Non‐fused Star‐shape Giant Trimer Electron Acceptors for Organic Solar Cells with Efficiency over 19%

Organic solar cells (OSCs) based on giant molecular acceptors (GMAs) have attracted extensive attention due to their excellent power conversion efficiency (PCE) and operation stability. However, the large conjugated plane of GMAs poses great challenges in regulating the solubility, over‐size aggregation and yield, which in turn further constrains their development in commercial products. Herein, we employ a non‐fused skeleton strategy to develop novel non‐fused star‐shape trimers (3BTT6F and 3BTT6Cl) for improving device performance. Single‐bond linkage can break the rigid planarity to form a 3D architecture, generating multidimensional charge transfer pathways. Importantly, the non‐fused skeleton strategy can not only significantly improve solubility and synthesis yield, but also effectively suppress molecular excessive aggregation. Consequently, due to the optimized film‐forming process and charge dynamics, 3BTT6F‐based binary device obtains a high PCE of 17.52%, which is significantly higher than the reported fully fused trimers. Excitingly, 3BTT6F‐based ternary device even obtains a top‐level PCE of 19.26%. Furthermore, the non‐fused star‐shape configuration also endows these acceptors with enhanced intermolecular interaction in the active layer, demonstrating excellent operational stability. Our work emphasizes the potential of non‐fused star‐shape trimers, providing a new pathway for achieving highly efficient and stable OSCs.