Acta Chim. Sinica ›› 2018, Vol. 76 ›› Issue (1): 49-54.

Article

### 超卤素掺杂立方相卤化物钙钛矿太阳能电池材料第一性原理研究

1. a 中国矿业大学(北京) 材料科学与工程学院 北京 100083;
b 中国矿业大学(北京) 化学与环境工程学院 北京 100083
• 投稿日期:2017-09-04 发布日期:2017-10-20
• 通讯作者: 吴苗苗, 杨志宾 E-mail:miaomwu@cumtb.edu.cn;yangzhibin0001@163.com
• 基金资助:

项目受国家重点研发计划（No.2017YFB0601904）、国家自然科学基金（No.11404395）、中央高校基本科研业务费专项基金（No.2013QJ01）和国家大学生创新训练（No.C201604020）资助.

### Superhalogen Substitutions in Cubic Halide Perovskite Materials for Solar Cells:A First-principles Investigation

Wu Miao Miaoa, Liu Shiqianga, Chen Haoa, Wei Xuehua, Li Mingyanga, Yang Zhibinb, Ma Xiangdonga

1. a Department of Materials Science and Engineering, China University of Mining and Technology(Beijing), Beijing 100083;
b School of Chemical and Environmental Engineering, China University of Mining and Technology(Beijing), Beijing 100083
• Received:2017-09-04 Published:2017-10-20
• Contact: 10.6023/A17090406 E-mail:miaomwu@cumtb.edu.cn;yangzhibin0001@163.com
• Supported by:

Project supported by the National Key Research and Development Program of China (No. 2017YFB0601904), the National Natural Science Foundation of China (No. 11404395), the Fundamental Research Funds for the Central Universities (No. 2013QJ01) and the National Training Program of Innovation and Entrepreneurship for Undergraduates (No. C201604020).

Halide perovskite (ABC3) solar cell has received a lot of attentions due to its excellent photoelectronic properties. It has been proven to be an effective way to modify halide perovskite materials' bandgap by replacing A or B ions with other equivalent ions. However, C ions have much fewer choices and are limited to halogen anions or pseudohalides anions. We designed a series of new cubic perovskite structures through substituting C anions by superhalogen clusters anions (BeX3-, MgX3-, BX4-, AlX4-, SiX5-, PX6-, X=F, Cl), and studied their structures and properties in first-principles way. Calculations were performed by using the Vienna ab initio simulation package (VASP) based on density functional theory. The DOS (Density of States) and bandgaps were calculated to analyze properties of the new perovskite structures. The results show that BeX3-, MgX3- (X=F, Cl) and SiCl5- could not remain its structure which means these three clusters are not superhalogen anions anymore after doping. The size and symmetry of superhalogen anions have influences on the structures of doped perovskites. The superhalogen anion whose symmetry is higher and size is closed to I- ion induces less distortions to doped perovskite structures. Comparing to the VBM (Valence Band Maximum) and CBM (Conduction Band Minimum) of CsPbI3, superhalogen anions substitutions could change the compositions of CBM and VBM and bandgaps. The bandgaps of superhalogen anions partial substitutions in halide perovskite become smaller compared to structures with superhalogen anions substituting completely. We demonstrate that the CsPb(PCl6)3, with a direct-bandgap of 1.58 eV located at M(0,0.5,0.5) point, could be a potential candidate material for solar cells. Its CBM mainly is dominated by Cl 3p states, P 3s states and Pb 6p states. The other doped perovskites with wide bandgaps may have potential applications in transistors or memristors. We hope that these results could provide theoretical guidance for synthesis of new perovskite materials for solar cells.