连续离子层吸附反应沉积后硫化法制备柔性铜锌锡硫薄膜太阳电池

孙凯文; 苏正华; 韩自力; 刘芳洋; 赖延清; 李劼; 刘业翔

doi:10.7498/aps.63.018801

摘要

在柔性钼箔衬底上采用连续离子层吸附反应法（successive ionic layer absorption and reaction）制备ZnS/Cu2SnSx叠层结构的预制层薄膜，预制层薄膜在蒸发硫气氛、 550 ℃ 温度条件下进行退火得到Cu2ZnSnS4吸收层. 分别采用EDS，XRD，Raman，SEM表征吸收层薄膜的成分、物相和表面形貌. 结果表明，退火后薄膜结晶质量良好，表面形貌致密. 用在普通钠钙玻璃上采用相同工艺制备的CZTS薄膜表征薄膜的光学和电学性能，表明退火后薄膜带隙宽度为1.49 eV，在可见光区光吸收系数大于104 cm-1，载流子浓度与电阻率均满足薄膜太阳电池器件对吸收层的要求. 用上述柔性衬底上的吸收层制备Mo foil/CZTS/CdS/i-ZnO/ZnO：Al/Ag结构的薄膜太阳电池得到2.42%的效率，是目前报道柔性CZTS太阳电池最高效率.

关键词:

Abstract

Cu2ZnSnS4 (CZTS) precursor thin films were prepared on a flexible Mo foil substrate via ZnS/Cu2SnSx stacked structure using successive ionic layer absorption and reaction (SILAR) method; the precursor thin films were annealed at 550 ℃ in sulfur atmosphere to obtain CZTS absorber layers. The chemical composition,crystallinity and surface morphology were characterized by EDS, XRD, Raman and SEM, respectively, indicating that the annealed films are highly crystallin and have compact morphology. In order to analyse the optical and electrical properties of the films, same processes were implemented on the soda glasses. Results reveal that the band gaps of the annealed films are 1.49 eV, the absorption coefficients are higher than 104 cm-1, and the carrier concentration as well as the electrical resistivity is suitable for fabrication of thin film solar cells. Flexible solar cells with a structure of Mo foil/CZTS/CdS/i-ZnO/ZnO: Al/Ag were fabricated by the above CZTS absorber layers, which demonstrated an efficiency of, 2.42%, the record efficiency of flexible CZTS solar cells as far as we know.

Keywords:

fexible thin film solar cells /
Cu2ZnSnS4 /
successive ionic layer absorption and reaction /
sulfurizing heat treatment

作者及机构信息

1.
中南大学冶金与环境学院, 长沙 410083;

2.
新南威尔士大学光伏与可再生能源工程学院, 悉尼 2052;

3.
深圳高性能电池材料与器件工程研究中心, 深圳 518057

基金项目: 国家自然科学基金青年科学基金（批准号：51204214）和中央高校基本科研业务费青年助推基金（批准号：2012QNZT022）资助的课题.

Authors and contacts

1.
School of Metallurgy and Enviroment, Central South University, Changsha 410083, China;

2.
School of Photovoltaic and Renewable Energy Engineering, University of New South Wales, Sydney, 2052 Australia;

3.
Engineering Research Center of High Performance Battery Materials and Devices, Shenzhen 518057, China

Funds: Project supported by the Young Scientists Fund of the National Natural Science Foundation of China (Grant No. 51204214) and the Fundamental Research Funds for the Central Universities of Ministry of Education of China (Grant No. 2012QNZT022).

参考文献

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施引文献

[1]	Zhang L, He Q, Xu C M, Xue Y M, Li C J Sun Y 2008 Chin. Phys. B 17 3138
[2]	Xu C M, Sun Y, Li F Y, Zhang L, Xue Y M, He Q, Liu H T 2007 Chin. Phys. 16 788
[3]	Li W, Sun Y, Liu W, Li F Y Zhou L 2006 Chin. Phys. 15 878
[4]	Chiril A, Buecheler S, Pianezzi F, Bloesch P, Gretener C, Uhl A R, Fella C, Kranz L, Perrenoud J, Seyrling S, Verma R, Nishiwaki S, Romanyuk Y E, Bilger G, Tiwari A N 2011 Nat. Mater 10 857
[5]	Tao C S, Jiang J, Tao M 2011 Sol. Energ. Mat. Sol. C 95 3176
[6]	Phipps G, Mikolajczak C, Guckes T 2008 Renewable Energy Focus 9 56
[7]	Shin B, Gunawan O, Zhu Y, Bojarczuk N A, Chey S J, Guha S 2013 Progress in Photovoltaics: Research and Applications 21 72
[8]	Todorov T K, Tang J, Bag S, Gunawan O, Gokmen T, Zhu Y, Mitzi D B 2013 Adv Energy Mater 3 34
[9]	Zhou Z, Wang Y, Xu D, Zhang Y 2010 Sol. Energ. Mat. Sol. C 94 2042
[10]	Tian Q, Xu X, Han L, Tang M, Zou R, Chen Z, Yu M, Yang J, Hu J 2012 Cryst. Eng. Comm. 14 3847
[11]	Katagiri H, Jimbo K, Yamada S, Kamimura T, Maw W S, Fukano T, Ito T, Motohiro T 2008 Appl. Phys. Express 1 041201
[12]	Chawla V, Clemens B 2012 38th IEEE Photovoltaic Specialists Conference (PVSC) Twxas, USA, June 3–8, 2012 p002990
[13]	Zhang K, Liu F Y, Lai Y Q, Li Y, Yan C, Zhang Z A, Li J, Liu Y X 2011 Acta Phys. Sin. 60 790 (in Chinese) [张坤, 刘芳洋, 赖延清, 李轶, 颜畅, 张治安, 李劼, 刘业翔 2011 60 790]
[14]	Xie D T, Zhao K, Wang L F, Zhu F, Quan S W, Meng T J, Zhang B C, Chen J E 2002 Acta Phys. Sin. 51 1377 (in Chinese) [谢大弢, 赵夔, 王莉芳, 朱凤, 全胜文, 孟铁军, 张保澄, 陈佳洱2002 51 1377]
[15]	Kishore Kumar Y B, Suresh Babu G, Uday Bhaskar P, Sundara Raja V 2009 Sol Energ. Mat. Sol. C 93 1230
[16]	Guo Q, Ford G M, Yang W C, Walker B C, Stach E A, Hillhouse H W, Agrawal R 2010 J. Am. Chem. Soc. 132 17384
[17]	Cao Y, Denny M S, Caspar J V, Farneth W E, Guo Q, Ionkin A S, Johnson L K, Lu M, Malajovich I, Radu D, Rosenfeld H D, Choudhury K R, Wu W 2012 J. Am. Chem. Soc. 134 15644
[18]	Ahmed S, Reuter K B, Gunawan O, Guo L, Romankiw L T, Deligianni H 2012 Adv. Energy Mater 2 253
[19]	Tanaka K, Fukui Y, Moritake N, Uchiki H 2011 Sol. Energ Mat. Sol. C 95 838
[20]	Li W, Ao J P, He Q, Liu F F, Li F Y, Li C J, Sun Y 2007 Acta. Phys. Sin. 56 5009 (in Chinese) [李微, 敖建平, 何青, 刘芳芳, 李凤岩, 李长健, 孙云 2007 56 5009]
[21]	Ki W, Hillhouse H W 2011 Adv. Energy Mater 1 732
[22]	Chen Q M, Li Z Q, Ni Y, Cheng S Y, Dou X M 2012 Chin. Phys. B 21 038401
[23]	Y.F N 1985 Appl. Surf. Sci. 22-23 Part 2 1061
[24]	Mali S S, Shinde P S, Betty C A, Bhosale P N, Oh Y W, Patil P S 2012 J. Phys. Chem. Solids 73 735
[25]	Shinde N M, Dubal D P, Dhawale D S, Lokhande C D, Kim J H, Moon J H 2012 Mater Res. Bull 47 302
[26]	Mali S S, Patil B M, Betty C A, Bhosale P N, Oh Y W, Jadkar S R, Devan R S, Ma Y R, Patil P S 2012 Electrochim. Acta 66 216
[27]	Jimbo K, Kimura R, Kamimura T, Yamada S, Maw W S, Araki H, Oishi K, Katagiri H 2007 Thin Solid Films 515 5997
[28]	Katagiri H 2005 Thin Solid Films 480-481 426
[29]	Paier J, Asahi R, Nagoya A, Kresse G 2009 Phys. Rev. B 79 115126
[30]	Chen S, Gong X G, Walsh A, Su-Huai W 2010 Appl. Phys. Lett. 96 021902
[31]	Redinger A, Berg D M, Dale P J, Siebentritt S 2011 J. Am. Chem. Soc. 133 3320
[32]	Lai Y Q, Kuang S S, Liu F Y, Zhang Z A, Liu J, Liu Y X 2010 Acta Phys. Sin. 59 1196 (in Chinese) [赖延清, 匡三双, 刘芳洋, 张治安, 刘军, 李劼, 刘业翔 2010 59 1196]
[33]	Ito K, Nakazawa T 1988 Jpn. J. Appl. Phys. 27 2094
[34]	Zhang J, Shao L 2009 Science in China Series E: Technological Sciences 52 269

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