Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, College of Chemistry, Chemical Engineering, and Materials Science, Soochow University, Suzhou 215123, China ; Suzhou Jufeng Electrical Insulation System Co. Ltd, Suzhou 215214, China.
Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Ministry of Education, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China.
Nanoscale Res Lett. 2014 May 4;9(1):208. doi: 10.1186/1556-276X-9-208. eCollection 2014.
We explore a facile and nontoxic hydrothermal route for synthesis of a Cu2ZnSnS4 nanocrystalline material by using l-cysteine as the sulfur source and ethylenediaminetetraacetic acid (EDTA) as the complexing agent. The effects of the amount of EDTA, the mole ratio of the three metal ions, and the hydrothermal temperature and time on the phase composition of the obtained product have been systematically investigated. The addition of EDTA and an excessive dose of ZnCl2 in the hydrothermal reaction system favor the generation of kesterite Cu2ZnSnS4. Pure kesterite Cu2ZnSnS4 has been synthesized at 180°C for 12 h from the reaction system containing 2 mmol of EDTA at 2:2:1 of Cu/Zn/Sn. It is confirmed by Raman spectroscopy that those binary and ternary phases are absent in the kesterite Cu2ZnSnS4 product. The kesterite Cu2ZnSnS4 material synthesized by the hydrothermal process consists of flower-like particles with 250 to 400 nm in size. It is revealed that the flower-like particles are assembled from single-crystal Cu2ZnSnS4 nanoflakes with ca. 20 nm in size. The band gap of the Cu2ZnSnS4 nanocrystalline material is estimated to be 1.55 eV. The films fabricated from the hierarchical Cu2ZnSnS4 particles exhibit fast photocurrent responses under intermittent visible-light irradiation, implying that they show potentials for use in solar cells and photocatalysis.
我们探索了一种简便无毒的水热合成方法，通过使用 L-半胱氨酸作为硫源和乙二胺四乙酸（EDTA）作为络合剂，合成 Cu2ZnSnS4 纳米晶材料。系统研究了 EDTA 的用量、三种金属离子的摩尔比以及水热温度和时间对产物相组成的影响。水热反应体系中添加 EDTA 和过量的 ZnCl2 有利于生成黄铜矿 Cu2ZnSnS4。在含有 2mmol EDTA 的反应体系中，在 180°C 下反应 12h，可得到纯黄铜矿 Cu2ZnSnS4，其 Cu/Zn/Sn 的摩尔比为 2:2:1。拉曼光谱证实，在黄铜矿 Cu2ZnSnS4 产物中不存在这些二元和三元相。水热法合成的黄铜矿 Cu2ZnSnS4 材料由尺寸为 250 至 400nm 的花状颗粒组成。结果表明，花状颗粒由尺寸约为 20nm 的单晶 Cu2ZnSnS4 纳米薄片组装而成。Cu2ZnSnS4 纳米晶材料的带隙估计为 1.55eV。由分级 Cu2ZnSnS4 颗粒制成的薄膜在间歇可见光照射下表现出快速光电流响应，这表明它们在太阳能电池和光催化方面具有应用潜力。
