Achieving High Fill Factor in Organic Photovoltaic Cells by Tuning Molecular Electrostatic Potential Fluctuation

Abstract In the field of organic photovoltaics (OPVs), significant progress has been made in tailoring molecular structures to enhance the open‐circuit voltage and the short‐circuit current density. However, there remains a crucial gap in the development of coordinated material design strategies focused on improving the fill factor (FF). Here, we introduce a molecular design strategy that incorporates electrostatic potential fluctuation to design organic photovoltaic materials. By reducing the fluctuation amplitude of IT‐4F, we synthesized a new acceptor named ITOC6‐4F. When using PBQx‐TF as a donor, the ITOC6‐4F‐based cell shows a markedly low recombination rate constant of 0.66×10 −14 cm 3 s −1 and demonstrates an outstanding FF of 0.816, both of which are new records for binary OPV cells. Also, we find that a small fluctuation amplitude could decrease the energetic disorder of OPV cells, reducing energy loss. Finally, the ITOC6‐4F‐based cell creates the highest efficiency of 16.0 % among medium‐gap OPV cells. Our work holds a vital implication for guiding the design of high‐performance OPV materials.