CuInS2纳米纸阵列薄膜的制备及生长机理

doi:10.7503/cjcu20140235

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (11): 2310.doi: 10.7503/cjcu20140235

• 研究论文: 无机化学 • 上一篇下一篇

CuInS₂纳米纸阵列薄膜的制备及生长机理

庄米雪^1,², 魏爱香^1,², 刘俊^1,^2,³(), 颜志强^1,², 招瑜^1,²

1. 广东工业大学材料与能源学院, 2. 广东省功能软凝聚态物质重点实验室, 广州 510006
3. 浙江大学硅材料国家重点实验室, 杭州 310027

收稿日期:2014-03-19 出版日期:2014-11-10 发布日期:2014-10-21
作者简介:联系人简介: 刘俊, 男, 博士, 讲师, 主要从事纳米材料的合成及纳米能源方面的研究. E-mail:gdutliu@gdut.edu.cn
基金资助:
国家自然科学基金青年基金(批准号: 51202037)和广东省教育厅科技创新项目(批准号: 2013KJCX0065)资助

Solvothermal Preparation and Growth Mechanism of CuInS₂ Thin Films of Nanosheet Array

ZHUANG Mixue^1,², WEI Aixiang^1,², LIU Jun^1,^2,^3,^*(), YAN Zhiqiang^1,², ZHAO Yu^1,²

1. School of Material and Energy, 2. Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter,Guangdong University of Technology, Guangzhou 510006, China
3. State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027, China

Received:2014-03-19 Online:2014-11-10 Published:2014-10-21
Contact: LIU Jun E-mail:gdutliu@gdut.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.51202037) and Science and Technology Innovation Project of Department of Education of Guangdong Province, China(No.2013KJCX0065)

摘要/Abstract

摘要：

采用溶剂热合成技术, 以氯化铜、硝酸铟和硫脲为反应物, 十六烷基三甲基溴化铵(CTAB)为阳离子表面活性剂, 草酸为还原剂, 无水乙醇为溶剂, 直接在掺氟的SnO₂透明导电玻璃(FTO)衬底上合成CuInS₂(CIS)薄膜. 采用扫描电子显微镜(SEM)、高分辨率透射电子显微镜(HRTEM)、 X射线衍射(XRD)、拉曼光谱、能量色散谱(EDS)、紫外-可见(UV-Vis)反射光谱和透射光谱对样品的形貌、结构、成分和光学性能进行分析. 结果表明, 在适当的反应物浓度下, 在FTO衬底上形成了垂直衬底生长的、具有良好结晶性能的黄铜矿结构的CIS纳米纸阵列薄膜. CIS薄膜中Cu, In, S的原子比为1.1:1:2.09, 在紫外-可见和近红外波段具有良好的光吸收特性, 禁带宽度约1.51 eV. 结合不同反应时间制备的CIS薄膜的形貌、结构和成分分析, 讨论了CIS纳米纸阵列薄膜的生长机理.

关键词: 溶剂热合成技术, CuInS2, 纳米纸阵列薄膜, 生长机理

Abstract:

CuInS₂(CIS) thin films of nanosheet array were deposited directly onto transparent conductive fluorine-doped tin oxide(FTO) substrates by solvothermal method using the precursors of copper(Ⅱ) chloride dihydrate, indium(Ⅲ) nitrate, thiourea, hexadecyl trimethyl ammonium bromide, oxalic acid, and ethanol. The morphology, crystallographic structure, chemical composition, and optical property of CIS thin films of nanosheet array were investigated using scanning electron microscopy(SEM), high resolution transmission electron microscopy(HRTEM), X-ray diffraction(XRD), Raman spectrum, energy dispersive spectrometry(EDS) and UV-Vis spectroscopy, respectively. It is revealed that highly uniform and dense vertical arrays of single crystalline nanosheets with chalcopyrite planes are formed. The atomic ratio of Cu/In/S is 1.1:1:2.09, very close to theoretical value of 1:1:2 of stoichiometric CIS. CIS thin films of nanosheet array have good light absorption characteristics at the UV-visible and near infrared wave range, and the optical band gap is found to be 1.51 eV. The growth mechanism of CIS thin films of nanosheet array was investigated according to the characterization of CIS thin films deposited at different reaction times.

Key words: Solvothermal synthesis, CuInS2, Nanosheet array, Growth mechanism

中图分类号:

O611

TrendMD:

庄米雪, 魏爱香, 刘俊, 颜志强, 招瑜. CuInS₂纳米纸阵列薄膜的制备及生长机理. 高等学校化学学报, 2014, 35(11): 2310.

ZHUANG Mixue, WEI Aixiang, LIU Jun, YAN Zhiqiang, ZHAO Yu. Solvothermal Preparation and Growth Mechanism of CuInS₂ Thin Films of Nanosheet Array. Chem. J. Chinese Universities, 2014, 35(11): 2310.

图/表 6

Fig.1 SEM images of vertically oriented CIS thin film of nanosheet array grown on FTO coated glass (A, B) Top-view; (C) cross-sectional view.

Fig.2 XRD pattern(A), Raman spectrum(B) and HRTEM images(C, D) of CIS thin film of nanosheet array Inset in (D) is the enlarged HRTEM image of the same nanosheet array.

Fig.3 Reflection(A) and transmission(B) spectra and (αhν)2-hν curve(C) of CIS thin film of nanosheet array

Fig.4 SEM images of FTO substrate(A) and thin films of CIS nanosheet array grown on FTO substrate with growth time of 20 min(B), 40 min(C), 1 h(D, G), 4 h(E, H) and 8 h(F, I) (A—F) Top view; (G—I) cross-section view.

Fig.5 XRD patterns of CIS thin films of nanosheet array(A) and powders(B) synthesized in reaction solution Reaction time/h: (A) a. 1, b. 4, c. 8, d. 14, e. 20; (B) a. 0, b. 1, c. 4, d. 8, e. 14, f. 20.

Table 1 Content of elements in the CIS thin films of nanosheet array and powders synthesized in reaction solution

Sample	Reaction time/h	Atomic fraction(%)			n(Cu):n(In):n(S)
Sample	Reaction time/h	Cu	In	S	n(Cu):n(In):n(S)
CIS thin film	4	12.24	30.90	56.86	0.40:1:1.84
	8	14.64	30.13	55.23	0.49:1:1.83
	14	26.21	23.84	49.95	1.10:1:2.09
	20	27.69	22.88	49.42	1.21:1:2.16
CIS powder	1	43.00	14.46	42.54	2.97:1:2.94
	4	29.40	18.13	52.47	1.62:1:2.89
	8	27.82	20.40	51.78	1.36:1:2.54
	14	28.37	21.93	49.70	1.29:1:2.27
	20	26.94	23.59	49.47	1.14:1:2.10

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CuInS₂纳米纸阵列薄膜的制备及生长机理

Solvothermal Preparation and Growth Mechanism of CuInS₂ Thin Films of Nanosheet Array

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