应变增强Nb掺杂SrTiO<sub>3</sub>薄膜热电性能

马云鹏; 庄华鹭; 李敬锋; 李千

doi:10.7498/aps.72.20222301

摘要

高性能热电材料的发展有望帮助解决未来能源危机, 且随着可穿戴器件的发展与应用, 热电材料和器件除了要具备更高的热-电转化性能以外, 还必须具有良好的柔性. 将热电材料制成薄膜既可以为微型器件供电, 也有潜力应用于柔性器件. 本文使用脉冲激光沉积方法, 在商用SrTiO₃ (STO)和La_0.3Sr_0.7Al_0.65Ta_0.35O₃ (LSAT)衬底上制备得到了不同厚度的高质量铌掺杂钛酸锶薄膜(Nb:STO), 并对薄膜的表面形貌、结构以及热电性能进行表征与测试. 结果显示, 使用LSAT作为衬底可以对薄膜施加面内压应变, 随着薄膜厚度的增大, 应变逐渐释放并接近于块体Nb:STO. 随着厚度的增大, 薄膜的热电性能逐渐提升, 在STO衬底上生长的208 nm厚样品的室温功率因子相比于52 nm样品提升了187%. 此外, 144 nm厚度的Nb:STO/LSAT薄膜室温塞贝克系数达到了265.95 μV/K, 这是由于衬底应变导致薄膜样品的能带变化. 本工作表明通过应变工程调控铌掺杂钛酸锶薄膜热电性能的可行性, 为后续提高此类薄膜材料的热电性能提供了一种新思路.

关键词:

脉冲激光沉积 /
热电 /
钛酸锶 /
薄膜

Abstract

The development of high-performance thermoelectric materials can help solve the energy crisis in the future. Thin-film thermoelectric materials can meet the requirement for flexibility of wearable devices while supplying electrical power to them. In this study, high-quality Nb-doped SrTiO₃ films (Nb:STO) with different thickness are prepared on SrTiO₃ (STO) and La_0.3Sr_0.7Al_0.65Ta_0.35O₃ (LSAT) substrates by pulsed laser deposition. The surface morphologies, crystal structures, and thermoelectric performances of the films are characterized. The results show that the thermoelectric performance of the strain-free film increase with thickness increasing. The power factor at room temperature increases by 187%. The Seebeck coefficient of the 144 nm-thick Nb:STO/LSAT sample with strain is greatly improved to $265.95\;{\text{μ}}{\rm{V}}/{\rm{K}}$ at room temperature, which is likely to be due to the strain induced changes in the energy band of the thin film. The improvement of the thermoelectric performances of Nb:STO thin films by strain engineering provides a new approach to improving the thermoelectric properties of oxide thin films.

Keywords:

作者及机构信息

清华大学材料学院, 新型陶瓷与精细工艺国家重点实验室, 北京　100084

通信作者: 李千, qianli_mse@tsinghua.edu.cn

基金项目: 国家重点研发计划(批准号: 2020YFA0309100)和国家自然科学基金委原创探索计划(批准号: 52150092)资助的课题.

Authors and contacts

State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

Corresponding author: Li Qian, qianli_mse@tsinghua.edu.cn

Funds: Project supported by the National Key Research and Development Program of China (Grant No. 2020YFA0309100) and the National Natural Science Foundation of China(Grant No. 52150092).

文章全文 : translate this paragraph

参考文献

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施引文献

图 1 不同厚度Nb:STO/STO薄膜生长状况表征　(a) XRD谱; (b) AFM形貌图; (c) EDS, 插表为原子摩尔比

Fig. 1. Characterization of Nb doped SrTiO₃ thin films on (001) SrTiO₃ substrates with different thicknesses: (a) XRD spectrum; (b) AFM image; (c) EDS, the inset is the measured element composition.

下载: 全尺寸图片幻灯片

图 2 不同厚度 Nb:STO/STO 薄膜在不同温度下的面内热电性能　(a)电导率; (b)载流子浓度; (c)塞贝克系数; (d)功率因子

Fig. 2. Temperature dependence of in-plane thermoelectric properties of Nb:STO/STO thin films with different thicknesses: (a) Conductivities; (b) carrier concentrations; (c) Seebeck coefficients; (d) power factors.

下载: 全尺寸图片幻灯片

图 3 NSTO/LSAT 薄膜生长状况表征　(a) AFM形貌图; (b) XRD谱; (c) 薄膜 c 轴晶格常数

Fig. 3. Characterization of Nb:STO/LSAT thin films: (a) AFM image; (b) XRD spectrum; (c) lattice parameters of the c axis.

下载: 全尺寸图片幻灯片

图 4 不同厚度Nb:STO/STO和Nb:STO/LSAT 薄膜在不同温度下的面内热电性能　(a) 电导率; (b) 塞贝克系数; (c) 功率因子; (d) 不同衬底、厚度薄膜的电导率对比

Fig. 4. Temperature dependence of in-plane thermoelectric properties of Nb:STO/STO and Nb:STO/LSAT thin films with different thicknesses: (a) Conductivities; (b) Seebeck coefficients; (c) power factors; (d) conductivity of thin films with different thicknesses and substrates.

下载: 全尺寸图片幻灯片

map

[1]	Utlu Z, Hepbasli A 2007 Renew. Sustain. Energy Rev. 11 1 Google Scholar
[2]	Zhang B, Wang J, Zou T, Zhang S, Yaer X, Ding N, Liu C, Miao L, Li Y, Wu Y 2015 J. Mater. Chem. C 3 11406 Google Scholar
[3]	Gao W, Zhu Y, Wang Y, Yuan G, Liu J M 2020 J. Materiomics 6 1 Google Scholar
[4]	Chiang C K, Fincher C R, Park Y W, Heeger A J, Shirakawa H, Louis E J, Gau S C, MacDiarmid A G 1977 Phys. Rev. Lett. 39 1098 Google Scholar
[5]	Fan Z, Du D, Yu Z, Li P, Xia Y, Ouyang J 2016 ACS Appl. Mater. Interfaces 8 23204 Google Scholar
[6]	Jalan B, Stemmer S 2010 Appl. Phys. Lett. 97 042106 Google Scholar
[7]	Ohta H, Kim S, Mune Y, Mizoguchi T, Nomura K, Ohta S, Nomura T, Nakanishi Y, Ikuhara Y, Hirano M, Hosono H, Koumoto K 2007 Nat. Mater. 6 129 Google Scholar
[8]	Pu J, Kanahashi K, Cuong N T, Chen C H, Li L J, Okada S, Ohta H, Takenobu T 2016 Phys. Rev. B 94 014312 Google Scholar
[9]	Li P, Li L, Zeng X C 2016 J. Mater. Chem. C 4 3106 Google Scholar
[10]	Zhang X, Liu B, Liu S, Li J, Liu R, Wang P, Dong Q, Li S, Tian H, Li Q, Liu B 2021 J. Alloys Compd. 867 158923 Google Scholar
[11]	Wang N, Li M, Xiao H, Gong H, Liu Z, Zu X, Qiao L 2019 Phys. Chem. Chem. Phys. 21 15097 Google Scholar
[12]	Xu R, Huang J, Barnard E S, Hong S S, Singh P, Wong E K, Jansen T, Harbola V, Xiao J, Wang B Y, Crossley S, Lu D, Liu S, Hwang H Y 2020 Nat. Commun. 11 3141 Google Scholar
[13]	Dong Z, Chen H, Qi M, Shen J, Liu W, Guo E, Li D, Zhang Y, Wu Z 2022 Laser Photonics Rev. 16 2100454 Google Scholar
[14]	Tikhomirov O, Jiang H, Levy J 2002 Phys. Rev. Lett. 89 147601 Google Scholar
[15]	Haeni J H, Irvin P, Chang W, Uecker R, Reiche P, Li Y L, Choudhury S, Tian W, Hawley M E, Craigo B, Tagantsev A K, Pan X Q, Streiffer S K, Chen L Q, Kirchoefer S W, Levy J, Schlom D G 2004 Nature 430 758 Google Scholar
[16]	Bhansali S, Khunsin W, Chatterjee A, Santiso J, Abad B, Martin-Gonzalez M, Jakob G, Sotomayor Torres C M, Chávez-Angel E 2019 Nanoscale Adv. 1 3647 Google Scholar
[17]	Janotti A, Steiauf D, Van de Walle C G 2011 Phys. Rev. B 84 201304 Google Scholar
[18]	Bellucci A, Mastellone M, Girolami M, Orlando S, Medici L, Mezzi A, Kaciulis S, Polini R, Trucchi D M 2017 Appl. Surf. Sci. 418 589 Google Scholar
[19]	Venkatasubramanian R, Siivola E, Colpitts T, O’Quinn B 2001 Nature 413 597 Google Scholar
[20]	Chen Z J, Zhou B Y, Li J X, Wen C L 2016 Appl. Surf. Sci. 386 389 Google Scholar
[21]	Varghese T, Hollar C, Richardson J, Kempf N, Han C, Gamarachchi P, Estrada D, Mehta R J, Zhang Y 2016 Sci. Rep. 6 33135 Google Scholar
[22]	Wunderlich W, Ohta H, Koumoto K 2009 Phys. B Condens. Matter 404 2202 Google Scholar
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[25]	Zhao T, Lu H B, Chen F, Dai S Y, Yang G Z, Chen Z H 2000 J. Cryst. Growth 212 451 Google Scholar
[26]	Kumar S R S, Barasheed A Z, Alshareef H N 2013 ACS Appl. Mater. Interfaces 5 7268 Google Scholar
[27]	Blennow P, Hagen A, Hansen K, Wallenberg L, Mogensen M 2008 Solid State Ion. 179 2047 Google Scholar
[28]	Chan N H, Sharma R K, Smyth D M 1981 J. Electrochem. Soc. 128 1762 Google Scholar
[29]	Culbertson C M, Flak A T, Yatskin M, Cheong P H Y, Cann D P, Dolgos M R 2020 Sci. Rep. 10 3729 Google Scholar
[30]	Chatterjee A, Lan Z, Christensen D V, Bauitti F, Morata A, Chavez-Angel E, Sanna S, Castelli I E, Chen Y, Tarancon A, Pryds N 2022 Phys. Chem. Chem. Phys. 24 3741 Google Scholar
[31]	Ohtomo A, Hwang H Y 2004 Appl. Phys. Lett. 84 1716 Google Scholar
[32]	Hicks L D, Dresselhaus M S 1993 Phys. Rev. B 47 12727 Google Scholar
[33]	许静, 何梓民, 杨文龙, 吴荣, 赖晓芳, 简基康 2022 71 197301 Google Scholar Xu J, He Z M, Yang W L, Wu R, Lai X F, Jian J K 2022 Acta Phys. Sin. 71 197301 Google Scholar
[34]	Matthews J, Blakeslee A 1974 J. Cryst. Growth 27 118 Google Scholar
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[36]	Zou D, Liu Y, Xie S, Lin J, Li J 2013 Chem. Phys. Lett. 586 159 Google Scholar

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应变增强Nb掺杂SrTiO₃薄膜热电性能