Enhanced charge transfer in a monolayer of the organic charge transfer complex TTF-TNAP on Au(111)

Electronic doping is a key concept for tuning the properties of organic materials. In bulk structures, the charge transfer between donor and acceptor is mainly given by the respective ionization potential and electron affinity. In contrast, monolayers of charge transfer complexes in contact with a metal are affected by an intriguing interplay of hybridization and screening at the metallic interface, determining the resulting charge state. Using scanning tunneling microscopy and spectroscopy, we characterize the electronic properties of the organic acceptor molecule 11,11,12,12-tetracyanonaptho-2,6-quinodimethane (TNAP) adsorbed on a Au(111) surface. The ordered islands remain in a weakly physisorbed state with no charge transfer interaction with the substrate. When the electron donor tetrathiafulvalene (TTF) is added, ordered arrays of alternating TNAP and TTF rows are assembled. In these structures, we find the lowest unoccupied molecular orbital (LUMO) of the free TNAP molecule shifted well below the Fermi level of the substrate. The TNAP is thus charged with more than one electron.