Organic Solar Cells with Over 19% Efficiency Enabled by a 2D‐Conjugated Non‐Fullerene Acceptor Featuring Favorable Electronic and Aggregation Structures

The π-expansion of non-fullerene acceptors is a promising method for boosting the organic photovoltaic performance by allowing the fine-tuning of electronic structures and molecular packing. In this work, highly efficient organic solar cells (OSCs) are fabricated using a 2D π-expansion strategy to design new non-fullerene acceptors. Compared with the quinoxaline-fused cores of AQx-16, the π-expanded phenazine-fused cores of AQx-18 induce more ordered and compact packing between adjacent molecules, affording an optimized morphology with rational phase separation in the blend film. This facilitates efficient exciton dissociation and inhibited charge recombination. Consequently, a power conversion efficiency (PCE) of 18.2% with simultaneously increasing Voc , Jsc , and fill factor is achieved in the AQx-18-based binary OSCs. Significantly, AQx-18-based ternary devices fabricated via a two-in-one alloy acceptor strategy exhibit a superior PCE of 19.1%, one of the highest values ever reported for OSCs, along with a high Voc of 0.928 V. These results indicate the importance of the 2D π-expansion strategy for the delicate regulation of the electronic structures and crystalline behaviors of the non-fullerene acceptors to achieve superior photovoltaic performance, aimed at significantly promoting further development of OSCs.