电解液pH值对电化学法制备的CIGS薄膜光电性能的影响

doi:10.3724/SP.J.1077.2013.12148

无机材料学报 ›› 2013, Vol. 28 ›› Issue (2): 141-145.DOI: 10.3724/SP.J.1077.2013.12148

电解液pH值对电化学法制备的CIGS薄膜光电性能的影响

孙保平, 庞山, 胡彬彬, 杨光红, 万绍明, 杜祖亮

(河南大学特种功能材料教育部重点实验室, 开封 475004)

收稿日期:2012-03-07 修回日期:2012-05-05 出版日期:2013-02-10 网络出版日期:2013-01-23
作者简介:孙保平(1984–), 男, 硕士研究生. E-mail: sbp2008@139.com
基金资助:
国家自然科学基金(10874040, 11274093, 21203055);教育部科技创新工程重大项目培育基金(708062);长江学者和创新团队发展计划(PCSIRT1126) National Natural Science Foundation of China (10874040, 11274093, 21203055);Cultivation Fund of Key Scientific and Technical Innovation Project, Ministry of Education of China (708062);Changjiang Scholars and Innovative Research Team in University (PCSIRT1126)

Influence of pH Value in Electrolyte on Photovoltaic Performance of CIGS Thin-films Prepared by Electrochemical Method

SUN Bao-Ping, PANG Shan, HU Bin-Bin, YANG Guang-Hong, WAN Shao-Ming, DU Zu-Liang

(Key Laboratory for Special Functional Materials of Ministry of Education, Henan University, Kaifeng 475004, China)

Received:2012-03-07 Revised:2012-05-05 Published:2013-02-10 Online:2013-01-23
About author:SUN Bao-Ping. E-mail: sbp2008@139.com

摘要/Abstract

摘要：

以F 掺杂透明导电玻璃(FTO)为基底, 利用一步电化学沉积法制备了Cu(In_1-_x,Ga_x)Se₂(CIGS)薄膜, 系统地研究了电解液pH值对CIGS薄膜的化学组分、结构及其光电性能的影响。结果显示通过改变电解液pH值可以有效调控薄膜中In和Ga的化学计量比。X射线衍射(XRD)分析和扫描电子显微镜(SEM)结果表明, pH值为2.0时制备的CIGS薄膜结晶性较好, 颗粒尺寸分布均匀。并且利用表面光伏技术研究了不同化学计量比对CIGS薄膜中光电荷动力学过程的影响, 结果表明n(Ga)/n(In+Ga)约为0.3时, CIGS薄膜的光电性能最好。

关键词: Cu(In_1-_xGa_x)Se₂薄膜, 一步电沉积法, pH值, 表面光伏

Abstract:

Cu(In_1-_x,Ga_x)Se₂(CIGS) films were prepared by one-step electrodeposition method on FTO glass substrates, and the influence of electrolytic pH on the chemical composition, structure and photovoltaic performance of CIGS thin-films were studied in detail. The results showed that the stoichiometry of In and Ga in the film could be effectively regulated by changing the pH value of the electrolyte. The X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) results showed that the CIGS thin-films had good crystallinity and uniform particle size distribution when the pH value was 2.0. The effect of different stoichiometries of the CIGS thin-films on the kinetics of photo-charges was also studied. The CIGS thin film with a stoichiometric ratio of 0.3 for Ga/(In + Ga) presented the strongest surface photovoltaic effect.

Key words: CIGS thin film, one-step electrodeposition method, pH, surface photovoltage

中图分类号:

O646

孙保平, 庞山, 胡彬彬, 杨光红, 万绍明, 杜祖亮. 电解液pH值对电化学法制备的CIGS薄膜光电性能的影响[J]. 无机材料学报, 2013, 28(2): 141-145.

SUN Bao-Ping, PANG Shan, HU Bin-Bin, YANG Guang-Hong, WAN Shao-Ming, DU Zu-Liang. Influence of pH Value in Electrolyte on Photovoltaic Performance of CIGS Thin-films Prepared by Electrochemical Method[J]. Journal of Inorganic Materials, 2013, 28(2): 141-145.

图/表 7

图1 在 (a) pH=2.4、(b) pH=2.2、(c) pH=2.0和(d) pH=1.8时制备的CIGS 薄膜SEM照片

Fig. 1 SEM images of CIGS thin films prepared at (a) pH=2.4, (b) pH=2.2, (c) pH=2.0 and (d) pH=1.8

Table 1 Analysis of different pH values solutions for prepared the CIGS thin film by EDS analysis (at%)

Sample	pH	Cu	In	Ga	Se	n(Cu)/n(In+Ga)	n(Ca)/n(In+Ga)
A	2.4	22.1	28.0	17.0	30.8	49.1	37.8
B	2.2	11.0	39.9	9.0	40.3	22.5	18.4
C	2.0	20.8	20.7	8.8	49.6	70.5	29.8
D	1.8	19.9	45.6	0	34.6	43.6	0

图2 500℃退火40 min后不同pH值电沉积CIGS 薄膜的XRD图谱

Fig. 2 XRD patterns of the CIGS thin films electrodeposited at different pH values after annealing 40 min at 500℃

图3 在不同pH值溶液中电沉积制备的CIGS薄膜的表面光电压谱图

Fig. 3 Surface photovoltage spectra of CIGS thin films prepared in solutions of different pH values by electrodeposition

图4 pH值为2.0条件下电沉积制备的CIGS薄膜在不同偏压下的表面光电压谱图

Fig. 4 Surface photovoltage spectra of CIGS film of pH value of 2.0 by electrodeposition under different biases voltage

图5 在不同pH 值溶液中电沉积制备的CIGS薄膜的瞬态表面光电压谱图(532 nm)

Fig. 5 Transient surface photovoltage spectra (532 nm) of CIGS thin films prepared in solutions of different pH values by electrodeposition

Table 2 The open-circuit photovoltage data of CIGS thin film solar cells

Electrolytic pH	2.4	2.2	2.0	1.8
V_oc/mV	7.6	55.5	66.0	47.5

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电解液pH值对电化学法制备的CIGS薄膜光电性能的影响

Influence of pH Value in Electrolyte on Photovoltaic Performance of CIGS Thin-films Prepared by Electrochemical Method

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