Intrachain Exciton Motion Can Compete with Interchain Hopping in Conjugated Polymer Films with a Strong J-Aggregate Property.

Understanding exciton diffusion properties in organic semiconductor films is crucial for organic solar cells because excitons need to diffuse to an electron donor/acceptor interface to dissociate into charges. We previously found that singlet excitons generated in the thin films of a novel naphthobisoxadiazole-based low-bandgap polymer PNOz4T exhibit two-dimensional exciton diffusion characteristics along the backbone and π-stacking directions owing to the HJ-aggregate property of PNOz4T. However, the diffusion constants along these directions could not be determined owing to the difficulty of data analysis. Herein, we present a detailed analysis based on a simulated annealing metaheuristic. We found that intrachain exciton motion can be faster than interchain hopping. On the basis of temperature dependence measurements, we found that exciton diffusion is more favorable at lower temperatures because the coherent component partly contributes to exciton motion.