Binary Organic Solar Cells with Exceeding 19% Efficiency via the Synergy of Polyfluoride Polymer and Fluorous Solvent

Abstract Rational molecular design and suitable device engineering are two important strategies to boost the efficiencies in organic solar cells (OSCs). Yet these two approaches are independently developed, while their synergy is believed to be more productive. Herein, a branched polyfluoride moiety, heptafluoroisopropoxyl group, is introduced into the side chains of conjugated polymers for the first time. Compared with the conventional alkyl chain, this polyfluoride chain can endow the resulting polymer namely PF7 with highly packing order and strong crystallinity owing to the strong polarization and fluorine‐induced interactions, while good solubility and moderate miscibility are retained. As a result, PF7 comprehensively outperforms the state‐of‐the‐art polymer PM6 in photovoltaic properties. More importantly, based on the solubility of heptafluoroisopropoxyl groups in fluorous solvents, a new post‐treatment denoted as fluorous solvent vapor annealing (FSVA) is proposed to match PF7. Differing from the existing post‐treatments, FSVA can selectively reorganize fluoropolymer molecules but less impact small molecules in blend films. By employing the synergy of fluoropolymer and fluorous solvent, the device achieves a remarkable efficiency of 19.09%, which is among the best efficiencies in binary OSCs. The polymer PF7 and the FSVA treatment exhibit excellent universality in various OSCs with different material combinations or device architectures.