Marked Passivation Effect of Naphthalene‐1,8‐Dicarboximides in High‐Performance Perovskite Solar Cells

Abstract As game‐changers in the photovoltaic community, perovskite solar cells are making unprecedented progress while still facing grand challenges such as improving lifetime without impairing efficiency. Herein, two structurally alike polyaromatic molecules based on naphthalene‐1,8‐dicarboximide (NMI) and perylene‐3,4‐dicarboximide (PMI) with different molecular dipoles are applied to tackle this issue. Contrasting the electronically pull–pull cyanide‐substituted PMI (9CN‐PMI) with only Lewis‐base groups, the push–pull 4‐hydroxybiphenyl‐substituted NMI (4OH‐NMI) with both protonic and Lewis‐base groups can provide better chemical passivation for both shallow‐ and deep‐level defects. Moreover, combined theoretical and experimental studies show that the 4OH‐NMI can bind more firmly with perovskite and the polyaromatic backbones create benign midgap states in the excited perovskite to suppress the damage by superoxide anions (energetic passivation). The polar and protonic nature of 4OH‐NMI facilitates band alignment and regulates the viscosity of the precursor solution for thicker perovskite films with better morphology. Consequently, the 4OH‐NMI‐passivated perovskite films exhibit reduced grain boundaries and nearly three‐times lower defect density, boosting the device efficiency to 23.7%. A more effective design of the passivator for perovskites with multi‐passivation mechanisms is provided in this study.