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We present experimental results and theoretical simulations of the adsorptionbehavior of the metal-organic precursor Co2(CO)8 on SiO2 surfaces afterapplication of two different pre-treatment steps, namely by air plasma cleaningor a focused electron beam pre-irradiation. We observe a spontaneousdissociation of the precursor molecules as well as auto-deposition of cobalt onthe pre-treated SiO2 surfaces. We also find that the differences in metalcontent and relative stability of these deposits depend on the pre-treatmentconditions of the substrate. Transport measurements of these deposits are alsopresented. We are led to assume that the degree of passivation of the SiO2surface by hydroxyl groups is an important controlling factor in thedissociation process. Our calculations of various slab settings usingdispersion corrected density functional theory support this assumption. Weobserve physisorption of the precursor molecule on a fully hydroxylated SiO2surface (untreated surface) and chemisorption on a partially hydroxylated SiO2surface (pre-treated surface) with a spontaneous dissociation of the precursormolecule. In view of these calculations, we discuss the origin of thisdissociation and the subsequent autocatalysis.

Spontaneous Dissociation of Co2(CO)8 and Autocatalytic growth of Co on SiO2 : A Combined Experimental and Theoretical Investigation