Asymmetric and Halogenated Fused‐Ring Electron Acceptor for Efficient Organic Solar Cells

Abstract Fused‐ring non‐fullerene electron acceptors (NFAs) boost the power conversion efficiencies (PCEs) of organic solar cells (OSCs). Asymmetric and halogenated NFAs have drawn increasing attention in recent years due to their unique optoelectronic properties. Starting from the symmetric NFA ITCC‐M, this work systematically designs and synthesizes an asymmetric counterpart ITCC‐M‐2F, halogenated counterpart ITCC‐Cl, and asymmetric and halogenated counterpart IDTT‐Cl‐2F. Among these NFAs, IDTT‐Cl‐2F shows the shallowest lowest unoccupied molecular orbital energy level, broader absorption range, and the tightest molecular packing. As a result, when blended with the donor PBDB‐T‐2Cl, IDTT‐Cl‐2F‐based OSCs yield the highest PCE of 13.3% with an open‐circuit voltage of 0.96 V, short‐circuit current of 19.20 mA cm –2 , and fill factor of 71.1%, which is the highest PCE of OSCs employing 2‐(2‐chloro‐6‐oxo‐5,6‐dihydro‐4H‐cyclopenta[b]thiophen‐4‐ylidene) malononitrile (ClIC) unit terminated NFA. The results demonstrate the synergistic effect of asymmetry and halogenation toward tuning of the optoelectronic properties of NFAs for high performance OSCs.