Transport, trapping, triplet fusion: thermally retarded exciton migration in tetracene single crystals

Efficient exciton migration is crucial for optoelectronic organic devices. While the transport of triplet excitons is generally slow compared to singlet excitons, triplet exciton migration in certain molecular semiconductors with endothermic singlet fission appears to be enhanced by a time-delayed regeneration of the more mobile singlet species via triplet fusion. This combined transport mechanism could be exploited for devices, but the interplay between singlet fission and triplet fusion, as well as the role of trap states is not yet well understood. Here, we study the spatiotemporal exciton dynamics in the singlet fission material tetracene by means of time resolved photoluminescence micro-spectroscopy on crystalline samples of different quality. Varying the temperature allows us to modify the dynamic equilibrium between singlet, triplet and trapped excitons. Supported by a kinetic model, we find that thermally activated dissociation of triplet pairs into free triplet excitons can account for an increase of the diffusion length below room temperature. Moreover, we demonstrate that trapping competes efficiently with exciton migration. Temperature and material quality strongly influence spatiotemporal exciton dynamics in the endothermic singlet fission material tetracene. Underlying transport mechanisms are disentangled by combining spectral and spatial data from TRPL experiments.