Te与In共掺杂对Cu2SnSe3热电性能的影响

doi:10.15541/jim20220039

无机材料学报 ›› 2022, Vol. 37 ›› Issue (10): 1079-1086.DOI: 10.15541/jim20220039 CSTR: 32189.14.10.15541/jim20220039

Te与In共掺杂对Cu₂SnSe₃热电性能的影响

任培安(), 汪聪, 訾鹏, 陶奇睿, 苏贤礼(), 唐新峰()

武汉理工大学材料复合新技术国家重点实验室, 武汉 430070

收稿日期:2022-01-24 修回日期:2022-03-04 出版日期:2022-10-20 网络出版日期:2022-04-07
通讯作者: 唐新峰, 教授. E-mail: tangxf@whut.edu.cn;
苏贤礼, 研究员. E-mail: suxianli@whut.edu.cn
作者简介:任培安(1996-), 男, 硕士研究生. E-mail: renpeian@whut.edu.cn
基金资助:
国家自然科学基金(51972256);国家自然科学基金(51872219);国家自然科学基金(51632006);国家重点研发计划(2018YFB0703600)

Effect of Te and In Co-doping on Thermoelectric Properties of Cu₂SnSe₃ Compounds

REN PeiAn(), WANG Cong, ZI Peng, TAO Qirui, SU Xianli(), TANG Xinfeng()

State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China

Received:2022-01-24 Revised:2022-03-04 Published:2022-10-20 Online:2022-04-07
Contact: TANG Xinfeng, professor. E-mail: tangxf@whut.edu.cn;
SU Xianli, professor. E-mail: suxianli@whut.edu.cn
About author:REN Peian (1996-), male, Master candidate. E-mail: renpeian@whut.edu.cn
Supported by:
National Natural Science Foundation of China(51972256);National Natural Science Foundation of China(51872219);National Natural Science Foundation of China(51632006);National Key Research and Development Program of China(2018YFB0703600)

摘要/Abstract

摘要：

Cu₂SnSe₃基化合物作为一种绿色环保的新型热电材料, 近年受到了研究者的广泛关注。然而, 本征Cu₂SnSe₃基化合物载流子浓度低、电性能较差。为优化Cu₂SnSe₃化合物的电热输运性能, 本研究采用熔融、退火结合放电等离子烧结技术制备了一系列Cu₂SnSe_3-_xTe_x (x=0~0.2)和Cu₂Sn_1-_yIn_ySe_2.9Te_0.1(y=0.005~0.03)样品, 研究了Te固溶和In掺杂对材料电热输运性能的影响。Te在Cu₂SnSe_3-_xTe_x (x=0~0.2)化合物中的固溶度为0.10, Te固溶显著增加了材料的载流子有效质量, 从本征Cu₂SnSe₃样品的0.2m_e增加到Cu₂SnSe_2.9Te_0.1样品的0.45m_e, 显著提高了材料的功率因子, Cu₂SnSe_2.99Te_0.01样品在300 K下获得最大功率因子为1.37 μW·cm^-1·K^-2。为了进一步提高材料的电传输性能, 本研究以Cu₂SnSe_2.9Te_0.1为基体并选取In在Sn位掺杂。In掺杂将Cu₂SnSe₃基化合物的载流子浓度从5.96×10¹⁸ cm^-3 (Cu₂SnSe_2.9Te_0.1)显著提高到2.06×10²⁰ cm^-3 (Cu₂Sn_0.975In_0.025Se_2.9Te_0.1)。调控载流子浓度促进了材料多价带参与电传输, 材料的电导率和载流子有效质量显著增加, 功率因子得到大幅度提升, 在473 K下Cu₂Sn_0.995In_0.005Se_2.9Te_0.1化合物获得最大功率因子为5.69 μW·cm^-1·K^-2。由于电输运行性能显著提升和晶格热导率降低, Cu₂Sn_0.985In_0.025Se_2.9Te_0.1样品在773 K下获得最大ZT为0.4, 较本征Cu₂SnSe₃样品提高了4倍。

关键词: Cu₂SnSe₃基化合物, Te掺杂, In掺杂, 热电性能

Abstract:

Recently, Cu₂SnSe₃-based compounds, as a new environment-friendly thermoelectric material, have attracted worldwide attentions. However, the pristine Cu₂SnSe₃ compound possesses relatively low carrier concentration and thus an inferior electronic transport properties. To optimize the thermoelectric properties of Cu₂SnSe₃- based compounds, herein, two series of Cu₂SnSe_3-_xTe_x (x=0-0.2) and Cu₂Sn_1-_yIn_ySe_2.9Te_0.1 (y=0.005-0.03) samples were synthesized through traditional melting-annealing technique combined with plasma activated sintering (PAS). The role of Te and In co-doping on the thermoelectric properties of Cu₂SnSe₃-based compounds were systematically investigated. The solubility limit of Te in the Cu₂SnSe_3-_xTe_x compounds is around 0.10. The substitution of Te on Se site significantly increases the effective mass of charge carrier from 0.2m_e for pristine Cu₂SnSe₃ compound to 0.45m_e for Cu₂SnSe_2.9Te_0.1 compound, which improves the power factor of the material. Cu₂SnSe_2.99Te_0.01 compound attains the maximum power factor of 1.37 μW·cm^-1·K^-2 at 300 K. To further improve the electronic transport properties of the material, Cu₂SnSe_2.9Te_0.1 was chosen as the matrix and In was selected to dope on Sn site. We found that doping with In significantly improves the carrier concentration of Cu₂SnSe₃-based compounds from 5.96×10¹⁸ cm^-3 for Cu₂SnSe_2.9Te_0.1 to 2.06×10²⁰ cm^-3 for Cu₂Sn_0.975In_0.025Se_2.9Te_0.1, which promotes the participation of multiple valence bands in the electronic transport. All these produce the great enhancements on the electrical conductivity, effective mass of charge carriers and power factor. As a result, Cu₂Sn_0.995In_0.005Se_2.9Te_0.1 compound obtains the maximum power factor of 5.69 μW·cm^-1·K^-2 at 473 K. Due to the significant improvement of electrical transport performance and the decrease in lattice thermal conductivity, the maximum ZT of 0.4 is achieved for Cu₂Sn_0.985In_0.025Se_2.9Te_0.1 compound at 773 K, which is 4 times higher than that of pristine Cu₂SnSe₃ compound.

Key words: Cu₂SnSe₃-based compound, Te doping, In doping, thermoelectric property

中图分类号:

TQ174

任培安, 汪聪, 訾鹏, 陶奇睿, 苏贤礼, 唐新峰. Te与In共掺杂对Cu₂SnSe₃热电性能的影响[J]. 无机材料学报, 2022, 37(10): 1079-1086.

REN PeiAn, WANG Cong, ZI Peng, TAO Qirui, SU Xianli, TANG Xinfeng. Effect of Te and In Co-doping on Thermoelectric Properties of Cu₂SnSe₃ Compounds[J]. Journal of Inorganic Materials, 2022, 37(10): 1079-1086.

图/表 11

图1 烧结后Cu2SnSe3-xTex样品的粉末XRD图谱(a)以及在2θ=53°附近的放大图(b)

Fig. 1 Powder XRD patterns of Cu2SnSe3-xTex samples after PAS sintering (a) and corresponding enlarge view near 2θ=53° (b)

图2 Cu2SnSe3 (a)与Cu2SnSe2.9Te0.1 (b)的自由断裂面场发射扫描电镜照片

Fig. 2 Field emission scanning electron microscopies of freshly fractured surfaces of samples Cu2SnSe3 (a) and Cu2SnSe2.9Te0.1 (b)

图3 Cu2SnSe2.9Te0.1 (a)与Cu2SnSe2.85Te0.15 (b)抛光面处的背散射电子图像及 Cu2SnSe2.9Te0.1样品的元素面分布图(c~f)

Fig. 3 Backscattered electron images of the polished surfaces for samples Cu2SnSe2.9Te0.1 (a) and Cu2SnSe2.85Te0.15 (b) with elemental distribution mappings of Cu2SnSe2.9Te0.1(c-f)

图4 Cu2SnSe3-xTex化合物的电导率(a)、Seebeck系数(b)和功率因子(c)随温度的变化曲线

Fig. 4 Temperature dependent electrical conductivity (a), Seebeck coefficient (b) and power factor (c) of Cu2SnSe3-xTex samples

表1 Cu2SnSe3-xTex在室温下的电导率(σ)、Seebeck系数(S)、载流子浓度(n)以及载流子迁移率(μ)

Table 1 Electrical conductivities (σ), Seebeck coefficients (S), carrier concentrations (n) and carrier mobilities (μ) of Cu2SnSe3-xTex samples at room temperature

Sample	σ/(×10⁴, S·m^-1)	S/ (μV·K^-1)	n/(×10¹⁷, cm^-3)	μ/(cm²· V^-1·s^-1)
Cu₂SnSe₃	0.02	472.18	6.25	24.92
Cu₂SnSe_2.99Te_0.01	0.08	408.07	24.34	21.04
Cu₂SnSe_2.96Te_0.04	0.13	294.12	53.77	15.68
Cu₂SnSe_2.93Te_0.07	0.07	402.62	40.29	10.14
Cu₂SnSe_2.9Te_0.1	0.11	298.21	59.63	11.67
Cu₂SnSe_2.85Te_0.15	0.10	356.49	21.27	27.98
Cu₂SnSe_2.8Te_0.2	0.13	241.73	24.05	21.64

图5 Cu2SnSe3-xTex与Cu2Sn1-yInySe2.9Te0.1样品的载流子浓度与Seebeck系数的关系曲线

Fig. 5 Relationship between carrier concentration and Seebeck coefficient for Cu2SnSe3-xTex and Cu2Sn1-yInySe2.9Te0.1 samples Colorful figure is available on website

图6 Cu2SnSe3-xTex的总热导率随温度的变化曲线

Fig. 6 Temperature dependent thermal conductivity for Cu2SnSe3-xTex samples

图7 Cu2SnSe3-xTex的ZT随温度的变化曲线

Fig. 7 Temperature dependent ZT for Cu2SnSe3-xTex samples

图8 Cu2Sn1-yInySe2.9Te0.1化合物的电导率(a)、Seebeck系数(b)和功率因子(c)随温度的变化曲线

Fig. 8 Temperature dependent electrical conductivity (a), Seebeck coefficient (b) and power factor (c) for Cu2Sn1-yInySe2.9Te0.1 samples

表2 Cu2Sn1-yInySe2.9Te0.1样品在室温下的电导率(σ)、Seebeck系数(S)、载流子浓度(n)以及载流子迁移率(μ)

Table 2 Electrical conductivities (σ), Seebeck coefficients (S), carrier concentrations (n) and carrier mobilities (μ) of Cu2Sn1-yInySe2.9Te0.1 samples at room temperature

Sample	σ/(×10⁴, S·m^-1)	S/ (μV·K^-1)	n/(×10¹⁹, cm^-3)	μ/(cm²·V^-1·s^-1)
Cu₂SnSe_2.9Te_0.1	0.11	298.21	0.59	11.68
Cu₂Sn_0.995In_0.005Se_2.9Te_0.1	0.97	220.50	4.35	13.95
Cu₂Sn_0.99In_0.01Se_2.9Te_0.1	1.26	185.79	7.15	10.99
Cu₂Sn_0.985In_0.015Se_2.9Te_0.1	1.50	159.47	11.36	8.25
Cu₂Sn_0.98In_0.02Se_2.9Te_0.1	1.67	152.91	10.54	10.08
Cu₂Sn_0.975In_0.025Se_2.9Te_0.1	2.07	130.39	20.60	6.28
Cu₂Sn_0.97In_0.03Se_2.9Te_0.1	2.27	120.35	20.00	7.09

图9 Cu2Sn1-yInySe2.9Te0.1化合物的热导率(a)和ZT(b)随温度的变化曲线

Fig. 9 Temperature dependent thermal conductivity (a) and ZT (b) for Cu2Sn1-yInySe2.9Te0.1 samples

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Te与In共掺杂对Cu₂SnSe₃热电性能的影响

Effect of Te and In Co-doping on Thermoelectric Properties of Cu₂SnSe₃ Compounds

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