Organic Planar Heterojunction Solar Cells and Photodetectors Tailored to the Exciton Diffusion Length Scale of a Non‐Fullerene Acceptor

Abstract While non‐fullerene acceptors (NFAs) have recently been demonstrated to exhibit long‐range exciton diffusion, most organic photovoltaic and photodetector studies still focus on blended polymer: NFA systems. Herein, a 40 nm exciton diffusion length for IT4F excitons is determined, and it is demonstrated that sharp interface, planar heterojunction (PHJ) IT4F/PM6 devices with the IT4F layer thickness matched to this diffusion length yield optimized photovoltaic and photodetector performance. The PHJ devices yield an enhanced device open‐circuit voltage relative to bulk heterojunction (BHJ) devices, associated with suppressed bimolecular recombination losses. The PHJ architecture also results in a ≈100‐fold increase in electroluminescence (EL) quantum efficiency relative to the BHJ device, correlated with a shift from charge transfer state EL for the BHJ to IT4F exciton dominated EL for the PHJ, attributed to significant hole injection from PM6 into IT4F. Of particular note, the PHJ architecture is shown to suppress dark leakage current, resulting in 83 times higher photodetector detectivity at −2 V bias than the equivalent BHJ device.