Ultrafast Bidirectional Charge Transport and Electron Decoherence at Molecule/Surface Interfaces: A Comparison of Gold, Graphene, and Graphene Nanoribbon Surfaces

We investigate bidirectional femtosecond charge transfer dynamics using the core–hole clock implementation of resonant photoemission spectroscopy from 4,4′-bipyridine molecular layers on three different surfaces: Au(111), epitaxial graphene on Ni(111), and graphene nanoribbons. We show that the lowest unoccupied molecular orbital (LUMO) of the molecule drops partially below the Fermi level upon core–hole creation in all systems, opening an additional decay channel for the core–hole, involving electron donation from substrate to the molecule. Furthermore, using the core–hole clock method, we find that the bidirectional charge transfer time between the substrate and the molecule is fastest on Au(111), with a 2 fs time, then around 4 fs for epitaxial graphene and slowest with graphene nanoribbon surface, taking around 10 fs. Finally, we provide evidence for fast phase decoherence of the core-excited LUMO* electron through an interaction with the substrate providing the first observation of such a fast bidirectional charge transfer across an organic/graphene interface