真空快速退火对CIGS太阳能电池性能的影响

doi:10.15541/jim20140182

无机材料学报 ›› 2015, Vol. 30 ›› Issue (1): 35-40.DOI: 10.15541/jim20140182

真空快速退火对CIGS太阳能电池性能的影响

田力¹, 张晓勇², 毛启楠², 李学耕², 于平荣¹, 王东¹

(1. 北京大学工学院, 北京 100871; 2. 普尼太阳能(杭州)有限公司, 杭州 310051)

收稿日期:2014-04-14 修回日期:2014-06-20 出版日期:2015-01-20 网络出版日期:2014-12-29
作者简介:田力(1984–), 男, 硕士研究生. E-mail: li.tian@optony.com
基金资助:
国家高技术研究发展计划(2012AA050702, 2013AA050904);国家重大科学研究计划(2011CB933300, 2013CB934004);国家自然科学基金(21371016);国家科技支撑计划(2011BAK16B01)

Effect of Vacuum Rapid Annealing Treatment on Performance of CIGS Solar Cells

TIAN Li¹, ZHANG Xiao-Yong², MAO Qi-Nan², LI Xue-Geng², YU Ping-Rong¹, WANG Dong¹

(1. College of Engineering, Peking University, Beijing 100871, China; 2. Optony Inc., Hangzhou 310051, China)

Received:2014-04-14 Revised:2014-06-20 Published:2015-01-20 Online:2014-12-29
About author:TIAN Li. E-mail: li.tian@optony.com
Supported by:
National High Technology Research and Development Program of China (2012AA050702, 2013AA050904);National Basic Research Program of China (2011CB933300, 2013CB934004);National Natural Science Foundation of China (21371016);National Key Technology Research and Development Program of Uinistry of Science and Technology of China (2011BAK16B01)

摘要/Abstract

摘要：

采用溅射后硒化法制备CIGS电池吸收层, 并在此基础上制备具有glass/Mo/CIGS/CdS/i-ZnO/ZnO:Al/Ni-Al结构的CIGS电池。实验研究了真空退火对电池性能的影响。通过优化退火条件, 电池光电转换效率从4.91%提高到14.01%。进一步研究发现, 退火有助于改善部分单层薄膜的性能, 但是其对电池性能的提升主要来自来于: 1) 退火促使Cd²⁺扩散进入CIGS表面取代V_Cu, 钝化浅能级缺陷的同时形成n-CIGS, 使p-n结进入CIGS层内部, 从而大幅减少了界面复合中心; 2) 退火使得CIGS表面吸附的H₂O分子脱附, 提高了CIGS电学和带隙均匀性, 从而改善电池的均匀性, 电池性能得到全面提升。

关键词: CuInxGa1-xSe, 退火, 溅射后硒化, 均匀性, 同质结

Abstract:

CIGS absorber layers were prepared by sequential sputtering/selenization method. Based on that, CIGS solar cells were fabricated with a structure of glass/Mo/CIGS/CdS/i-ZnO/ZnO:Al/Ni-Al grid. The influences of annealing treatment on the performance of CIGS solar cells were investigated. By optimizing annealing condition, the cell efficiency increased from 4.91% to 14.01%. Further investigation revealed that the post-annealing treatment had two advantages. Firstly, it facilitated the diffusion of Cd ions into CIGS surface to substitute the Cu vacancies. Thus, the surface of CIGS converted from p-type to n-type conduction, leading to the shift of p-n junction from CIGS/CdS interface into the CIGS layer. Therefore, the recombination centers at the p-n junction were greatly reduced. Secondly, most H₂O molecules being adsorbed on the CIGS surface were eliminated by annealing, which improved the uniformity of electrical properties and band-gap of CIGS layer, resulting better performance of CIGS solar cell.

Key words: CuInxGa1-xSe, annealing, sputtering/selenization sequential method, uniformity, homojunction

中图分类号:

TM914

田力, 张晓勇, 毛启楠, 李学耕, 于平荣, 王东. 真空快速退火对CIGS太阳能电池性能的影响[J]. 无机材料学报, 2015, 30(1): 35-40.

TIAN Li, ZHANG Xiao-Yong, MAO Qi-Nan, LI Xue-Geng, YU Ping-Rong, WANG Dong. Effect of Vacuum Rapid Annealing Treatment on Performance of CIGS Solar Cells[J]. Journal of Inorganic Materials, 2015, 30(1): 35-40.

图/表 12

表 1 退火前后电池I-V数据对比

Table 1 Comparison of I-V data before and after annealing

Parameter^*	Before annealing							After annealing
Parameter^*	1#	2#	3#	4#	5#	6#	Ave	1#	2#	3#	4#	5#	6#
V_oc/mV	402	419	417	412	417	415	414	468	471	519	568	470	367
J_sc/mA	33	27	32	29	32	31	31	35	35	37	38	35	16
R_s/Ω	6.2	7.42	7.1	5.2	7.1	7.2	6.7	4.2	4.1	3.6	2.7	6.5	10.9
R_sh/Ω	34	61	38	33	38	37	40	57	244	345	1480	58	45
FF	0.364	0.386	0.354	0.410	0.354	0.349	0.370	0.449	0.494	0.521	0.649	0.373	0.344
η/%	4.83	4.35	4.67	4.91	4.67	4.42	4.64	7.25	7.99	10.19	14.01	6.07	1.38
(Δη/η₀)/%	-	-	-	-	-	-	0	56	72	120	202	31	-70

图 1 退火前后电池I-V曲线对比图

Fig. 1 I-V curves of cell as a function of annealing time

图 2 退火前后CIGS吸收层的透射谱

Fig. 2 Transmission spectrum of CIGS absorber layers before and after annealing

表 2 退火前后CIGS吸收层的电学性质

Table 2 Electrical properties of CIGS absorber layers before and after annealing

*	n/ (×10¹⁶, cm^-1)	μ /(cm²·V^-1·s^-1)	ρ /(Ω·cm)	Type -
As-grown	7.92	2.15	37.63	P
Annealed	3.16	4.32	46.32	P
24 h	5.44	2.45	42.65	P

表 3 退火前后电池均匀性数据对比

Table 3 Comparison of uniformity data before and after annealing

*	RSD_V_oc/%	RSD_J_sc/%	RSD_FF/%	RSD_η/%
As-grown	3.94	3.35	7.77	8.71
Annealed	2.60	2.29	5.14	7.24

图 3 电池A与电池D的I-V曲线对比图

Fig. 3 I-V curves of cell A and cell D

图 4 退火前后CdS层的透射谱

Fig. 4 Transmission spectra of CdS layers before and after annealing

图 5 CIGS电池退火前后量子效率谱

Fig. 5 External quantum efficiency of CIGS cells before and after annealing

图 6 电池A与电池B的 I-V曲线对比图

Fig. 6 I-V curves of cell A and cell B

图 7 ZnO/AZO窗口层退火前后透射谱对比图

Fig. 7 Transmission spectra of ZnO/AZO before and after annealing

表 4 退火前后AZO层的电学性质

Table 4 Electrical properties of AZO layers before and after annealing

	n /(×10²⁰, cm^-3)	μ /(cm²·V^-1·s^-1)	ρ /(×10^-3, Ω·cm)	T_e /%
As-grown	3.17	11.64	1.69	78.6
Annealing	4.55	10.81	1.28	79.8
(Δx/x₀)/%	43.4	-7.1	-24.3	1.6

图 8 电池B和电池C 的I-V曲线对比图

Fig. 8 I-V curves of cell B and cell C

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真空快速退火对CIGS太阳能电池性能的影响

Effect of Vacuum Rapid Annealing Treatment on Performance of CIGS Solar Cells

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