中文摘要：

在过去60多年中,人们对半导体的研究集中在一元、二元和三元半导体方面,最近,出于寻找新型廉价、环保、高效光伏转换材料的需要,Cu2ZnSnS4类Ⅰ2-Ⅱ-Ⅳ- Ⅵ4型四元硫族半导体吸引了人们越来越多的关注,它在光催化和热电等多方面的应用也不断被发掘.然而,对于这类四元半导体的基本性质,如晶体结构和电子结构,人们知之甚少,很多研究还停留在经验阶段.文章首先简要回顾了这类半导体的由来和在应用方面的最新进展,然后详细介绍了文章作者对这类四元半导体的第一性原理计算研究工作的进展,其中包括：系统研究了这类硫族半导体在从二元向三元再向四元的演化过程中晶体结构和电子能带结构变化的规律,总结了元素成分对其影响的一般趋势,并结合实验结果分析了这类四元半导体晶格结构表征和带隙测量中易于出现的混淆;文章作者还以Cu2ZnSnS4为例,考察了这类四元化合物相对二元、三元化合物的相稳定性和本征缺陷性质.文章介绍的研究结果将为一系列Ⅰ2-Ⅱ-Ⅳ- Ⅵ4型四元半导体的深入研究提供基础.

英文摘要：

In the past sixty years,most of the studies about semiconductors focused on the elementary,binary and ternary semiconductors.Recently in searching for cheap,environmentally-friendly and high-efficiency solar cell absorbers,quaternary chalcogenides I2-II-IV-VI4,such as Cu2ZnSnS4,have drawn more and more attention,and their potential application as different functional materials are being explored.However,their fundamental material properties have not been well studied.In this paper,after giving a simple introduction to the history and application of I2-II-IV-VI4 semiconductors,we will review our first-principles calculation study on these semiconductors,which includes,（i）revealed the general rules in the change of crystal and electronic structure as the number of elements increases from 2 to 4,and found clear chemical trends in their dependence on the composition elements,（ii）discussed the possible confusion in the previous structure characterization and band gap measurement,（iii）studied the phase stability of the representative compound Cu2ZnSnS4 relative to the competitive binary and ternary compounds,as well as the properties of its intrinsic defects.We believe the results presented in this paper will offer some hints for the future study of the series of I2-II-IV-VI4 semiconductors.