Cu2ZnSnS4纳米晶及其薄膜的制备*

doi:10.11901/1005.3093.2013.335

材料研究学报

2014, Vol. 28

Issue (2): 153-160 DOI: 10.11901/1005.3093.2013.335

本期目录 | 过刊浏览

Cu₂ZnSnS₄纳米晶及其薄膜的制备^*

夏冬林(

),郑宇辰,黄波,赵修建

武汉理工大学硅酸盐建筑材料国家重点实验室武汉 430070

Preparation and Characterization of Cu₂ZnSnS₄Nanocrystals and Thin Films

Donglin XIA(

),Yuchen ZHENG,Bo HUANG,Xiujian ZHAO

State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070

引用本文:

夏冬林,郑宇辰,黄波,赵修建. Cu₂ZnSnS₄纳米晶及其薄膜的制备^*[J]. 材料研究学报, 2014, 28(2): 153-160.
Donglin XIA, Yuchen ZHENG, Bo HUANG, Xiujian ZHAO. Preparation and Characterization of Cu₂ZnSnS₄Nanocrystals and Thin Films[J]. Chinese Journal of Materials Research, 2014, 28(2): 153-160.

全文: PDF(5841 KB) HTML

摘要:

以乙酰丙酮铜(Cu(AcAc)₂)、乙酸锌(Zn(CH₃COO)₂2H₂O)、氯化亚锡(SnCl₂2H₂O)、升华硫(S粉)和十二硫醇为原料, 用热注射法合成了Cu₂ZnSnS₄(CZTS)纳米晶。再将Cu₂ZnSnS₄纳米晶制成胶体墨水, 用旋涂法制备出Cu₂ZnSnS₄薄膜。用X射线衍射(XRD)仪、拉曼光谱(RS)仪、透射电镜(TEM)、扫描电镜(SEM)、X射线能量色散谱仪(EDS)和紫外-可见光谱(UV-Vis)分光光度计对CZTS纳米晶及薄膜的晶体结构、微观形貌、化学组成及光学性能进行表征, 研究了注射温度对纳米晶结构、形貌、晶粒大小以及化学组成的影响以及热处理时间对Cu₂ZnSnS₄薄膜结构、形貌、化学组成和光学性能的影响。结果表明, 在注射温度为180℃时合成的CZTS纳米晶为锌黄锡矿结构, 平均粒径为18 nm。在500℃热处理2 h所制备出的薄膜, 在可见光范围内其吸收系数高达10⁴ cm^-1, 禁带宽度为1.45 eV。

关键词 ：无机非金属材料, Cu₂ZnSnS₄, 热注射法, 纳米晶, 旋涂法

Abstract：

The Cu₂ZnSnS₄ (CZTS) nanocrystallites were synthesized by hot injection method with starting materials of copper (II) acetylacetonate [Cu (AcAc)₂], zinc acetate [Zn(CH₃COO)₂2H₂O], tin(II) chloride dehydrate [SnCl₂2H₂O], elemental sulfur (S) and dodecanethiol. Then CZTS thin films were prepared by spin coating method. The crystallographic structure, morphology, chemical composition and optical properties of CZTS nanocrystallites and their thin films were characterized by X-ray diffraction (XRD), Raman spectrum (RS), transmission electron microscopy (TEM), scanning electron microscope (SEM) with energy dispersive X-Ray spectroscopy (EDS) and UV-Vis transmittance spectroscopy. The influence of injection temperature on the crystallographic structure, morphology, grain size and chemical composition of CZTS nanocrystallites, and the influence of annealing time on the crystallographic, morphology, chemical composition and optical properties of CZTS thin films were investigated respectively. The results show that the CZTS nanocrystallites synthesized at 180 ℃ were consisted of single phase kesterite with an average grain size 18 nm, while the CZTS thin film after annealing at 500℃ for 2h exhibits an absorption coefficient of 10⁴ cm^-1 for the visible light and an optical band gap of 1.45 eV.

Key words： inorganic non-metallic materials Cu₂ZnSnS₄ hot injection method nanocrystallite spin coating method

收稿日期: 2013-05-20

基金资助:* 国家自然科学重点基金20101j0121 资助项目。

作者简介: 本文联系人: 夏冬林

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https://www.cjmr.org/CN/10.11901/1005.3093.2013.335 或 https://www.cjmr.org/CN/Y2014/V28/I2/153

图1 不同注射温度CZTS纳米晶的XRD图谱

图2 不同注射温度CZTS纳米晶的Raman光谱

图3 样品A1的TEM和HRTEM照片

图4 样品A2的TEM和HRTEM照片

图5 样品A1的TEM和HRTEM照片

图6 样品A1的TEM和HRTEM照片

表1 不同注射温度下制备的CZTS纳米晶的EDS结果(原子分数, %)

图7 不同热处理时间CZTS薄膜的XRD图谱

图8 不同热处理时间CZTS薄膜的SEM照片

表2 不同热处理时间下制备的CZTS薄膜的EDS结果(原子分数, %)

图9 不同热处理时间CZTS薄膜的紫外可见吸收光谱

图10 不同热处理时间CZTS薄膜的(ahn)2~(hn)曲线

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