Chain Engineering of Benzodifuran-Based Wide-Bandgap Polymers for Efficient Non-Fullerene Polymer Solar Cells

Two novel benzo[1,2-b:4,5-b' ]difuran (BDF)-based wide-bandgap polymers, PBDFT-FBz and PBDFF-FBz, featuring a difluorobenzotriazole (FBz) acceptor unit, are designed and synthesized. The first attempt through main-chain engineering to alter thiophene units to furan units in the main chain of PBDFT-FBz, and further side-chain engineering eliminate the 2-ethylthiophenyl side chains of PBDFT-FBz by 2-ethylfuryl side chains to generate the "all-furan" polymer PBDFF-FBz. By taking the benefit of the oxygen atom in furan, both PBDFT-FBz and PBDFF-FBz exhibit lower HOMO energy levels and enhanced polymer chain interactions compared to their benzo[1,2-b:4,5-b' ]dithiophene (BDT)-based counterparts. As a result, while applying both polymers in non-fullerene polymer solar cells with non-fullerene acceptor m-ITIC, both devices exhibit highly promising photovoltaic performance. The power conversion efficiency (PCE) in the PBDFT-FBz device reaches 7.57% with increased open circuit voltage (V_oc ) and fill factor (FF) compared to the PCE of 5.98% in its BDT counterpart (J52). A further increased PCE is obtained (8.79%) in the PBDFF-FBz:m-ITIC device, which shows ≈47% enhancement in device performance compared to that of J52. The large increase in photovoltaic performance is attributed to the lower-lying HOMO energy levels and better chain interactions in these BDF-based polymers.