A New Wide Bandgap Donor Polymer for Efficient Nonfullerene Organic Solar Cells with a Large Open‐Circuit Voltage

: Significant progress has been made in nonfullerene small molecule acceptors (NF-SMAs) that leads to a consistent increase of power conversion efficiency (PCE) of nonfullerene organic solar cells (NF-OSCs). To achieve better compatibility with high-performance NF-SMAs, the direction of molecular design for donor polymers is toward wide bandgap (WBG), tailored properties, and preferentially ecofriendly processability for device fabrication. Here, a weak acceptor unit, methyl 2,5-dibromo-4-fluorothiophene-3-carboxylate (FE-T), is synthesized and copolymerized with benzo[1,2-b:4,5-b']dithiophene (BDT) to afford a series of nonhalogenated solvent processable WBG polymers P1-P3 with a distinct side chain on FE-T. The incorporation of FE-T leads to polymers with a deep highest occupied molecular orbital (HOMO) level of -5.60-5.70 eV, a complementary absorption to NF-SMAs, and a planar molecular conformation. When combined with the narrow bandgap acceptor ITIC-Th, the solar cell based on P1 with the shortest methyl chain on FE-T achieves a PCE of 11.39% with a large Voc of 1.01 V and a Jsc of 17.89 mA cm-2. Moreover, a PCE of 12.11% is attained for ternary cells based on WBG P1, narrow bandgap PTB7-Th, and acceptor IEICO-4F. These results demonstrate that the new FE-T is a highly promising acceptor unit to construct WBG polymers for efficient NF-OSCs.