n型SnS热电材料的制备与性能研究

doi:10.15541/jim20180293

无机材料学报 ›› 2019, Vol. 34 ›› Issue (3): 321-327.DOI: 10.15541/jim20180293

n型SnS热电材料的制备与性能研究

黄志成^1,2, 姚瑶¹, 裴俊^1,2, 董金峰², 张波萍¹, 李敬锋², 尚鹏鹏³

1. 北京科技大学材料科学与工程学院, 北京新能源材料与技术重点实验室北京 100083;
2. 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;
3. 山东农业大学化学与材料科学学院泰安 271018

收稿日期:2018-06-29 修回日期:2018-08-03 出版日期:2019-03-20 网络出版日期:2019-02-26
作者简介:黄志成(1994-), 男, 硕士研究生. E-mail: z.c.huang@foxmail.com
基金资助:
国家重点研发计划(2018YFB0703600);国家自然科学基金(11474176)

Preparation and Thermoelectric Property of n-type SnS

HUANG Zhi-Cheng^1,2, YAO Yao¹, PEI Jun^1,2, DONG Jin-Feng², ZHANG Bo-Ping¹, LI Jing-Feng², SHANG Peng-Peng³

1. The Beijing Municipal Key Laboratory of New Energy Materials and Technologies, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China;
2. State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China;
3. College of Chemistry and Material Science, Shandong Agricultural University, Taian 271018, China;

Received:2018-06-29 Revised:2018-08-03 Published:2019-03-20 Online:2019-02-26
About author:HUANG Zhi-Cheng. E-mail: z.c.huang@foxmail.com
Supported by:
National Key Research and Development Program of China (2018YFB0703600);National Natural Science Foundation of China (11474176).

摘要/Abstract

摘要：

SnS由低毒、廉价、高丰度的元素组成, 在热电研究领域受到广泛关注。采用机械合金化(MA)结合放电等离子烧结(SPS)工艺制备了n型SnS_1-_xCl_x(x=0, 0.02, 0.03, 0.04, 0.05, 0.06)多晶块体热电样品, 并研究了Cl^-掺杂量对SnS物相、微观结构以及电热输运性能的影响。结果表明: Cl^-的引入会提高电子浓度, 使SnS由本征p型转变为n型半导体。随着Cl^-掺杂量的增加, n型SnS半导体室温下的霍尔载流子浓度从6.31×10¹⁴ cm^-3 (x=0.03)增加到7.27×10¹⁵cm^-3 (x=0.06)。x=0.05样品在823 K取得最大的电导率为408 S·m^-1, 同时具有较高的泽贝克系数为-553 μV•K^-1, 使其获得最大功率因子为1.2 μW·cm^-1·K^-2。Cl^-的掺入会引入点缺陷, 散射声子, 使晶格热导率κ_lat由0.67 W·m^-1·K^-1(x=0)降至0.5 W·m^-1·K^-1 (x=0.02)。x=0.04样品在823 K获得了最大ZT为0.17, 相比于x=0样品(ZT~0.1)提高了70%。

关键词: SnS, Cl掺杂, n型半导体, 热电性能

Abstract:

SnS composed of low toxicity, low-cost and earth-abundant elements, has extensive attention in the field of thermoelectric research. The n-type SnS_1-_xCl_x(x=0, 0.02, 0.03, 0.04, 0.05, 0.06) polycrystalline bulk thermoelectric samples were prepared by mechanical alloying (MA) combined with Spark Plasma Sintering (SPS). Effect of Cl^- amounts on the phase structure, microstructure and thermoelectric transport properties were systematically studied. Results show that introduction of Cl^- enhances electron concentration which makes intrinsic p-type SnS change to n-type. With the amount of Cl^- increasing, the Hall carrier concentration of n-type SnS semiconductor increases from 6.31×10¹⁴cm^-3 (x=0.03) to 7.27×10¹⁵cm^-3 (x=0.06) at room temperature. The maximum electrical conductivity of 408 S•m^-1 the relatively high Seebeck coefficient of -553 μV•K^-1 are obtained at 823 K for x=0.05 sample, which produces the maximum power factor of 1.2 μW·cm^-1·K^-2. Addition of Cl^- can introduce point defects to scatter phonons, which makes the lattice thermal conductivity reduce from 0.67 W·m^-1·K^-1 (x=0) to 0.5 W·m^-1·K^-1 (x=0.02). The highest ZT~0.17 is obtained at 823 K for x=0.04 sample, which is 70% higher than that (ZT~0.1) of the pristine SnS.

Key words: SnS, Cl-doped, n-type semiconductor, thermoelectric properties

中图分类号:

TB34

黄志成, 姚瑶, 裴俊, 董金峰, 张波萍, 李敬锋, 尚鹏鹏. n型SnS热电材料的制备与性能研究[J]. 无机材料学报, 2019, 34(3): 321-327.

HUANG Zhi-Cheng, YAO Yao, PEI Jun, DONG Jin-Feng, ZHANG Bo-Ping, LI Jing-Feng, SHANG Peng-Peng. Preparation and Thermoelectric Property of n-type SnS[J]. Journal of Inorganic Materials, 2019, 34(3): 321-327.

图/表 7

图1 SnS1-xClx(x=0, 0.02, 0.03, 0.04, 0.05, 0.06)块体平行于压力方向样品的XRD图谱

Fig. 1 XRD patterns of the SnS1-xClx(x=0, 0.02, 0.03, 0.04, 0.05, 0.06) bulks at (a) 20°-70°, (b) 31.3°-31.8°and (c) 56.5°-56.8°, which was measured along the hot pressing direction

图2 SnS1-xClx(x=0, 0.02, 0.03, 0.04, 0.05, 0.06)块体的晶格常数(点), 晶胞体积(柱状图)及其标准卡片(PDF#39-0354)值(虚线)随x值变化图

Fig. 2 Lattice parameters (dots) and cell volume (histogram) of the SnS1-xClx(x=0, 0.02, 0.03, 0.04, 0.05, 0.06) bulks samples along with those of the standard card (dashed lines) for SnS (PDF#39-0354)

表1 SnS1-xClx名义成分、实际成分及室温下霍尔系数, 载流子浓度, 迁移率

Table 1 Room temperature nominal composition, real composition, Hall coefficient, Hall carrier concentration, and mobility for SnS1-xClx

x	Nominal comp.	Real comp.	R_H/(cm³•C^-1)	n_H/cm^-3	μ_H/(cm²•V^-1•s^-1)
0	SnS	SnS_0.97	1.55×10³	4.03×10¹⁵	1.29
0.02	SnS_0.98Cl_0.02	SnS_0.95Cl	1.43×10⁵	4.35×10¹³	2.83
0.03	SnS_0.97Cl_0.03	SnS_0.97Cl_0.005	-9.9×10³	6.31×10¹⁴	2.34
0.04	SnS_0.96Cl_0.04	SnS_0.95Cl_0.009	-7.19×10³	8.68×10¹⁴	3.04
0.05	SnS_0.95Cl_0.05	SnS_0.93Cl_0.021	-9.22×10²	6.78×10¹⁵	3.18
0.06	SnS_0.94Cl_0.06	SnS_0.92Cl_0.022	-8.6×10²	7.27×10¹⁵	3.60

图3 x=0.03样品的(a)背散射(BSE)照片, (b)区域1, 2的EDS图谱, 以及(c)~(d) S, Sn元素分布图

Fig. 3 (a) The back-scattered electron (BSE) image of the polished surface, (b) EDS spectra taken from position 1 and 2 and (c)~(d) elemental distributions of S, Sn for x=0.03 sample

图4 SnS1-xClx块体的断口SEM照片 (a) x=0, (b) x=0.02, (c) x=0.03, (d) x=0.04, (e) x=0.05, (f) x=0.06; (g) SnS1-xClx晶粒尺寸(圆圈)和相对密度(方块)随x值变化曲线

Fig. 4 SEM images of the fractured surface morphologies for (a) x=0, (b) x=0.02, (c) x=0.03, (d) x=0.04, (e) x=0.05, (f) x=0.06, and (g) change of grain size (circle) and relative density (square) with x for SnS1-xClx bulk samples

图5 SnS1-xClx(x=0, 0.02, 0.03, 0.04, 0.05, 0.06)块体的(a)泽贝克系数, (b)载流子浓度-泽贝克系数关系曲线, (c)电导率和(d)功率因子随温度变化曲线

Fig. 5 Temperature dependence of (a) Seebeck coefficient, (b) relation curve of Hall carrier concentration - Seebeck coefficient, (c) electrical conductivity, and (d) power factor for SnS1-xClx (x=0, 0.02, 0.03, 0.04, 0.05, 0.06)

图6 SnS1-xClx(x=0, 0.02, 0.03, 0.04, 0.05, 0.06)块体(a)热扩散系数, (b)总热导率, (c)晶格热导率和(d)热电优值随温度变化曲线

Fig. 6 Temperature dependence of (a) thermal diffusivity, (b) total thermal conductivity, (c) lattice thermal conductivity, and (d) ZT for SnS1-xClx(x=0, 0.02, 0.03, 0.04, 0.05 0.06)

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n型SnS热电材料的制备与性能研究

Preparation and Thermoelectric Property of n-type SnS

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