Charge localization control of electron-hole recombination in multilayer two-dimensional Dion-Jacobson hybrid perovskites

• Published in: Journal of materials chemistry. A, Materials for energy and sustainability Vol. 8; no. 18; pp. 9168 - 9176
• Main Authors: Shi, Ran, Zhang, Zhaosheng, Fang, Wei-Hai, Long, Run
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 12.05.2020
• Subjects: Bonding strength; Coupled modes; Coupling (molecular); Density functional theory; Excitation; hydrogen; Hydrogen bonding; Localization; Molecular dynamics; Multilayers; Optoelectronics; Perovskites; Photovoltaic cells; Recombination; Solar cells; Wave functions
• ISSN: 2050-7488; 2050-7496; 2050-7496
• DOI: 10.1039/d0ta01944e

Two-dimensional (2D) Dion-Jacobson (DJ) organic-inorganic hybrid halide perovskites hold great potential for optoelectronics and solar cells. Interestingly, experimental excited-state lifetime is longer in (3AMP)(MA) n −1 Pb n I 3 n +1 than (4AMP)(MA) n −1 Pb n I 3 n +1 (3AMP = 3-(aminomethyl)piperidinium, 4AMP = 4-(aminomethyl)piperidinium, MA = CH 3 NH 3 + ) regardless of the value of n despite 3AMP having a smaller bandgap. Using ab initio nonadiabatic (NA) molecular dynamics combined with time-domain density functional theory, we focus on the n = 2 perovskite and demonstrate that stronger hydrogen bonding interaction and larger octahedral tilting cause significant delocalization of the hole wave function in (4AMP)(MA)Pb 2 I 7 and accelerates the electron-hole recombination by a factor of 5 compared to (3AMP)(MA)Pb 2 I 7 due to an increased NA coupling. The inorganic component stretching mode and coupled inorganic and organic collective motions accelerate decoherence to sub-4 fs in the two materials. The simulations rationalize the experimentally observed puzzle of excited-state lifetime in the 2D DJ perovskite and suggest a rational way to optimize the performance of perovskite devices. Significant charge delocalization in the Dion-Jacobson (4AMP)(MA)Pb 2 I 7 perovskite enhances non-adiabatic coupling and accelerates non-radiative electron-hole recombination.