Phonon-Assisted Nonradiative Recombination Tuned by Organic Cations in Ruddlesden-Popper Hybrid Perovskites

Significant efforts have been devoted to further increasing the photoconversion efficiency of two-dimensional (2D) organic-inorganic halide perovskites, which are promising photovoltaic materials with superior stability but lower efficiency compared to their three-dimensional counterparts. One of the main factors that limit their photoconversion efficiency is the nonradiative recombination of photoexcited carriers. A widely used strategy for tuning the photoconversion efficiency of 2D perovskites is exchanging various organic cations. However, due to mixed effects contributed to by extrinsic factors, such as defect concentration and sample morphology, experiments alone are insufficient to explain the role of organic cations in phonon-assisted carrier recombination. With time-domain simulations based on first-principles nonadiabatic molecular dynamics, we investigate six prototypical 2D Ruddlesden-Popper perovskites to reveal the impact of organic cations on tuning the nonradiative recombination time through displacing inorganic ions and affecting electron-phonon coupling. The phonon-assisted band-to-band nonradiative recombination time is on the order of a few hundred nanoseconds and can be tuned up to 5 times by modifying organic cations. A distinct correlation between the pure-dephasing time and inorganic atom distortions induced by the motion of organic parts is revealed. Compared to the pure-dephasing time, nonadiabatic coupling (NAC) associated with the strength of electron-phonon coupling plays a more important role in determining the nonradiative carrier recombination time. Notably, fluorinated organic spacers increase the NAC between frontier electronic states and speed up the nonradiative recombination process.