CZTS基单晶材料研究进展和展望

摘要/Abstract

摘要： Ⅰ₂-Ⅱ-Ⅳ-Ⅵ₄型半导体铜锌锡硫(CZTS)在成本、组成元素丰度、毒性和稳定性等方面具有突出优势,被认为是一种很有前途的太阳能吸收材料,应用于绿色和经济的光伏领域。尽管Cu₂ZnSn(S,Se)₄拥有与黄铜矿相似的晶体结构和光电性能,但其转换效率却远远低于Cu(In,Ga)Se₂(23.5%)。传统研究多数集中在多晶薄膜材料和器件的光电性能,导致材料关键缺陷态甄别及其能带调控规律尚不清晰,成为限制CZTS基光电器件性能的瓶颈。本文综述了CZTS基单晶材料,详细介绍了其晶体结构和物理性质,概述了移动加热器法、碘输运法和熔盐法制备高质量单晶的工艺,多型纳米晶库的研究,以及天然锌黄锡矿的物性研究。根据制备的CZTS基单晶材料讨论了其光学和电学性能。最后总结了CZTS基单晶材料在半导体器件的应用及目前存在的问题,为提高Ⅰ₂-Ⅱ-Ⅳ-Ⅵ₄型半导体材料器件的性能提供可能的发展方向。

关键词: 铜锌锡硫, 天然锌黄锡矿, 缺陷态, 光电性质, 移动加热器法, 碘输运法, 熔盐法

Abstract: Ⅰ₂-Ⅱ-Ⅳ-Ⅵ₄ type semiconductor copper-zinc-tin-sulfur (CZTS) has outstanding advantages in terms of cost, constituent element abundance, toxicity and stability, and is considered as a promising solar energy harvesting material for green and cost-effective photovoltaic applications. Cu₂ZnSn(S,Se)₄ possesses chalcopyrite-like crystal structure and photoelectric performance. Nevertheless, the champion efficiency is still far behind its counterpart Cu(In,Ga)Se₂(23.5%). The current research in this field focus on the optoelectronic properties of polycrystalline thin film materials and devices, leads to unclear identification of defect states and regulation of energy bands, which has become a bottleneck for breakthroughs in the performance of CZTS-based optoelectronic devices. This article reviews the research progress of CZTS-based single crystal materials, introduces its crystal structure and physical properties in detail, and summarizes the preparation technology of high-quality single crystal by travelling heater method, iodine transport method and flux method. The research on multi-type nanocrystal library and the physical properties of natural kesterite are also introduced. The optical and electrical properties of the prepared CZTS-based single crystal materials are discussed. Finally, the article summarizes the application of CZTS-based single crystal materials in semiconductor devices, points out the existing problems, and provides possible development directions for improving the performance of Ⅰ₂-Ⅱ-Ⅳ-Ⅵ₄ semiconductor material devices.

Key words: copper-zinc-tin-sulfur, natural kesterite, defect state, photoelectric property, travelling heater method, iodine transport method, flux method

中图分类号:

O78
O474

傅文峰, 朱旭鹏, 廖峻, 汝强, 薛书文, 张军. CZTS基单晶材料研究进展和展望[J]. 人工晶体学报, 2024, 53(1): 12-24.

FU Wenfeng, ZHU Xupeng, LIAO Jun, RU Qiang, XUE Shuwen, ZHANG Jun. Research Progress and Prospect of CZTS-Based Single Crystal Materials[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(1): 12-24.

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