r‐NG●‐Regulated Electron‐Phonon Coupling to Enhance Hot‐Hole Injection for Inverted Perovskite Solar Cells

Abstract Extracting hot‐carriers before they relax back to the band edge will reduce thermal dissipation above the bandgap, which is one of the primary sources of efficiency loss in perovskite solar cells (PSCs). It requires slow cooling of hot‐carriers together with the efficient extraction of hot‐carriers. Here, a novel interface engineering is demonstrated by embedding radical‐containing nanographene (r‐NG ● ) between perovskite and poly[bis(4‐phenyl)(2,4‐dimethoxyphenyl)‐amine] (PTOAA) to harvest this excess energy. This strategy accelerates the extraction rate of the hot‐hole (3 times that of control at 400 K) by augmenting the relaxation channel, which is related to the “quasi‐SOMO” energy state of r‐NG ● . Nonadiabatic molecular dynamics calculation further revealed that radical character promotes the rotation of the cation in perovskite, which contributes to generating strong nonadiabatic couplings and multiple phonon modes. In addition, the band bending effect of buried perovskite and improved conductivity of PTOAA also facilitate exciton dissociation and hole collection efficiency (97.5%). Consequently, the resultant r‐NG ● decorated PSCs delivered an impressive efficiency of 24.20%, along with better thermal and humidity stability. Moreover, it can maintain 93% of its initial efficiency after 300 hours of illumination.