How Morphology Affects Singlet Fission in Crystalline Tetracene

The dependence of exciton dynamics on the crystalline morphology of tetracene is investigated using time-resolved photoluminescence. Single crystals exhibit relatively slow singlet decays with times that range from 130 to 300 ps depending on the sample. This decay has an activation energy of ∼450 cm(-1) over the temperature range of 200-400 K. Single-crystal samples also exhibit more pronounced quantum beats due to the triplet pair spin coherences. Polycrystalline thin films grown by thermal evaporation have singlet decay times on the order of 70-90 ps with a much weaker temperature dependence. Many thin-film samples also exhibit a red-shifted excimer-like emission. When a polycrystalline thin film is thermally annealed to produce larger crystal domains, single-crystal behavior is recovered. We hypothesize that the different dynamics arise from the ability of singlet excitons in the thin films to sample regions with defects or packing motifs that accelerate singlet fission.