On the critical competition between singlet exciton decay and free charge generation in non-fullerene-based organic solar cells with low energetic offsets

In this era of non-fullerene acceptor (NFA) based organic solar cells, reducing voltage losses while maintaining high photocurrents is the holy grail of current research. Recent focus lies in understanding the manifold fundamental mechanisms in organic blends with minimal energy offsets - particularly the relationship between ionization energy offset ({\Delta}IE) and free charge generation. We quantitatively probe this relationship in multiple NFA-based blends by mixing Y5 and Y6 NFAs with PM6 of varying molecular weights, covering a 15% to 1% power conversion efficiency (PCE) range and a progression of {\Delta}IE. Spectroelectrochemistry reveals a critical {\Delta}IE of approximately 0.3 eV, below which the PCE sharply declines. Transient absorption spectroscopy consistently reveals that a smaller {\Delta}IE slows the dissociation of the NFA's local singlet exciton (LE) into free charges, albeit restorable by an electric field. Bias-dependent time delayed collection experiments quantify the free charge generation efficiency, while photoluminescence quantum efficiency measurements assess photocurrent loss from LE decay. Combined with transient photoluminescence experiments, we find that the decay of singlet excitons is the primary competition to free charge generation in low-offset NFA-based organic solar cells, with neither noticeable losses from charge-transfer (CT) decay nor evidence for LE-CT hybridization. Our experimental data align with Marcus theory calculations, supported by density functional theory simulations, for zero-field free charge generation and exciton decay efficiencies. We find that efficient photocurrent generation generally requires that the CT state is located below the LE, but that this restriction is lifted in systems with a small reorganization energy for charge transfer.