General Nondestructive Passivation by 4‐Fluoroaniline for Perovskite Solar Cells with Improved Performance and Stability

Abstract Hybrid perovskite thin films are prone to producing surface vacancies during the film formation, which degrade the stability and photovoltaic performance. Passivation via post‐treatment can heal these defects, but present methods are slightly destructive to the bulk of 3D perovskite due to the solvent effect, which hinders fabrication reproducibility. Herein, nondestructive surface/interface passivation using 4‐fluoroaniline (FAL) is established. FAL is not only an effective antisolvent candidate for surface modification, but also a large dipole molecule (2.84 Debye) with directional field for charge separation. Density functional theory calculation reveals that the nondestructive properties are attributed to both the conjugated amine in aromatic ring and the para ‐fluoro‐substituent. A hot vapor assisted colloidal process is employed for the post‐treatment. The molecular passivation yields an ultrathin protection layer with a hydrophobic fluoro‐substituent tail and thus enhances the stability and optoelectronic properties. FAL post‐treated perovskite solar cell (PSC) delivers a 20.48% power conversion efficiency under ambient conditions. Micro‐photoluminescence reveals that passivation activates the dark defective state at the surface and interface, delivering the impact picture of boundary on the local carriers. This work demonstrates a generic nondestructive chemical approach for improving the performance and stability of PSCs.