Growth and ordering of Ni(II) diphenylporphyrin monolayers on Ag(111) and Ag/Si(111) studied by STM and LEED

The room temperature self-assembly and ordering of (5,15-diphenylporphyrinato) nickel(II) (NiDPP) on the Ag(111) and Ag/Si(111)-(root 3 x root 3)R30 degrees surfaces have been investigated using scanning tunnelling microscopy and low-energy electron diffraction. The self-assembled structures and lattice parameters of the NiDPP monolayer are shown to be extremely dependent on the reactivity of the substrate, and probable molecular binding sites are proposed. The NiDPP overlayer on Ag(111) grows from the substrate step edges, which results in a single-domain structure. This close-packed structure has an oblique unit cell and consists of molecular rows. The molecules in adjacent rows are rotated by approximately 17 degrees with respect to each other. In turn, the NiDPP molecules form three equivalent domains on the Ag/Si(111)-(root 3 x root 3)R30 degrees surface, which follow the three-fold symmetry of the substrate. The molecules adopt one of three equivalent orientations on the surface, acting as nucleation sites for these domains, due to the stronger molecule-substrate interaction compared to the case of the Ag(111). The results are explained in terms of the substrate reactivity and the lattice mismatch between the substrate and the molecular overlayer.