液相辅助热压烧结制备Cu(In, Ga)Se2靶材的研究

doi:10.15541/jim20160186

无机材料学报 ›› 2016, Vol. 31 ›› Issue (10): 1141-1146.DOI: 10.15541/jim20160186

液相辅助热压烧结制备Cu(In, Ga)Se₂靶材的研究

黄耀芹¹, 郑国源¹, 莫淑一¹, 何丽秋², 王东生², 龙飞¹

(1. 桂林理工大学材料科学与工程学院, 广西高校有色金属清洁冶炼与综合利用重点实验室, 桂林 541004; 2. 广西地凯光伏能源有限公司, 南宁 530003)

收稿日期:2016-03-28 修回日期:2016-05-02 出版日期:2016-10-20 网络出版日期:2016-09-23
作者简介:黄耀芹(1991–), 女, 硕士研究生. E-mail: m15296818093@163.com
基金资助:
广西自然科学基金(2014GXNSFFA118004);教育部“新世纪优秀人才支持计划”(NCET-12-0655)

Liquid-assisted Hot-pressed Sintering of Cu(In, Ga)Se₂ Targets

HUANG Yao-Qin¹, ZHENG Guo-Yuan¹, MO Shu-Yi¹, HE Li-Qiu², WANG Dong-Sheng², LONG Fei¹

(1. Guangxi Key Laboratory in Universities of Clean Metallurgy and Comprehensive Utilization for Non-ferrous Metals Resources, College of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, China; 2. Guangxi Dikai PV Energy Co., Ltd, Nanning 530003, China)

Received:2016-03-28 Revised:2016-05-02 Published:2016-10-20 Online:2016-09-23
About author:HUANG Yao-Qin. E-mail: m15296818093@163.com
Supported by:
Guangxi Natural Science Foundation (2014GXNSFFA118004);The Program for New Century Excellent Talents in University (NCET-12-0655)

摘要/Abstract

摘要：

采用CuIn_0.7Ga_0.3Se₂、In_0.7Ga_0.3Se和CuSe为原料, 一步热压烧结法制备CIGS靶材。通过阿基米德法、XRD、Raman、SEM和EDS等测试方法研究了CuSe液相辅助烧结对靶材的相对密度、物相组成、结构、形貌以及成份的影响。结果表明, 加入CuSe在高温下产生液相能显著促进烧结, 比不加入CuSe的体系的烧结温度下降了50℃。当烧结温度为575℃时, 获得的靶材相对密度为96.18%, 物相单一纯净, 微观结构致密, 晶粒发育良好。以摩尔比为Cu : In : Ga : Se=23.0 : 18.2 : 6.5 : 52.3的靶材, 通过溅射-热处理法制备CIGS薄膜, 并完成AZO/ZnO/ CdS/CIGS/Mo单电池的组装(0.25 cm²), 获得了9.6%的光电转换效率。

关键词: CIGS, 热压烧结, 靶材, 转换效率

Abstract:

CIGS target was prepared by one step hot-pressing sintering using CuIn_0.7Ga_0.3Se₂, In_0.7Ga_0.3Se and CuSe as precursor powder. Archimedes method, XRD, Raman, SEM, and EDS were carried out to investigate the effects of liquid-assisted sintering on the relative density, phase, structure, morphology, and composition of CIGS target. The results showed that CuSe would turn into liquid phase when temperature was increased to the liquid phase points. The liquid phase can significantly reduce sintering temperature (about 50℃ dropping) and accelerate the sintering process. When sintered at 575℃, the target can obtain the relative density of 96.18%, single phase, dense microstructure with good grain growth. In addition, using the target with molar ratio of Cu : In : Ga : Se =23.0 : 18.2 : 6.5 : 52.3, CIGS thin films were also prepared by sputtering-heat treatment, followed assembled into AZO/ZnO/CdS/CIGS/Mo solar cell. The fabricated CIGS solar cells presented a photoelectric conversion efficiency of 9.6%.

Key words: CIGS, hot-pressing sintering, target, conversion efficiency

中图分类号:

TN304

黄耀芹, 郑国源, 莫淑一, 何丽秋, 王东生, 龙飞. 液相辅助热压烧结制备Cu(In, Ga)Se₂靶材的研究[J]. 无机材料学报, 2016, 31(10): 1141-1146.

HUANG Yao-Qin, ZHENG Guo-Yuan, MO Shu-Yi, HE Li-Qiu, WANG Dong-Sheng, LONG Fei. Liquid-assisted Hot-pressed Sintering of Cu(In, Ga)Se₂ Targets[J]. Journal of Inorganic Materials, 2016, 31(10): 1141-1146.

图/表 8

图1 A、B配方在不同温度烧结所得靶材的XRD图谱

Fig. 1 XRD patterns of targets sintered at different temperatures from formula A and B powders

图2 A、B配方在不同烧结温度所得靶材的XRD衍射峰第一强峰的半高宽

Fig. 2 FWHM of main diffraction peak of targets sintered at different temperatures from formula A and B powders

图3 A、B配方在不同温度烧结所得靶材的Raman图谱

Fig. 3 Raman spectra of the targets sintered at different temperatures from formula A and B powders

图4 不同烧结温度所得靶材的相对密度

Fig. 4 Relative density of targets sintered at different temperatures

图5 不同配方在不同温度烧结所得CIGS靶材的断面形貌FESEM照片

Fig. 5 Cross-sectional FESEM images of CIGS targets sintered at different temperatures from different formula powders (a) Formula A, T=600℃; (b) Formula A, T=625℃; (c) Formula B, T=550℃; (d) Formula B, T=575℃

图6 液相辅助烧结晶粒生长发育原理示意图

Fig. 6 Principle diagram of the crystal growth in liquid-assisted sintering

表1 不同配方所得靶材的成份比例与烧失量

Table 1 Composition proportion and loss on ignition table of targets by different formula

Sample	Additive CuSe	Temperature /℃	Cu / at%	In / at%	Ga /at%	Se / at%	Loss on ignition / %
Raw material	No	--	24.98	17.52	7.49	50.01	--
a	No	550	25.18	17.44	7.49	49.89	3.11
b	No	575	24.96	17.41	7.56	50.07	3.44
c	No	600	25.22	17.43	7.39	49.96	3.75
d	No	625	25.19	17.49	7.59	49.73	3.88
Raw material	Yes	--	25.02	17.49	7.47	50.02	--
e	Yes	525	24.98	17.46	7.48	50.08	0.49
f	Yes	550	24.89	17.42	7.45	50.24	0.59
g	Yes	575	25.04	17.52	7.55	49.89	0.67
h	Yes	600	25.12	17.48	7.52	49.88	0.74
i	Yes	625	24.78	17.38	7.45	50.39	0.83

图7 溅射-热处理制备的CIGS薄膜XRD图(a), 拉曼光谱图(b)和表面FESEM照片(c), 单电池的I-V曲线图(d), 以及截面的FESEM照片(e)

Fig. 7 XRD pattern(a), Raman pattern(b) and plan view (c) of CIGS thin film preparation by sputtering-heat treatment, and its I-V pattern(d) and cross-sectional view (e) FESEM image of a single battery

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液相辅助热压烧结制备Cu(In, Ga)Se₂靶材的研究

Liquid-assisted Hot-pressed Sintering of Cu(In, Ga)Se₂ Targets

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