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 CSTR: 32189.14.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

参考文献 23

[1]	Jackson P, Hariskos D, Lotter E, et al. New world record efﬁciency for Cu(In, Ga)Se2 thin-film solar cells beyond 20%. Prog. Photovolt: Res. Appl., 2011, 19(7): 894-897.
[2]	Antonio L, Steven H. Handbook of Photovoltaic Science and Engineering, 2nd. San Francisco: Wiley, 2011: 546-599.
[3]	Bhattacharya R N, Oh M K, Kim Y. CIGS-based solar cells prepared from electrodeposited precursor ﬁlms. Sol. Energ. Mat. Sol. C , 2012, 98: 198-202.
[4]	Niki S, Contreras M, Repins I, et al. CIGS absorbers and processes. Prog. Photovolt: Res. Appl., 2010, 18(6): 453-466.
[5]	Repins I, Contreras M A, Egaas B, et al. 19.9%-efﬁcient ZnO/CdS/CuInGaSe2 solar cell with 81.2% fill factor. Prog. Photovolt: Res. Appl. 2008, 16: 235-239.
[6]	ZHANG Li, SUN Yun, HE Qing, et al. Three-step co-evaporation process of absorbing layer of Cu(In,Ga)Se2 integrated battery. Acta Energ. Sol. Sin., 2006, 27(9): 895-899.
[7]	Kaelin M, Rudmann D, Kurdesau F, et al. CIS and CIGS layers from selenized nanoparticle precursors. Thin Solid Films, 2003, 431-432: 58-62.
[8]	Kapur V K, Bansal A, Le P, et al. Non-vacuum processing of CuIn1-xGaxSe2 solar cells on rigid and flexible substrates using nanoparticle precursor inks. Thin Solid Films, 2003, 431-432: 53-57.
[9]	Xia D L, Zhao X J, Li J Z. Influence of Na-citrate’s concentration on Cu(In, Ga)Se2 thin films by electrodeposition. J. Synth. Cryst., 2005, 34(4): 704-708.
[10]	Calixto M E, Sebastian P J, Bhattacharya R N, et al. Compositional and optoelectronic properties of CIS and CIGS thin films formed by electrodeposition. Mat. Sol. C, 1999, 59(1/2): 75-84.
[11]	Ganchev M, Kois J, Kaelin M, et al. Preparation of Cu(In,Ga)Se2 layers by selenization of electrodeposited Cu-In-Ga precursors. Thin Solid Films, 2006, 511-512: 325-327.
[12]	AO Jian-Ping, SUN Guo-Zhong, YAN Li, et al. The characteristics of one-step electrochemical deposition of Cu(In1-x, Gax)Se2 thin films. Acta Phys. Chim. Sin., 2008, 24(6): 1073-1079.
[13]	龙飞. CIGS 薄膜太阳电池材料的材料学特征及光伏性能. 武汉: 武汉理工大学博士论文, 2009.
[14]	Kwak W C, Han S H, Kim T G, et al. Electrodeposition of Cu(In,Ga)Se2 crystals on high-density CdS nanowire arrays for photovoltaic applications. Cryst. Growth Des., 2010, 10(12): 5297-5301.
[15]	WANG Xin-Chun, WANG Guang-Jun, PANG Shan, et al. PH value on composition, structure and optical and electrical properties of CuInSe2 films by electrodeposition. Chin. J. Inorg. Chem., 2011, 27(12): 2437-2442.
[16]	Bhattachary R N, Fernandez A M. CuIn1-xGaxSe2-based photovoltaic cells from electrodeposited precursor ﬁlms. Sol. Energ. Mat. Sol. C, 2003, 76: 331-337.
[17]	WANG Xin-Chun, HU Bin-Bin, WANG Guang-Jun, et al. Using alcohol as solvent to prepare CIGS films by electrodeposition. Acta Phys.- Chim. Sin., 2011, 27(12): 2826-2830.
[18]	Long F, Wang W M, Du J J, et al. CIS(CIGS) thin films prepared for solar cells by one-step electrodeposition in alcohol solution. Phys.: Conf. Ser., 2009, 152: 12074-012078.
[19]	Kois J, Ganchev M, Kaelin M, et al. Electrodeposition of Cu-In-Ga thin metal films for Cu(In, Ga)Se2 based solar cells. Thin Solid Films, 2008, 516(18): 5948-5952.
[20]	Gabor A M, Tuttle J R, Albin D S, et al. High-efficiency CulnxGa1-xSe2 solar cells made from (Inx,Ga1-x)2 Se3. Appl. Phys. Lett., 1994, 65(2): 198-200.
[21]	Hermann A M, Mansour M, Badri V, et al. Deposition of smooth Cu(In,Ga)Se2 films from binary multilayers. Thin Solid Films, 2000, 361-362: 74-78.
[22]	Seto J Y W. The electrical properties of polycrystalline silicon films. J. Appl. Phys., 1975, 46(12): 5247-5254.
[23]	TANG Xue-Jiao, CHOU Jing-Yao, HAN Chang-Xiu, et al. Experimental study on the new technology for electroplating copper without cyanide. Nat. Univ. Nankaiensis., 2006, 39(6): 37-40.

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

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 23

相关文章 8

编辑推荐

Metrics

本文评价

[1]	杨雁, 李盛涛. 共沉淀法制备CaCu₃Ti₄O₁₂陶瓷[J]. 无机材料学报, 2010, 25(8): 835-839.
[2]	吴疆,林红,李建保,李俊峰. pH值对溶胶凝胶法制备莫来石纳米粉体微观形貌的影响[J]. 无机材料学报, 2009, 24(5): 1077-1080.
[3]	柏源,孙红旗,金万勤. pH值对氮掺杂TiO₂物化性质和光催化活性的影响[J]. 无机材料学报, 2008, 23(2): 387-392.
[4]	邢精成,王文邓,卞建江,杨建华,黄富强. BaTi_nO_2n+1光催化性能和结构关系的研究[J]. 无机材料学报, 2007, 22(6): 1075-1078.
[5]	李必慧,唐一文,张新,姜云,罗利娟,贾志勇. 水热法制备氧化锌阵列及其形貌控制[J]. 无机材料学报, 2007, 22(3): 403-406.
[6]	韩春蕊,吕伟丽,吴秀勇,傅洵,胡正水. 以PSA-A乳胶粒为模板批量制备TiO₂空心球[J]. 无机材料学报, 2005, 20(6): 1409-1416.
[7]	赵九蓬,李垚,强亮生,王彪,张贺新. 有机凝胶法低温合成纳米Sr_xBa_1-xNb₂O₆粉体[J]. 无机材料学报, 2004, 19(1): 75-80.
[8]	栾伟玲,高濂,郭景坤. pH值对BaTiO₃纳米粉体性能的影响[J]. 无机材料学报, 1999, 14(2): 287-290.