铜掺杂Cu<sub>2</sub>SnSe<sub>4</sub>的热电输运性能

郑丽仙; 胡剑峰; 骆军

doi:10.7498/aps.69.20200861

摘要

Cu₂SnSe₄化合物具有本征的低热导率和可调控的电导率, 同时不含稀贵元素、无毒和价格低廉, 具有作为中温区热电材料的潜力. 本文通过高能球磨结合放电等离子烧结制备了Cu₂SnSe₄以及Cu掺杂的Cu_2+xSnSe₄块体材料($ 0.2\leqslant x \leqslant 1 $). 研究了Cu掺杂填充Cu/Sn位置上1/4本征空位对Cu_2+xSnSe₄热电性能的影响, 发现Cu/Sn中1/4空位能够被Cu完全填满(x = 1), 且Cu掺杂能够大幅度地提升(可达两个数量级)样品的电导率, 从而显著提高了功率因子. 同时, 发现在大Cu掺杂量范围($ 0.1 \leqslant x \leqslant 0.8 $)内, Cu_2+xSnSe₄电导率增长与掺杂量增加呈线性关系, 且载流子迁移率随Cu掺杂量的增加而增加. 进一步的研究发现, 载流子在Cu_2+xSnSe₄中的电输运行为遵循电子-声子耦合的小极化子模型.

关键词:

Abstract

Cu₂SnSe₄ compound, as a non-toxic inexpensive thermoelectric material, has low thermal conductivity and adjustable conductivity, which promises to have a high-efficiency thermoelectric application in a medium-temperature range. The Cu-doped bulk samples of Cu₂₊_xSnSe₄(0 ≤ x ≤ 1) compounds are synthesized by a fast method, i.e. by combining high energy ball milling with spark plasma sintering. In this work, the thermoelectric properties of Cu-doped Cu₂SnSe₄ compound are investigated. The experimental results reveal that the intrinsic vacancy at Cu/Sn site of Cu₂SnSe₄ can be completely filled by Cu (i.e. x = 1 in Cu₂₊_xSnSe₄). The crystal structures of all Cu₂₊_xSnSe₄ samples have the same space group F3m as that of the undoped Cu₂SnSe₄. The electrical conductivity of Cu₂₊_xSnSe₄ increases rapidly with the content of Cu doped at intrinsic vacancy increasing, concretely, it increases by two orders of magnitude and reaches a maximum value at x = 0.8. The increase in electrical conductivity results in the significant improvement in power factor. The observed results display that the increase in electrical conductivity is a nonlinear relationship with Cu-doping content in a range of 0 < x < 0.1, but is linearly related to the Cu-doping content in a range of 0.1 ≤ x ≤ 0.8. Meanwhile, the carrier (hole) concentration is observed to reach a maximum value at x = 0.2 and then slightly decreases at x = 0.8. The rapid increase in electrical conductivity with Cu-doping content increasing may be attributed to the intensifying of Cu-Se bond network that plays a dominant role in controlling hole transport in Cu₂SnSe₄. The carrier mobility also increases with the Cu-doping content increasing in the range of 0 ≤ x ≤ 0.8, which is in contrast to the common scenarios in thermoelectric materials that the carrier mobility decreases with the increase in the carrier concentration. Furthermore, the carrier transport mechanism of Cu₂₊_xSnSe₄ sample is revealed to be able to be described by the small polaron hopping model, which means the strong coupling between electron and phonon. The analysis of thermal conductivities of the Cu₂₊_xSnSe₄ samples reveals that the relationship between the electronic thermal conductivity and the electrical conductivity cannot be described by the classical Wiedemanmn-Franz law, which may be attributed to the formation of electron-phonon coupled small polaron. Therefore, the coupling between electron and phonon inside the Cu₂₊_xSnSe₄ structure strongly influences the behaviors of carrier transmission and thermal conductivity.

Keywords:

作者及机构信息

1.
上海大学材料科学与工程学院, 上海　200444

2.
上海大学材料基因组工程研究院, 上海　200444

通信作者: 胡剑峰, jianfenghu@shu.edu.cn

Authors and contacts

1.
School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China

2.
Materials Genome Institute, Shanghai University, Shanghai 200444, China

Corresponding author: Hu Jian-Feng, jianfenghu@shu.edu.cn

文章全文

参考文献

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施引文献

图 1 Cu₂SnSe₄的晶体结构

Fig. 1. Crystal structure of Cu₂SnSe₄.

下载: 全尺寸图片幻灯片

图 2 Cu₂₊_xSnSe₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1)的(a) 室温XRD图谱、(b) 晶胞参数、(c) SEM和EDS元素分布图

Fig. 2. (a) XRD patterns, (b) cell parameter and (c) SEM images and EDS mappings of the Cu₂₊_xSnSe₄ samples (x = 0, 0.2, 0.4, 0.6, 0.8, 1) at room temperature.

下载: 全尺寸图片幻灯片

图 3 样品Cu₂₊_xSnSe₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1)的(a) 电导率、(b) 小极化子模型拟合、(c) Seebeck系数和(d) 功率因子, 其中Re.代表文献[30]结果

Fig. 3. Temperature dependence of (a) electrical conductivity, (b) the small polaron hopping model fitting, (c) Seebeck coefficient and (d) power factor (PF) for the samples of Cu₂₊_xSnSe₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1). Re. represents the results of Ref [30]

下载: 全尺寸图片幻灯片

图 4 (a) Cu₂₊_xSnSe₄ (x = 0, 0.03^[30], 0.06^[30], 0.1^[30], 0.2, 0.4, 0.6, 0.8, 1)在323 K的电导率和极化子激活能 (插图为标记处放大图); (b) Cu₂₊_xSnSe₄部分样品的室温载流子浓度和迁移率

Fig. 4. (a) Electrical conductivity and activation energy for the sample of Cu₂₊_xSnSe₄ (x = 0, 0.03^[30], 0.06^[30], 0.1^[30], 0.2, 0.4, 0.6, 0.8, 1) at 323 K; (b) carrier concentration and carrier mobility of Cu₂₊_xSnSe₄ at room temperature.

下载: 全尺寸图片幻灯片

图 5 样品Cu₂₊_xSnSe₄(x = 0, 0.2, 0.4, 0.6, 0.8, 1)的热导率随温度的变化

Fig. 5. Temperature dependence of total thermal conductivity for the sample of Cu₂₊_xSnSe₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1)

下载: 全尺寸图片幻灯片

图 6 样品Cu₂₊_xSnSe₄(x = 0, 0.2, 0.4, 0.6, 0.8, 1)的ZT随温度的变化

Fig. 6. Temperature dependence of the figure of merit for the sample of Cu₂₊_xSnSe₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1).

下载: 全尺寸图片幻灯片

[1]	DiSalvo F J 1999 Science 285 703 Google Scholar
[2]	Dehkordi A M, Zebarjadi M, He J, Tritt T M 2015 Mater. Sci. Eng., R 97 1 Google Scholar
[3]	Snyder G J, Toberer E S 2008 Nat. Mater. 7 105 Google Scholar
[4]	Sussardi A, Tanaka T, Khan A U 2015 J. Materiomics 1 196 Google Scholar
[5]	Gayner C, Kar K K 2016 Prog. Mater. Sci. 83 330 Google Scholar
[6]	Rowe D M 2005 Thermoelectrics Handbook: Macro to Nano (1st Ed.) (Boca Raton: CRC press) Chaper 1 pp3−6
[7]	Chasmar R P, Stratton R 1959 Int. J. Electron. 7 52 Google Scholar
[8]	Rowe D M, Min G E 1998 J. Power Sources 73 193 Google Scholar
[9]	Pan R, Yamei L, Jian H, et al. 2018 Inorg. Chem. Front. 5 2380 Google Scholar
[10]	Hebert S, Berthebaud D, Daou R, et al. 2016 J. Phys. Condens. Matter 28 013001 Google Scholar
[11]	Qiu P, Shi X, Chen L 2016 Energy Storage Mater. 3 85 Google Scholar
[12]	Ma R, Liu G, Li Y, et al. 2018 J. Asian Ceram. Soc. 6 13 Google Scholar
[13]	Ibanez M, Cadavid D, Anselmi-Tamburini U, et al. 2013 J. Mater. Chem. A 1 1421 Google Scholar
[14]	Song J M, Liu Y, Niu H L, et al. 2013 J. Alloys Compd. 581 646 Google Scholar
[15]	Fan J, Carrillo-Cabrera W, Akselrud L, et al. 2013 Inorg. Chem. 52 11067 Google Scholar
[16]	Janicek P, Kucek V, Kasparova J, et al. 2019 J. Electron. Mater. 48 2112 Google Scholar
[17]	Plirdpring T, Kurosaki K, Kosuga A, et al. 2012 Adv. Mater. 24 3622 Google Scholar
[18]	Zhu Y C, Liu Y, Ren G K, et al. 2018 Inorg. Chem. 57 6051 Google Scholar
[19]	Liu F S, Zheng J X, Huang M J, et al. 2014 Sci. Rep. 4 5774 Google Scholar
[20]	Shi X Y, Xi L L, Fan J, et al. 2010 Chem. Mater. 22 6029 Google Scholar
[21]	Li Y Y, Liu G H, Li J T, et al. 2016 New J. Chem. 40 5394 Google Scholar
[22]	Fan J, Liu HL, Shi X Y, et al. 2013 Acta Mater. 61 4297 Google Scholar
[23]	Lu X, Morelli D T, 2012 J. Electron. Mater. 41 1554 Google Scholar
[24]	Raju C, Falmbigl M, Rogl P, et al. 2014 Mater. Chem. Phys. 147 1022 Google Scholar
[25]	Prasad S K, Rao A, Gahtori B, et al. 2016 Mater. Res. Bull. 83 160 Google Scholar
[26]	Li Y Y, Liu G H, Cao T F, et al. 2016 Adv. Funct. Mater. 26 6025 Google Scholar
[27]	Marcano G, Rincón C, Marın G, et al. 2002 J. Appl. Phys. 92 1811 Google Scholar
[28]	Wahab L A, El-Den M B, Farrag A A, et al. 2008 J. Phys. Chem. Solids 70 604 Google Scholar
[29]	Baiyin M, Naren J, Gang G, et al. 2013 Inorg. Chem. Commun. 35 135 Google Scholar
[30]	Li W, Lin S, Zhang X, et al. 2016 Chem. Mater. 28 6227 Google Scholar
[31]	范宝新, 聂玉昕, 杨国桢 2009 中国大百科全书·物理学 (第二版) (北京: 中国大百科全书出版社) 第759页 Fan B X, Nie Y X, Yang G Z 2009 Chinese Encyclopedia: Physics (2nd Ed.) (Beijing: Encyclopedia of China Publishing House) p759 (in Chinese)
[32]	Lee S K, Yang H F, Hong J, et al. 2017 Science 355 371 Google Scholar

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铜掺杂Cu₂SnSe₄的热电输运性能