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. In the past more than 60 years, the research on semiconductors has focused on the univalent, binary and ternary semiconductors. Recently, out of the search for new inexpensive, environmentally friendly and highly efficient photovoltaic conversion materials, the Cu2ZnSnS4 type I2-II-IV- VI4 Quaternary chalcogenide semiconductors attract more and more people’s attention, and it’s photocatalytic and thermoelectric and other applications are also constantly being explored.However, the basic properties of such quaternary semiconductors, such as crystal structure and electronic structure, People know little about it, and many researches are still at the empirical stage.Firstly, the article briefly reviews the origin and application of these kinds of semiconductors, and then introduces the author’s first-principles calculations of this kind of quaternary semiconductors The work includes the systematic study of the regularity of the crystal structure and electron band structure of these chalcogenides during their evolution from binary to ternary to quaternary and summarizes the general influence of elemental composition on them Trend and combined with the experimental results analysis of such quaternary semiconductor lattice structure characterization and bandgap measurement prone to confusion; the author also Cu2ZnSnS4 as an example, the test Such quaternary compound relative binary and ternary compounds of the phase stability and the intrinsic nature of the defect. Findings article describes a series of experiments will provide the basis for Ⅰ2-Ⅱ-Ⅳ- Ⅵ4 type of quaternary semiconductor.