Direct observation of photocarrier electron dynamics in C₆₀ films on graphite by time-resolved two-photon...

Time-resolved two-photon photoemission (TR-2PPE) spectroscopy is employed to probe the electronic states of a C₆₀ fullerene film formed on highly oriented pyrolytic graphite (HOPG), acting as a model two-dimensional (2D) material for multi-layered graphene. Owing to the in-plane sp²-hybridized nature of the HOPG, the TR-2PPE spectra reveal the energetics and dynamics of photocarriers in the C₆₀ film: after hot excitons are nascently formed in C₆₀ via intramolecular excitation by a pump photon, they dissociate into photocarriers of free electrons and the corresponding holes, and the electrons are subsequently detected by a probe photon as photoelectrons. The decay rate of photocarriers from the C₆₀ film into the HOPG is evaluated to be 1.31 × 10¹² s^-1, suggesting a weak van der Waals interaction at the interface, where the photocarriers tentatively occupy the lowest unoccupied molecular orbital (LUMO) of C₆₀. The photocarrier electron dynamics following the hot exciton dissociation in the organic thin films has not been realized for any metallic substrates exhibiting strong interactions with the overlayer. Furthermore, the thickness dependence of the electron lifetime in the LUMO reveals that the electron hopping rate in C₆₀ layers is 3.3 ± 1.2 × 10¹³ s^-1.