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18.5% Efficiency Organic Solar Cells with a Hybrid Planar/Bulk Heterojunction

The donor:acceptor heterojunction has proved as the most successful approach to split strongly bound excitons in organic solar cells (OSCs). Establishing an ideal architecture with selective carrier transport and suppressed recombination is of great importance to improve the photovoltaic efficiency while remains a challenge. Herein, via tailoring a hybrid planar/bulk structure, highly efficient OSCs with reduced energy losses (Elosss) are fabricated. A p‐type benzodithiophene‐thiophene alternating polymer and an n‐type naphthalene imide are inserted on both sides of a mixed donor:acceptor active layer to construct the hybrid heterojunction, respectively. The tailored structure with the donor near the anode and the acceptor near the cathode is beneficial for obtaining enhanced charge transport, extraction, and suppressed charge recombination. As a result, the photovoltaic characterizations suggest a reduced nonradiative Eloss by 25 meV, and the best OSC records a high efficiency of 18.5% (certified as 18.2%). This study highlights that precisely regulating the structure of donor:acceptor heterojunction has the potential to further improve the efficiencies of OSCs.