Supramolecular self-assembly of metal-free naphthalocyanine on Au(111)

The self-assembly of metal-free naphthalocyanine (H2Nc) on the Au(111) surface is studied under ultrahigh vacuum conditions at room temperature using a combination of scanning tunnelling microscopy (STM), low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). The STM measurements reveal that the molecules form a well-ordered, defect-free structure with a square-like unit cell at monolayer coverage with their molecular plane parallel to the substrate plane. The molecular lattice direction is aligned along one of the principal directions of the underlying Au(111) substrate while the molecular orientation remains unchanged for different domains. XPS measurements show that there is no significant difference in the electronic structure of H2Nc between monolayer and multilayer coverage. Combining the information obtained from STM, LEED and XPS measurements demonstrates that the self-assembled structure of H2Nc on Au(111) is mainly stabilized by intermolecular interactions while the molecule–substrate interactions are responsible for the rotational alignment of the molecules with respect to the principal Au directions.