Controlled Nucleation and Oriented Crystallization of Methylammonium‐Free Perovskites via In Situ Generated 2D Perovskite Phases

Abstract Enhancing stability while maintaining high efficiency is among the primary challenges in the commercialization of perovskite solar cells (PSCs). Here, a crystal growth technique assisted by in situ generated 2D perovskite phases has been developed to construct high‐quality 2D/3D perovskite films. The in situ generated 2D perovskite serve as templates for regulating the nucleation and oriented crystal growth in the α‐FAPbI3‐rich film. This led to a high film quality with much reduced trap density and an ultralong carrier lifetime. The obtained perovskite film shows excellent stability under extreme environment conditions (T = 200 °C, RH = 75 ± 5%). The corresponding PSC achieved an efficiency of 26.16% (certified 25.84%), along with excellent operational stability (T93 > 1300 h, T ≅ 50 °C) as well as outstanding high and low temperature cycle stability.