Carrier‐Selectivity‐Dependent Charge Recombination Dynamics in Organic Photovoltaic Cells with a Ferroelectric Blend Interlayer

Interfacial energetics determines the performance of organic photovoltaic (OPV) cells based on a thin film of organic semiconductor blends. Here, an approach to modulating the “carrier selectivity” at the charge collecting interfaces and the consequent variations in the nongeminate charge carrier recombination dynamics in OPV devices are demonstrated. A ferroelectric blend interfacial layer composed of a solution‐processable ferroelectric poly­mer and a wide bandgap semiconductor is introduced as a tunable electron selective layer in inverted OPV devices with non‐Ohmic contact electrodes. The direct rendering of dipole alignment within the ferroelectric blend layer is found to increase the carrier selectivity of the charge collecting interfaces up to two orders of magnitude. Transient photovoltaic analyses reveal that the increase of carrier selectivity significantly reduces the diffusion and recombination among minority carriers in the vicinity of the electrodes, giving rise to the 85% increased charge carrier lifetime. Furthermore, the carrier‐selective charge extraction leads to the constitution of the internal potential within the devices, even with energetically identical cathodes and anodes. With these carrier‐selectivity‐controlled interlayers, the devices based on various photoactive materials commonly display significant increments in the device performances, especially with the high fill factor of up to 0.76 under optimized conditions.