The Molecular Additive N‐Acetyl‐L‐Phenylalanine Delays the Crystallization and Suppresses the Phase Impurity for Achieving Triple‐Cation Perovskite Solar Cells with Efficiency Over 25%

Abstract The crystallization process plays an important role in the formation of high‐quality perovskite film for achieving efficient perovskite solar cells (PSCs), especially in the formation of mixed‐cation perovskite film, as there are normally more phase impurities than in pure CH(NH 2 ) 2 PbI 3 (FAPbI 3 ) film. Herein, a molecular additive strategy, i.e., introducing non‐planar molecule N‐acetyl‐L‐phenylalanine (APO) into the lead iodide (PbI 2 ) precursor solution, is proposed to modulate crystallization kinetics and inhibit the generation of phase impurities of metastable pretreated perovskite film. The delayed crystallization process promotes a sufficient reaction between organic salts solution and inorganic Pb‐I framework, and perovskite phase decomposition is prevented by forming strong hydrogen bonds between ─NH and I, resulting in the formation of uniform film with large‐size crystal grains and high‐purity crystalline phase. Ultimately, the target PSC devices achieve an impressive power conversion efficiency (PCE) of 25.05%, which is among the highest values of triple‐cation (FAMACs) PSCs. Meanwhile, PSC modules with 10.8 cm 2 obtain a PCE of 20.35%. Furthermore, the unencapsulated PSCs retain 94% of the initial efficiency after 40 days of storage under ambient conditions with 20% RH and also yield superior operational stability under light soaking at maximum power point tracking (MPPT) in nitrogen (N 2 ) atmosphere.