Enhancing the Efficiency of Flexible, Large‐Area, ITO‐Free Organic Photovoltaic Devices

Abstract The development of flexible ITO‐free devices is crucial for the industrial advancement of organic photovoltaic (OPV) technology. Here, a novel ITO‐free device architecture is proposed, and ITO‐free OPV devices are realized on glass substrates with performance comparable to that of ITO‐based devices. It is also demonstrated that the performance of ITO‐free devices on polyethylene terephthalate (PET) substrates is limited due to the higher surface roughness of PET, leading to high voltage losses, low device quantum efficiency, and high device leakage current. To address the issue of high roughness on the PET surface, a polyimide (PI) modification strategy is developed and the PI‐modified PET is employed as the substrate to construct flexible ITO‐free OPV devices and large‐area modules with an active area of up to 16.5 cm². This approach leads to decreased trap‐assisted recombination losses, enhanced exciton dissociation efficiency, and a reduced density of pinholes in flexible OPV devices, resulting in improved photovoltaic performance under both strong and weak illumination conditions. The outcomes of this work are expected to advance the industrial development of flexible organic photovoltaic technology.