Molecular Packing and Dielectric Property Optimization through Peripheral Halogen Swapping Enables Binary Organic Solar Cells with an Efficiency of 18.77

Peripheral halogen regulations can endow non‐fullerene acceptors (NFAs) with enhanced features as organic semi‐conductors and further boost efficient organic solar cells (OSCs). Herein, based on a remarkable molecular platform of CH14 with more than six halogenation positions, a preferred NFA of CH23 is constructed by synergetic halogen swapping on both central and end units, rendering the overall enlarged molecular dipole moment, packing density and thus relative dielectric constant. Consequently, the CH23‐based binary OSC reaches an excellent efficiency of 18.77% due to its improved charge transfer/transport dynamics, much better than that of 17.81% for the control OSC of CH14. This work demonstrates the great potential for further achieving state‐of‐the‐art OSCs by delicately regulating the halogen formula on these newly explored CH‐series NFAs. A non‐fullerene acceptor of CH23 is constructed simply by peripheral halogen swapping on a high‐performance molecular platform of CH14. Due to enhanced dielectric features and intermolecular interactions, CH23‐based binary organic solar cells achieve an excellent efficiency of 18.77%, exhibiting the best value for the newly explored CH‐series non‐fullerene acceptors.