非绝热分子动力学模拟A位阳离子对钙钛矿热载流子弛豫的影响

doi:10.7503/cjcu20190701

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (3): 439.doi: 10.7503/cjcu20190701

• 庆祝《高等学校化学学报》复刊40周年专栏 • 上一篇下一篇

非绝热分子动力学模拟A位阳离子对钙钛矿热载流子弛豫的影响

贺进禄,龙闰,方维海

北京师范大学化学学院, 理论与计算光化学教育部重点实验室, 北京 100875

收稿日期:2019-12-23 出版日期:2020-03-10 发布日期:2020-02-07
通讯作者: 龙闰,方维海
作者简介:龙闰, 男, 博士, 教授, 博士生导师, 主要从事非绝热动力学方法发展及凝聚相材料激发态动力学研究. E-mail: runlong@bnu.edu.cn|方维海, 男, 博士, 教授, 博士生导师, 中国科学院院士, 主要从事非绝热动力学方法发展及其应用研究. E-mail: fangwh@bnu.edu.cn
基金资助:
国家自然科学基金资助(Nos. 21573022);国家自然科学基金资助(Nos. 21688102);国家自然科学基金资助(Nos. 21590801);国家自然科学基金资助(Nos. 21520102005)

A-site Cation Effects on Hot Carrier Relaxation in Perovskites by Nonadiabatic Molecular Dynamics Simulations ^†

HE Jinlu,LONG Run,FANG Weihai

College of Chemistry, Key Laboratory of Theoretical & Computational Photochemistry of Ministry of Education, Beijing Normal University, Beijing 100875, China

Received:2019-12-23 Online:2020-03-10 Published:2020-02-07
Contact: Run LONG,Weihai FANG
Supported by:
† Supported by the National Natural Science Foundation of China(Nos. 21573022);† Supported by the National Natural Science Foundation of China(Nos. 21688102);† Supported by the National Natural Science Foundation of China(Nos. 21590801);† Supported by the National Natural Science Foundation of China(Nos. 21520102005)

摘要/Abstract

摘要：

钙钛矿具有优异的光学和电学性质, 近年来成为太阳能电池领域的研究热点. 大量实验报道钙钛矿热载流子弛豫时间变化顺序为CsPbBr₃>MAPbBr₃(MA=CH₃NH₃)>FAPbBr₃[FA=HC(NH₂)₂], 但A位阳离子(Cs ⁺, MA ⁺, FA ⁺)对弛豫快慢的影响机制仍不明确. 采用基于含时密度泛函理论的非绝热动力学方法研究了上述3种钙钛矿热电子和热空穴的能量弛豫动力学, 计算得到的热载流子弛豫时间与实验结果吻合. 结果表明, A位阳离子通过静电和氢键作用影响其与无机Pb—Br骨架的电子-振动耦合, 使非绝热耦合强度遵从FAPbBr₃>MAPbBr₃>CsPbBr₃的变化趋势, 进而使热载流子弛豫时间尺度变化趋势与之相同, 表明合理选择A位阳离子可以优化钙钛矿太阳能电池的性能.

关键词: 钙钛矿, A位阳离子, 热载流子能量弛豫, 非绝热动力学, 含时密度泛函理论

Abstract:

In recent years, perovskites have become a research hotspot in the field of solar cells due to their excellent optical and electrical properties. A large number of experiments reported that hot carries relaxation times follow the trend CsPbBr₃>MAPbBr₃(MA=CH₃NH₃)>FAPbBr₃[FA=HC(NH₂)₂]. However, the underlying mechanism of the A-site cation(Cs ⁺, MA ⁺, FA ⁺) effects on the relaxation time remains unclear, the hot electrons and holes relaxation of the three perovskiteswere investigated using time-domain density functional theory combined with nonadiabatic molecular dynamics. The obtained time scales agreed well with experiment. This is because A-site cation affects electronic-vibrational coupling with the inorganic Pb—Br framework via electrostatic interaction and hydrogen bond, leading to the strength of nonadiabatic coupling decreasing from FAPbBr₃ to MAPbBr₃, to CsPbBr₃. As a result, the hot carrier relaxation times decreases as the same trend. The study suggests that rational choice of A-site cations provides an excellent strategy to the optimize the performance of perovskite solar cells.

Key words: Perovskite, A-site cation, Hot carrier energy relaxation, Nonadiabatic molecular dynamics, Time-dependent density functional theory

中图分类号:

O641

TrendMD:

贺进禄, 龙闰, 方维海. 非绝热分子动力学模拟A位阳离子对钙钛矿热载流子弛豫的影响. 高等学校化学学报, 2020, 41(3): 439.

HE Jinlu, LONG Run, FANG Weihai. A-site Cation Effects on Hot Carrier Relaxation in Perovskites by Nonadiabatic Molecular Dynamics Simulations ^†. Chem. J. Chinese Universities, 2020, 41(3): 439.

图/表 5

Fig.1 Schematic diagram of hot carrier energy relaxation dynamics in the perovskite system

Fig.2 Simulation cell showing the optimized geometry and a representative snapshot of molecular dynamics at 300 K of CsPbBr3, MAPbBr3 and FAPbBr3

Fig.3 Projected density of states(PDOS) of CsPbBr3(A), MAPbBr3(B) and FAPbBr3(C) systems

Fig.4 Time evolution of the energy decay dynamics of hot electrons with 0.4 eV(A)and 0.6 eV(C) excess energies, and hot holes with 0.4 eV(B) and 0.6 eV(D) excess energies

Fig.5 Average magnitude of the nonadiabatic couplings for hot electrons and holes relaxation within conduction band and valence band of the CsPbBr3, MAPbBr3 and FAPbBr3

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非绝热分子动力学模拟A位阳离子对钙钛矿热载流子弛豫的影响

A-site Cation Effects on Hot Carrier Relaxation in Perovskites by Nonadiabatic Molecular Dynamics Simulations ^†

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非绝热分子动力学模拟A位阳离子对钙钛矿热载流子弛豫的影响

A-site Cation Effects on Hot Carrier Relaxation in Perovskites by Nonadiabatic Molecular Dynamics Simulations †

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A-site Cation Effects on Hot Carrier Relaxation in Perovskites by Nonadiabatic Molecular Dynamics Simulations ^†