Femtosecond Dynamics of Photoexcited C₆₀ Films

The well known organic semiconductor C₆₀ is attracting renewed attention due to its centimeter-long electron diffusion length and high performance of solar cells containing 95% fullerene, yet its photophysical properties remain poorly understood. We elucidate the dynamics of Frenkel and intermolecular (inter-C₆₀) charge-transfer (CT) excitons in neat and diluted C₆₀ films from high-quality femtosecond transient absorption (TA) measurements performed at low fluences and free from oxygen or pump-induced photodimerization. We find from preferential excitation of either species that the CT excitons give rise to a strong electro-absorption (EA) signal but are extremely short-lived. The Frenkel exciton relaxation and triplet yield strongly depend on the C₆₀ aggregation. Finally, TA measurements on full devices with applied electric field allow us to optically monitor the dissociation of CT excitons into free charges for the first time and to demonstrate the influence of cluster size on the spectral signature of the C₆₀ anion.