ABSTRACT Interfacial redox activity between the high‐valence Ni states in NiO X and the A/X site ions of perovskite, along with imbalanced charge extraction at the NiO X /perovskite interface, induces severe non‐radiative recombination in inverted perovskite solar cells (PSCs), limiting their efficiencies and stability. To overcome these challenges, we rationally designed two donor‐acceptor (D‐A) molecular modifiers, viz. TPA‐IM and TPA‐FM, incorporating distinct electron‐withdrawing acceptor units to modulate molecular dipoles and interfacial interaction. Combined theoretical and experimental characterization reveals that strong ─C≡N···Ni and ─C≡N···Pb 2+ coordination promotes parallel molecular alignment, enabling bilateral defect passivation and efficient interfacial charge redistribution. This redistribution enhances the Ni 3+ /Ni 2+ ratio, tailors the interfacial energy landscape, and strengthens the built‐in electric field, thereby facilitating efficient hole extraction and suppressing non‐radiative recombination. Notably, TPA‐FM, featuring stronger intramolecular charge‐transfer (ICT) and superior molecular packing, forms a compact and uniform interfacial layer that effectively suppresses detrimental redox reactions. Consequently, TPA‐FM‐modified devices exhibit improved perovskite quality, reduced trap‐state densities, and minimized non‐radiative voltage losses, achieving a high PCE of 25.73% along with enhanced operational stability and suppressed ion migration. This work establishes a molecular design strategy to mitigate interfacial redox processes and optimize energy‐level alignment at the NiO x /perovskite interface for durable inverted PSCs.
Adhikari et al. (Wed,) studied this question.