简单的溶胶–凝胶法制备致密的铜锌锡硫硒薄膜

doi:10.3724/SP.J.1077.2014.14065

无机材料学报 ›› 2014, Vol. 29 ›› Issue (7): 781-784.DOI: 10.3724/SP.J.1077.2014.14065 CSTR: 32189.14.SP.J.1077.2014.14065

• • 上一篇

简单的溶胶–凝胶法制备致密的铜锌锡硫硒薄膜

张克智, 陶加华, 刘俊峰, 何俊, 董宇晨, 孙琳, 杨平雄, 褚君浩

华东师范大学电子工程系, 极化材料与器件教育部重点实验室, 上海 200241)

收稿日期:2014-02-11 出版日期:2014-07-20 网络出版日期:2014-06-20
作者简介:张克智. E-mail: zhangkz227@126.com

Compact Cu₂ZnSn(S,Se)₄ Thin Films Fabricated by a Simple Sol-Gel Technique

ZHANG Ke-Zhi, TAO Jia-Hua, LIU Jun-Feng, HE Jun, DONG Yu-Chen, SUN Lin, YANG Ping-Xiong, CHU Jun-Hao

(Key Laboratory of Polar Materials and Devices, Ministry of Education, Department of Electronic Engineering, East China Normal University, Shanghai 200241, China)

Received:2014-02-11 Published:2014-07-20 Online:2014-06-20
About author:ZHANG Ke-Zhi (1982–), male, PhD candidate. E-mail: zhangkz227@126.com
Supported by:
National Natural Science Foundation of China (61106064);Science and Technology Commission of Shanghai Municipality Project (11ZR1411400, 10JC1404600)

摘要/Abstract

摘要：

采用溶胶–凝胶后硒化法制备了铜锌锡硫硒薄膜, 其薄膜表面平整、无裂纹。通过简化铜锌锡硫前驱体溶胶的制备以及后退火时避免使用硫化氢气体（H₂S）等方法使铜锌锡硫硒薄膜的制备工艺得到简化。选用低毒有机物乙二醇为溶剂，Cu(CH₃COO)₂、Zn(CH₃COO)₂、SnCl₂•2H₂O和硫脲为原料, 制备铜锌锡硫前驱体溶胶。XRD、Raman、EDX和SEM 分析表明制备的铜锌锡硫硒薄膜为锌黄锡矿结构, 所有薄膜均贫铜富锌, 用0.2 g硒粉、硒化20 min得到的铜锌锡硫硒薄膜其结晶较好, 表面晶粒可达1.0 μm左右。透射光谱分析结果表明, 随硒含量的增加, 铜锌锡硫硒薄膜的光学带隙从1.51 eV减小到1.14 eV。

关键词: 溶胶–凝胶, 铜锌锡硫硒, 薄膜, 硒化

Abstract:

Cu₂ZnSn(S_1-_xSe_x)₄ (CZTSSe) thin films with a compact and crack-free morphology and large-grain are obtained via a green Sol-Gel process and post-selenization. The fabrication of CZTSSe films is simplified by predigesting preparation process of Cu₂ZnSnS₄ (CZTS) precusor solution and avoiding using sulfurization. Low-toxic ethylene glycol is selected as solvent, and Cu(CH₃COO)₂, Zn(CH₃COO)₂, SnCl₂•2H₂O and thiourea are used as raw materials. Energy dispersive X-ray analyzer (EDX), X-ray diffraction (XRD) and Raman spectra results indicate that all of CZTSSe thin films with the kesterite structure are of Cu-poor and Zn-rich states. Optical band gap (E_opt) of the CZTSSe thin films decreases from 1.51 to 1.14 eV with increasing Se content.

Key words: Sol-Gel, CZTSSe, thin film, selenization

中图分类号:

TQ174

张克智, 陶加华, 刘俊峰, 何俊, 董宇晨, 孙琳, 杨平雄, 褚君浩. 简单的溶胶–凝胶法制备致密的铜锌锡硫硒薄膜[J]. 无机材料学报, 2014, 29(7): 781-784.

ZHANG Ke-Zhi, TAO Jia-Hua, LIU Jun-Feng, HE Jun, DONG Yu-Chen, SUN Lin, YANG Ping-Xiong, CHU Jun-Hao. Compact Cu₂ZnSn(S,Se)₄ Thin Films Fabricated by a Simple Sol-Gel Technique[J]. Journal of Inorganic Materials, 2014, 29(7): 781-784.

图/表 5

Table 1 Chemical compositions of CZTSSe thin films

Sample	Added Se content during post-annealing /g	Post-annealing time /min	Cu/(Zn+Sn)	Zn/Sn	(S+Se)/metal	x Se/(S+Se)
CZTSSe0	0	20	0.871	1.16	1.01	0
CZTSSe1	0.10	10	0.868	1.13	1.05	0.46
CZTSSe2	0.10	20	0.873	1.15	1.10	0.75
CZTSSe3	0.10	30	0.862	1.16	1.11	0.88
CZTSSe4	0.20	20	0.869	1.14	1.11	0.91

Fig. 1 XRD patterns of Cu2ZnSn(S1-xSex)4 thin films with different x

Fig. 2 Raman spectra of Cu2ZnSn(S1-xSex)4 thin films with different x

Fig. 3 SEM surface morphologies of CZTS thin films (a)-(e) represent the samples CZTSSe0-CZTSSe4, respectively

Fig. 4 The (αhv)2 plots and optical band gap of Cu2ZnSn (S1-xSex)4 thin films with different x

参考文献 10

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简单的溶胶–凝胶法制备致密的铜锌锡硫硒薄膜

Compact Cu₂ZnSn(S,Se)₄ Thin Films Fabricated by a Simple Sol-Gel Technique

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简单的溶胶–凝胶法制备致密的铜锌锡硫硒薄膜

Compact Cu2ZnSn(S,Se)4 Thin Films Fabricated by a Simple Sol-Gel Technique

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Compact Cu₂ZnSn(S,Se)₄ Thin Films Fabricated by a Simple Sol-Gel Technique