Tuning molecule-substrate coupling via deposition of metal adatoms

Organic-inorganic hybrids constitute an important class of functional materials. The fundamentals at the molecular levels are, however, relatively unexplored. PTCDA (perylene-3,4,9,10-tetracarboxylic dianhydride) is a colorant and extensively applied in organic-based optoelectronic devices. PTCDA/Cu(111) and Fe-PTCDA/Cu(111) metal-organic hybrid monolayers are studied by low temperature scanning tunneling microscopy and spectroscopy (STS) and density functional theory (DFT). The former exhibits Moiré pattern-modulated molecular density of states while the latter adapts a commensurate adlattice. Both imaging and spectroscopic results suggest a strong hybridization between PTCDA molecules and Cu(111) substrate. Weak PTCDA-Cu(111) coupling can be obtained by the introduction of Fe adatoms. Compared to PTCDA/Cu(111), STS spectra of Fe-PTCDA/Cu(111) exhibit a higher energy and sharper features of the frontier orbitals. Together with the DFT results, we found that the PTCDA-Cu(111) coupling is attenuated by the presence of Fe adatoms and Fe-PTCDA coordination.