Multi-Selenophene-Containing Narrow Bandgap Polymer Acceptors for All-Polymer Solar Cells with over 15% Efficiency and High Reproducibility

All-polymer solar cells (all-PSCs) progressed tremendously due to recent advances in polymerized small molecule acceptors (PSMAs), and their power conversion efficiencies (PCEs) have exceeded 15%. However, the practical applications of all-PSCs are still restricted by a lack of PSMAs with a broad absorption, high electron mobility, low energy loss, and good batch-to-batch reproducibility. A multi-selenophene-containing PSMA, PFY-3Se, was developed based on a selenophene-fused SMA framework and a selenophene π-spacer. Compared to its thiophene analogue PFY-0Se, PFY-3Se shows a ≈30 nm red-shifted absorption, increased electron mobility, and improved intermolecular interaction. In all-PSCs, PFY-3Se achieved an impressive PCE of 15.1% with both high short-circuit current density of 23.6 mA cm⁻² and high fill factor of 0.737, and a low energy loss, which are among the best values in all-PSCs reported to date and much better than PFY-0Se (PCE=13.0%). Notably, PFY-3Se maintains similarly good batch-to-batch properties for realizing reproducible device performance, which is the first reported and also very rare for the PSMAs. Moreover, the PFY-3Se-based all-PSCs show low dependence of PCE on device area (0.045–1.0 cm²) and active layer thickness (110–250 nm), indicating the great potential toward practical applications.