Dimerized M‐Series Acceptors with Low Diffusion Coefficients for Efficient and Stable Polymer Solar Cells

Abstract As the simplest oligomeric acceptors, dimerized acceptors (DAs) are easier to synthesize, and more importantly, they can retain good intermolecular interaction and photovoltaic properties of their parent small‐molecule acceptors (SMAs). Nevertheless, currently most efficient DAs are derived from banana‐shaped acceptors and they might suffer from inferior device stability with high diffusion coefficients. Herein, we design and synthesize two planar DAs (DMT‐FH and DMT‐HF) by bridging two linear‐shaped M‐series SMAs with a thiophene unit. The effects of fluorination position on the diffusion coefficients, power conversion efficiencies (PCEs) and stability of the DAs are systematically studied. Our results suggest that DMT‐HF with fluorination on the ending indanone groups shows enhanced intermolecular interactions, improved PCE and stability compared with the counterpart (DMT‐FH) with fluorination on the central indanone groups. Further optimization on the DMT‐HF‐based devices yields an outstanding PCE of 17.17 %, which is the highest among all linear‐shaped SMA‐based DAs. Notably, with the low diffusion coefficient (3.36×10 −24 cm 2 s −1 ) of DMT‐HF, the resulting device retains over 93 % of the initial PCE after 5000 h of continuous heating at 85 °C, suggesting its excellent thermal stability. The results highlight the importance of intermolecular interaction and fluorination for achieving efficient and stable polymer solar cells.