Molecular Design Motifs of Non-Fullerene Acceptors for Mitigating All Inherent Non-Ideal Energy Losses in Organic Photovoltaics

Non-fullerene acceptors (NFAs) have demonstrated a great potential for the transcendence of performance limits in organic photovoltaics. Despite the tremendous efforts, however, synthetic control of non-ideal recombination losses on the photovoltage are still elusive and thus lag far behind the inorganic counterparts. Here, a rational design strategy of non-fullerene acceptors is presented to overcome the limitations derived from the inherent excited state properties of organic molecules. Spectroscopic studies on a series of chemical analogs of ladder-type fused acceptors reveal that the radiative efficiency of non-fullerene acceptors is predominantly determined by the inherently strong electron-vibration coupling of their bound excited states, rather than the redistribution of molecular orbitals itself. In this sense, regardless of intramolecular charge transfer characteristics, the incorporation of rigid, and planar moiety with wide π plane is found to promote the dominance of long-lived and weakly-bound excited states in the photophysical process, in which the mitigated non-radiative decays of NFAs can be directly translated into that of charge-transfer states. Furthermore, the incorporation of such chemical moiety can minimize the evolution of subgap broadening in the bulk heterojunction blends, lowering the contribution of non-ideal radiative losses. As a result, the model systems demonstrate the non-radiative loss down to 180–190 meV, without sacrificing photocurrent generations, reaching that of inorganic counterparts. © 2024 Wiley-VCH GmbH.