甲胺基-甲脒基混合钙钛矿的第一性原理研究

doi:10.3866/PKU.WHXB201801082

物理化学学报 >> 2019, Vol. 35 >> Issue (1): 69-75.doi: 10.3866/PKU.WHXB201801082

甲胺基-甲脒基混合钙钛矿的第一性原理研究

毕富珍^1,²,郑晓³,任志勇^2,*()

¹ 中国科学技术大学，化学物理系，合肥微尺度物质科学国家实验室，合肥 230026
² 北京计算科学研究中心，北京 100094
³ 贵州师范学院，贵州省纳米材料模拟与计算重点实验室，应用物理研究所，贵阳 550018

收稿日期:2017-11-27 发布日期:2018-06-13
通讯作者: 任志勇 E-mail:yamcy@csrc.ac.cn
基金资助:
国家自然科学基金(21673017);国家自然科学基金(21673017);国家重点基础研究发展计划(2014CB921402)

First-Principles Study of Mixed Cation Methylammonium-Formamidinium Hybrid Perovskite

Fuzhen BI^1,²,Xiao ZHENG³,Chiyung YAM^2,*()

¹ Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China
² Beijing Computational Science Research Center, Beijing 100094, P. R. China
³ Guizhou Provincial Key Laboratory of Computational Nano-Material Science, Institute of Applied Physics, Guizhou Normal College, Guiyang 550018, P. R. China

Received:2017-11-27 Published:2018-06-13
Contact: Chiyung YAM E-mail:yamcy@csrc.ac.cn
Supported by:
the National Natural Science Foundation of China(21673017);the National Natural Science Foundation of China(21673017);National Basic Research Program of China(2014CB921402)

摘要/Abstract

摘要：

有机铅卤钙钛矿APbX₃的稳定性是制约其应用的重要因素，对APbX₃钙钛矿中A和X采用不同种类离子混合的化学组分调控是改进其稳定性最有效的方式之一。其中，A位点采用不同比例的甲脒离子(FA)和甲胺离子(MA)是当前研究的热点方向。本文通过第一性原理计算，系统研究了FA_1-xMA_xPbI₃体系的结构和光电性质。研究发现FA与MA的混合增加体系的稳定性，其中FA_0.5MA_0.5PbI₃最稳定。通过分析不同混合比例的结构，揭示了晶格常数随x的增加线性减小；以及带隙随x减小而线性增加。此外，计算结果发现MA所占比例增加时吸收光谱蓝移。研究表明通过FA和MA离子的混合能有效调控钙钛矿的光电性质，从而获得更有效的钙钛矿太阳能电池。

关键词: 第一性原理, 有机-无机钙钛矿, 化学组分调控, 电子结构, 光电性质

Abstract:

Organic-inorganic hybrid perovskites have attracted substantial attention due to their outstanding performance in solar energy conversion and optoelectronic applications. However, the poor stability of organic lead halide perovskites (APbX₃, A: organic cations; X: halide anions) hinders their practical application. Compositional engineering, optimizing the concentration of different A and/or X, is one of the most effective ways to enhance the stability of APbX₃. In particular, mixing formamidinium (FA) and methylammonium (MA) cations has been widely investigated. Here, we performed first-principles calculations to systematically investigate the structures and optical properties of FA_1-xMA_xPbI₃. We obtained several stable crystal structures of FA_1-xMA_xPbI₃ in the cubic phase for different ratios of FA and MA cations. By analyzing the structures of these mixed cation perovskites, we revealed that the lattice parameters decreased linearly with increasing concentration of MA cations, which was consistent with previous experimental results. For APbX₃ perovskites, the Goldschmidt tolerance factor has been shown to be an effective index for predicting the stability. The mixing of organic cations is an effective method for adjusting this factor and thus the stability of these perovskite materials. In this work, the formation energy difference (∆E) was calculated and our results showed that mixing of FA and MA cations could increase the thermodynamic stability compared to pure FAPbI₃ and MAPbI₃. FA_0.5MA_0.5PbI₃ was found to be the most stable of all composites investigated. Furthermore, the band gap decreased with increasing proportion of FA cations, indicating an effective strategy for extending the absorption range of organic-inorganic hybrid perovskites into the infra-red region of the solar spectrum. By analyzing the Pb―I bond lengths for different FA : MA ratios, we showed that the decrease of band gap mainly comes from the increase of the maximum valence band energy. In addition, the effective masses were similar, irrespective of the cation mixture, indicating that the mixing of organic cations does not affect the carrier transport mechanism in this material. Density of states (DOS) analysis revealed that the DOS of valence band edge increased with increasing proportion of FA cations, enhancing transitions between the valence and conduction bands. Finally, detailed analysis of the optical absorption coefficients of all composition was performed; the absorption spectra were blue shifted with increasing MA cation concentration. These results demonstrated the possibility of controlling the optoelectronic properties of organometallic lead halide perovskites by mixing FA and MA cations and hence, further improving the efficiency of perovskite solar cells.

Key words: First-principle calculations, Organic-inorganic hybrid perovskite, Compositional engineering, Electronic structure theory, Optical properties

毕富珍,郑晓,任志勇. 甲胺基-甲脒基混合钙钛矿的第一性原理研究[J]. 物理化学学报, 2019, 35(1), 69-75. doi: 10.3866/PKU.WHXB201801082

Fuzhen BI,Xiao ZHENG,Chiyung YAM. First-Principles Study of Mixed Cation Methylammonium-Formamidinium Hybrid Perovskite[J]. Acta Phys. -Chim. Sin. 2019, 35(1), 69-75. doi: 10.3866/PKU.WHXB201801082

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201801082

https://www.whxb.pku.edu.cn/CN/Y2019/V35/I1/69

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甲胺基-甲脒基混合钙钛矿的第一性原理研究

First-Principles Study of Mixed Cation Methylammonium-Formamidinium Hybrid Perovskite

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