Simple Nonfused Ring Electron Acceptors with 3D Network Packing Structure Boosting the Efficiency of Organic Solar Cells to 15.44%

Abstract Three nonfused ring electron acceptors (NFREAs; 2Th‐2F, BTh‐Th‐2F, and 2BTh‐2F) with thieno3,2‐ b thiophene bearing two bis(4‐butylphenyl)amino substituents as the core, 3‐octylthiophene or 3‐octylthieno3,2‐ b thiophene as the spacer, and 3‐(1,1‐dicyanomethylene)‐5,6‐difluoro‐1‐indanone as the terminal group are designed and synthesized. The molar extinction coefficient of acceptors and the electron mobility of blend films gradually increase with increasing π‐conjugation length. Moreover, 2BTh‐2F displays a planar molecular conformation assisted by S···N and S···O intramolecular interactions. More importantly, the molecular stacking changes from 2D packing for the 2Th‐2F analog to 3D network packing for 2BTh‐2F. Due to these comprehensive merits, 2BTh‐2F:PBDB‐T‐based organic solar cells give a high power conversion efficiency of 14.53%. More impressively, when D18 is used as the donor polymer, the power conversion efficiency is further enhanced to 15.44%, which is the highest value reported for solar cells based on NFREAs.