Charge transfer dynamics in molecular solids and adsorbates driven by local and non-local excitations

► We determine the charge transfer times within the molecular layers of C6F6 adsorbed on Cu(111). ► We compare the results from time resolved two-photon photoemission with the core-hole-clock spectroscopy. ► A comprehensive analysis of charge transfer dynamics is provided. ► For smaller adsorbate coverages (2 ML), charge transfer occurs onto the substrate. ► For thick overlayers (6-10 ML) intermolecular charge transfer is predominant.