The formation of self-assembled monolayer and multilayer using redox-active Ru complex molecules with phosphonic acids on SiO2 surface has been examined using X-ray photoelectron spectroscopy (XPS), ellipsometry, and time of flight secondary mass-ion spectroscopy (TOF-SIMS). We found that an introduction of a Zr adlayer leads to higher surface molecular density of Ru complex SAMs on the SiO2 surface, compared to that of obtained from the direct adsorption of Ru complex monolayer on the SiO2 surface. We further tried to fabricate a multilayer film using this molecule with Zr(IV) ion acting as a chemical glue by a successive immersion process. The XPS data revealed that the molecular densities of the multilayers were also higher for the immobilization with Zr adlayer between Ru complex and SiO2 surface than those without the Zr adlayer, suggesting that Zr adlayer is effective in forming highly packed molecular layer of phosphonic acids on SiO2 surface. We found the film growth reached a saturation point after 6 layers on the SiO2 surface. The film growth saturation can be explained by a molecular domain boundary effect encountered due to the large tilt angle of the molecular layer. (C) 2009 Elsevier B.V. All rights reserved.