Highly‐Efficient 2D Nonfullerene Acceptors Enabled by Subtle Molecular Tailoring Engineering

The conjugate expansion of nonfullerene acceptors is considered to be a promising approach for improving organic photovoltaic performance because of its function in tuning morphological structure and molecular stacking behavior. In this work, two nonfullerene acceptors are designed and synthesized using a 2D π-conjugate expansion strategy, thus enabling the construction of highly-efficient organic solar cells (OSCs). Compared with YB2B (incorporating dibromophenanthrene on the quinoxaline-fused core), YB2T (incorporating dibromobenzodithiophene on the quinoxaline-fused core) has red-shifted spectral absorption and better charge transport properties. Moreover, the more orderly and tightly intermolecular stacking of YB2T provides the possibility of forming a more suitable phase separation morphology in blend films. Through characterization and analysis, the YB2T-based blend film is found to have higher exciton dissociation efficiency and less charge recombination. Consequently, the power conversion efficiency (PCE) of 17.05% is achieved in YB2T-based binary OSCs, while YB2B-based devices only reached 10.94%. This study demonstrates the significance of the aromatic-ring substitution strategy for regulating the electronic structure and aggregation behavior of 2D nonfullerene acceptors, facilitating the development of devices with superior photovoltaic performance.