Tuning ultrafast electron injection dynamics at organic-graphene/metal interfaces

The properties of novel and prospective 2D materials are dramatically influenced by the interaction with a substrate. For example, the electronic hybridization of silicene states on Ag(111) or graphene ones on Ni(111) disrupts the Dirac fermions of the freestanding layers. This calls for efficient approaches to tune the interaction strength at the interface. Here we focus on the case of graphene functionalized by organic molecules and grown on Ni(111) and on the interfacial charge transfer dynamics. This is investigated by X-ray resonant photoemission spectroscopy, that is able to measure electron transfer rates occurring within few femtoseconds, and by a theoretical framework based on density-functional theory [1,2]. We use 4,4’-bipyridine as the prototypical molecule for these explorations as the energy level alignment of core-excited molecular orbitals allows ultrafast injection (τ=4fs) of electrons from the substrate to the molecule adsorbed on epitaxial graphene/Ni(111), which is characterized by a strong hybridization between C and metal states. We demonstrate that this interface can be decoupled by the addition of a second layer of graphene, where the one in contact with the metal acts as a buffer layer and the one in contact with the molecule is less hybridized with Ni underneath. As a result, the ultrafast injection of electrons from the substrate to the molecule is ∼4 times slower on weakly coupled bilayer graphene than on epitaxial graphene. Through our experiments and calculations, we can attribute this to a difference in the density of states close to the Fermi level between graphene and bilayer graphene. We therefore show how graphene coupling with the substrate influences charge transfer dynamics between organic molecules and graphene interfaces. [1] G. Fratesi, C. Motta, M. I. Trioni, G. P. Brivio, and D. Sánchez-Portal, J. Phys. Chem. C 118, 8775 (2014) [2] D. Cvetko, G. Fratesi, G. Kladnik, A. Cossaro, G.P. Brivio, L. Venkataraman, and A. Morgante, Phys. Chem. Chem. Phys. 18, 22140 (2016) [3] A. Ravikumar, G. Kladnik, M. Müller, A. Cossaro, G. Bavdek, L. Patera, D. Sánchez-Portal, L. Venkataraman, A. Morgante, G. P. Brivio, D. Cvetko, and G. Fratesi, Nanoscale 10, 8014 (2018).