Wide‐Bandgap Polymers with a C(sp3)─F Polyfluoride Backbone Enable High‐Efficient Ternary Organic Solar Cells

Abstract Fluorination strategy is demonstrated to be a successful approach for optimizing the electron distribution and morphology of organic photovoltaic materials. The previous works focus on introducing only a few C(sp 2 )─F bonds into conjugated backbone or C(sp 3 )─F bonds into sidechains. Herein, a new strategy by introducing C(sp 3 )─F polyfluoride unit into the backbone is proposed, wherein the fluorine atoms are not involved into the conjugation but can promote the intermolecular interaction between backbones. Two wide‐bandgap fluoropolymers are prepared and employed as the third component for ternary organic solar cells. As expected, even if there are six fluorine atoms in a single repeat unit, the relevant fluoropolymers possess complementary absorption and aligned energy levels. More importantly, the polyfluoride backbone affords adequate non‐covalent interactions, consequently enhancing the polymer aggregation and packing order, which is verified by a fibril‐like morphology in the blend film with the host polymer PM6 and only 10 wt.% fluoropolymer. In addition, the decreased surface energy caused by polyfluoride unit is beneficial for the improvement of domain purity and the formation of nanoscale phase separation between donor and acceptor materials. As a result, the fluoropolymer‐assisted ternary device displays a higher efficiency of 18.74% compared with the binary device (17.39%).