Adsorption and photodecomposition of Mo(CO)6 on Si(111) 7×7: An infrared reflection absorption spectroscopy study

The adsorption and photodecomposition of Mo(CO)6 adsorbed on Si(111) 7×7 surfaces has been studied with Auger electron spectroscopy, temperature programmed desorption, low energy electron diffraction and infrared reflection absorption spectroscopy in a single external reflection configuration. The external-reflection technique is demonstrated to have adequate sensitivity to characterize submonolayer coverages of photogenerated Mo(CO)x fragments. It is proposed that the first layer of Mo(CO)6 adsorbs in ordered islands with a Mo(CO)6 atop each adatom of the 7×7 reconstructed Si surface. UV irradiation of these islands produces a carbonyl fragment, identified as chemisorbed Mo(CO)5. The Mo(CO)5 thermally decarbonylates via two subcarbonyl intermediates with little CO dissociation. Photolysis of thicker layers results in the formation of Mox(CO)y dimers/polymers, as evidenced by the appearance of bridging CO, which is attributed to a facile association reaction. The dimer/polymer species correlate with deposition of C and O on the surface.