Fast Field-Insensitive Charge Extraction Enables High Fill Factors in Polymer Solar Cells

Fill factor (FF) is a determining parameter for the power conversion efficiency (PCE) of organic solar cells (OSC). So far, nonfullerene (NF) OSCs with state-of-the-art PCEs exhibit FFs <0.8, lower than the values of Si or perovskite solar cells. The FFs directly display the dependence of photocurrent on bias, meaning that the competition between charge extraction and recombination is modulated by internal electric potential (Vin). Here, we report a study to understand key parameters/properties affecting the device FF based on seven groups of NF-OSCs consisting of widely used PBDBT-2F or PTB7-Th donors and representative NF-acceptors with FFs ranging from 0.60 to 0.78 and PCEs from 10.27 to 16.09%. We used field-dependent transient photocurrent measurements to reveal that fast and field-insensitive charge extraction at low Vin is an essential prerequisite for obtaining high FFs (0.75–0.8), which is enabled by balanced charge transport in steady and reduced bimolecular charge recombination in high purity phases. With bias-dependent quantum efficiency analysis, we further show that the recombination loss at low Vin in the devices with low FFs tends to be more significant involving excitons generated in the donor phase of blends. Our results provide relevance for how to improve the FF toward the boost of photovoltaic performance in NF-OSCs.