Binding Energy of Triplet Excitons in Nonfullerene Acceptors: The Effects of Fluorination and Chlorination

One strategy to improve the photovoltaic properties of nonfullerene acceptors (NFAs), employed in state-of-art organic solar cells, is the rational fluorination or chlorination of these molecules. Although this modification improves important acceptor properties, little is known about the effects on the triplet states. Here, we combine the polarizable continuum model with an optimally tuned range-separated hybrid functional to investigate this issue. We find that fluorination or chlorination of NFAs decreases the degree of the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) overlap along these molecules. Consequently, the energy gap between T₁ and S₁ states, ΔE_ST = E_S1 - E_T1, also decreases. This effect reduces the binding energy of triplet excitons, which favors their dissociation into free charges. Furthermore, the reduction of ΔE_ST can contribute to mitigating the losses produced by the nonradiative deactivation of the T₁ excitons. Interestingly, although Cl has a lower electronegativity than F, chlorination is more effective to reduce ΔE_ST. Since the chlorination of NFAs is easier than fluorination, Cl substitution can be a useful approach to enhance solar energy harvesting using triplet excitons.