B位掺杂提升CsSnI_(3)钙钛矿结构和电荷稳定性的第一性原理研究  

First-principles study on enhancing the structural and electronic stability of CsSnI_(3) by B-site doping

作　　者：赵思健 葛治中 杨旭东[1] ZHAO Si-Jian;GE Zhi-Zhong;YANG Xu-Dong(School of Materials Science and Engineering,Shanghai Jiao Tong University,Shanghai 200240,China)

机构地区：[1]上海交通大学材料科学与工程学院,上海200240

出　　处：《原子与分子物理学报》2025年第6期144-152,共9页Journal of Atomic and Molecular Physics

基　　金：国家重点研究计划(2018YFB1500104);国家自然科学基金(12274284,11911530142)。

摘　　要：全无机CsSnI_(3)钙钛矿拥有理想的带隙宽度(1.3 eV),光电转化效率理论峰值达到33%.目前CsSnI_(3)太阳能电池的发展受制于的CsSnI_(3)的结构不稳定性和Sn^(2+)易被氧化为Sn^(4+)的问题.研究基于第一性原理,详细探讨了一系列金属元素对CsSnI_(3)进行B位掺杂改性的方案,旨在提升CsSnI_(3)结构稳定性,并抑制CsSnI_(3)中Sn^(2+)被氧化为Sn^(4+)的问题.计算结果表明,在CsSnI_(3)钙钛矿B位掺杂三价金属Sb、Bi能够阻碍CsSnI_(3)相变生成Cs_(2)SnI_6,并且抑制Sn^(2+)的氧化;尤其在晶格中存在锡空位缺陷时,Sb、Bi掺杂对于Sn^(4+)形成的抑制效果更为显著.同时,低浓度的Sb、Bi掺杂不会改变CsSnI_(3)的直接带隙特性,且带隙宽度变化较小,因此能够在维持CsSnI_(3)优良光电活性的基础上进一步提高结构和电荷的稳定性.研究结果为实现高效且稳定的CsSnI_(3)钙钛矿太阳能电池提供了重要的理论指导.The all-inorganic CsSnI_(3)perovskite exhibits an ideal bandgap width of 1.3 eV and a theoretical peak photoelectric conversion efficiency of_(3)3%.However,the development of CsSnI_(3)solar cells is hindered by the structural instability of CsSnI_(3)and the facile oxidation of Sn 2+to Sn 4+.In this study,based on first-principles calculations,a series of metal elements for B-site doping modification of CsSnI_(3)are systematically investigated to enhance the structural stability of CsSnI_(3)and suppress the oxidation of Sn 2+.The results show that the B-site doping of Sb and Bi in CsSnI_(3)can impede the phase transition of CsSnI_(3)to Cs 2 SnI 6 and inhibit the oxidation of Sn 2+to Sn 4+.The inhibitory effect of Sb and Bi doping on the formation of Sn 4+is even more significant in the presence of tin vacancies.Moreover,low concentrations of Sb and Bi doping do not alter the direct bandgap characteristics of CsSnI_(3)with minimal changes in bandgap width,thus enabling optimization of structural stability and charge stability while maintaining the excellent photoelectric activity of CsSnI_(3).The findings provide important theoretical guidance for achieving efficient and stable CsSnI_(3)perovskite solar cells.

关 键 词：全无机锡基钙钛矿 第一性原理 B位掺杂 相稳定性 电子结构 

分 类 号：O482[理学—固体物理]