Multifunctional Glutathione Enables ISOS‐Robust Inverted Perovskite Solar Cells via Dipole Engineering and Redox‐Driven Self‐Healing

ABSTRACT Self‐assembled monolayer (SAM)‐based inverted perovskite solar cells (PSCs) suffer from a persistent efficiency‐stability trade‐off issue, which limits their commercialization. Herein, we propose a synergistic stabilizing strategy using reduced glutathione (GSH) as a multifunctional additive, integrating dipole modulation and redox‐driven self‐healing. GSH enables cross‐scale regulation: inducing interfacial dipole via a concentration gradient, passivating bulk defects through Pb 2+ coordination, optimizing crystallization kinetics, providing chemical protection against O 2 • − and moisture, and establishing a GSH/oxidized glutathione (GSSG)‐Ni 2+ /Ni 3+ redox cycle for self‐healing at the NiO x /SAM interface. Moreover, the interaction between GSSG and NiO x opens an additional hole transport channel, effectively suppressing device performance degradation induced by ultraviolet (UV) irradiation and thermally‐triggered cleavage of hydroxy groups in the SAM. Benefiting from the aforementioned advantages endowed by GSH, the small‐area cell (4 mm 2 ) achieved a high efficiency of 26.17%, while the 12.50 cm 2 minimodule reached 23.14%—among the highest values reported for modules with comparable active areas. Target devices also exhibit exceptional ISOS (International Summit on Organic Photovoltaic Stability) protocols stability: retaining 69.8% (ISOS‐T‐1, 200 h), 91.0% (ISOS‐D‐1, 1056 h), and 78.44% (ISOS‐L‐2, 336 h) of their initial efficiency. This work breaks the efficiency‐stability trade‐off and offers a “dynamic regulation‐static protection” design principle for PSCs.