The high flexibility of organic molecules offers great potential for designing the optical properties of optically active materials for the next generation of optoelectronic and photonic applications. However, despite successful implementations of molecular materials in today’s display and photovoltaic technology, many fundamental aspects of the light-to-charge conversion in molecular materials have still to be uncovered. Here, we focus on the ultrafast dynamics of optically excited excitons in C60 thin films depending on the molecular coverage and the light polarization of the optical excitation. Using time- and momentum-resolved photoemission with femtosecond extreme ultraviolet (fs-XUV) radiation, we follow the exciton dynamics in the excited states while simultaneously monitoring the signatures of the excitonic charge character in the renormalization of the molecular valence band structure. Optical excitation with visible light results in the instantaneous formation of charge-transfer (CT) excitons, which transform stepwise into Frenkel-like excitons at lower energies. The number and energetic position of the CT and Frenkel-like excitons within this cascade process are independent of the molecular coverage and the light polarization of the optical excitation. In contrast, the depopulation times of the CT and Frenkel-like excitons depend on the molecular coverage, while the excitation efficiency of CT excitons is determined by the light polarization. Our comprehensive study reveals the crucial role of CT excitons for the excited-state dynamics of homomolecular fullerene materials and thin films.

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Using time- and momentum-resolved photoemission, we investigated the formation and ultrafast relaxation process of excitons in molecular materials. We uncovered stepwise transitions between charge transfer and Frenkel excitons with different charge character and spatial distributions.