Biselenophene Imide: Enabling Polymer Acceptor with High Electron Mobility for High-Performance All-Polymer Solar Cells

The shortage of narrow band gap polymer acceptors with high electron mobility is the major bottleneck for developing efficient all-polymer solar cells (all-PSCs). Herein, we synthesize a distannylated electron-deficient biselenophene imide monomer (BSeI-Tin) with high purity/reactivity, affording an excellent chance to access acceptor–acceptor (A–A) type polymer acceptors. Copolymerizing BSeI-Tin with dibrominated monomer Y5-Br, the resulting A–A polymer PY5-BSeI shows a higher molecular weight, narrower band gap, deeper-lying frontier molecular orbital levels and larger electron mobility than the donor–acceptor type counterpart PY5-BSe. Consequently, the PY5-BSeI-based all-PSCs deliver a remarkable efficiency of 17.77 % with a high short-circuit current of 24.93 mA cm⁻² and fill factor of 75.83 %. This efficiency is much higher than that (10.70 %) of the PY5-BSe-based devices. Our study demonstrates that BSeI is a promising building block for constructing high-performance polymer acceptors and stannylation of electron-deficient building blocks offers an excellent approach to developing A–A type polymers for all-PSCs and even beyond.