LAUSR

The limited selection pool of high‐performance wide bandgap (WBG) polymer donors is a bottleneck problem of the nonfullerene acceptor (NFA) based organic solar cells (OSCs) that impedes the further improvement of their photovoltaic performances. Herein, a series of new WBG polymers, namely PH‐BTz, PS‐BTz, PF‐BTz, and PCl‐BTz, are developed by using the bicyclic difluoro‐benzo[d]thiazole (BTz) as the acceptor block and benzo[1,2‐b:4,5‐b′]dithiophene (BDT) derivatives as the donor units. By introducing S, F, and Cl atoms to the alkylthienyl sidechains on BDT, the resulting polymers exhibit lowered energy levels and enhanced aggregation properties. The fluorinated PBTz‐F not only exhibits a low‐lying HOMO level, but also has stronger face‐on packing order and results in more uniform fibril‐like interpenetrating networks in the related PF‐BTz:L8‐BO blend. A high‐power conversion efficiency (PCE) of 18.57% is achieved. Moreover, PBTz‐F also exhibits a good batch‐to‐batch reproducibility and general applicability. In addition, ternary blend OSCs based on the host PBTz‐F:L8‐BO blend and PM6 guest donor exhibits a further enhanced PCE of 19.54%, which is among the highest values of OSCs.