energy 141 88
Google Scholar
[9] An D C, Chen S P, Lu Z X, Li R, Chen W, Fan W H, Wang W X, Wu Y C 2019 ACS Appl. Mater. Interfaces 11 27788
Google Scholar
[10] Peng H, Kioussis N, Snyder G J 2014 Phys. Rev. B 89 195206
Google Scholar
[11] Qian X, Xiao Y, Zheng L, Qin B C, Zhou Y M, Pei Y L, Yuan B F, Gong S K, Zhao L D 2017 RSC Adv. 7 17682
Google Scholar
[12] Arai K, Matsubara M, Sawada Y, Sakamoto T, Kineri T, Kogo Y, Iida T, Nishio K 2012 J. Electron. Mater. 41 1771
Google Scholar
[13] Valery V K 2006 Reliability Issues in Electrical Contacts (Boca Raton: CRC Press) pp205−259
[14] Rowe D M 2006 Thermoelectrics Handbook (London: Taylor & Francis Group press) pp13−20
[15] Liu W, Zhang Q, Yin K, Chi H, Zhou X Y, Tang X F, Uher C 2013 J. Solid State Chem. 203 333
Google Scholar
[16] Hsieh H C, Wang C H, Lin W C, Chakroborty S, Lee T H, Chu H S, Wu A T 2017 J. Alloys Compd. 728 1023
Google Scholar
[17] Singh A, Bhattacharya S, Thinaharan C, Aswal D K, Gupta S K, Yakhmi J V, Bhanumurthy K 2009 J. Phys. D: Appl. Phys. 42 015502
Google Scholar
[18] Li H Y, Jing H Y, Han Y D, Lu G Q, Xu L Y, Liu T 2016 Mater. Des. 89 604
Google Scholar
[19] Ferreres X R, Yamini S A, Nancarrow M, Zhang C 2016 Mater. Des. 107 90
Google Scholar
[20] 胡晓凯, 张双猛, 赵府, 刘勇, 刘玮书 2019 无机材料学报 34 269
Google Scholar
Hu X K, Zhang S M, Zhao F, Liu Y, Liu W S 2019 J. Inorg. Mater. 34 269
Google Scholar
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