Compromising Charge Generation and Recombination with Asymmetric Molecule for High‐Performance Binary Organic Photovoltaics with Over 18% Certified Efficiency

Abstract Balancing the charge generation and recombination constitutes a major challenge to break the current limit of organic photovoltaics (OPVs). To address this issue, an asymmetric non‐fullerene acceptor, namely the AC9, is developed and high‐performance OPV with a champion efficiency of 18.43% (18.1% certified) is demonstrated. This represents the record value among binary OPVs. Comprehensive analysis on exciton dissociation, charge collection, carrier transport, and recombination has been carried out, unveiling that the improved device performance of asymmetric AC9‐based OPVs is originated from a better compromise between charge generation and non‐radiative charge recombination, compared with the corresponding symmetric ones. This work provides a high‐performing molecule and paves the way for high‐performance OPVs through asymmetric molecular design.