Fully Non‐Fused Ring Electron Acceptors Enable Effective Additive‐Free Organic Solar Cells with Enhanced Exciton Diffusion Length

Abstract Low‐cost photovoltaic materials and additive‐free, non‐halogenated solvent processing of photoactive layers are crucial for the large‐scale commercial application of organic solar cells (OSCs). However, high‐efficiency OSCs that possess all these advantages remain scarce due to the lack of insight into the structure‐property relationship. In this work, three fully non‐fused ring electron acceptors (NFREAs), DTB21, DTB22, and DTB23, are reported by utilizing a simplified 1,4‐di(thiophen‐2‐yl)benzene (DTB) core with varied alkoxy chain lengths on the thiophene bridge. The material‐only costs of these acceptors are only 11–13$ per gram. Importantly, DTB22 has an exciton diffusion length ( L D ) of up to 25.5 nm. The DTB21 and DTB23 exhibit decreased L D s of 20.1 and 23.1 nm, respectively. After blending with the polymer donor PBQx‐TF, the PBQx‐TF:DTB22 film exhibits the fastest hole transfer and the longest carrier recombination lifetime among these OSCs. Consequently, the optimal PBQx‐TF:DTB22‐based OSC achieves an excellent PCE of 17.00%, which is among the highest values for fully NFREAs. In contrast, the PBQx‐TF:DTB21‐ and PBQx‐TF:DTB23‐based OSCs show relatively lower PCEs of 15.13% and 15.63%, respectively. Notably, all these OSCs are fabricated using toluene as the solvent, without any additives. Additionally, the DTB22‐based OSC also demonstrates good stability, retaining 95% of its initial efficiency after 500 h without encapsulation in a glovebox.