  The electronic structure of ZnPc, from sub-monolayers to thick films, on bare
and iodated Pt(111) is studied by means of X-ray photoelectron spectroscopy
(XPS), X-ray absorption spectroscopy (XAS) and scanning tunneling microscopy
(STM). Our results suggest that at low coverage ZnPc lies almost parallel to
the Pt(111) substrate, in a non-planar configuration induced by Zn-Pt
attraction, leading to an inhomogeneous charge distribution within the molecule
and charge transfer to the molecule. ZnPc does not form a complete monolayer on
the Pt surface, due to a surface-mediated intermolecular repulsion. At higher
coverage ZnPc adopts a tilted geometry, due to a reduced molecule-substrate
interaction. Our photoemission results illustrate that ZnPc is practically
decoupled from Pt, already from the second layer. Pre-deposition of iodine on
Pt hinders the Zn-Pt attraction, leading to a non-distorted first layer ZnPc in
contact with Pt(111)-I $\left(\sqrt{3}\times\sqrt{3}\right)$ or Pt(111)-I
$\left(\sqrt{7}\times\sqrt{7}\right)$, and a more homogeneous charge
distribution and charge transfer at the interface. On increased ZnPc thickness
iodine is dissolved in the organic film where it acts as an electron acceptor
dopant.

Materials Science;Chemical Physics