Equilibrium structure and shape of Ag and Pt nanoparticles grown on silica surfaces: From experimental investigations to the determination of a metal-silica potential.

A combination of experimental and numerical investigations on metallic silver and platinum nanoparticles deposited on silica substrates is presented, with a focus on metal-substrate interactions. Experimentally, the nanoparticles, obtained by ultra-high vacuum atom deposition, are characterized by grazing-incidence small-angle x-ray scattering and high resolution transmission electronic microscopy to determine their structure and morphology and, in particular, their aspect ratio (height/diameter), which quantifies the metal-substrate interaction, from the as-grown to equilibrium state. Numerically, the interactions between the metal and the silica species are modeled with the Lennard-Jones (12, 6) potential, with two parameters for each metal and silica species. The geometric parameters were found in the literature, while the energetic parameters were determined from our experimental measurements of the aspect ratio. The parameters are as follows: σAg-O = 0.278 nm, σAg-Si = 0.329 nm, ɛAg-O = 75 meV, and ɛAg-Si = 13 meV for Ag-silica and σPt-O = 0.273 nm, σPt-Si = 0.324 nm, ɛPt-O = 110 meV, and ɛPt-Si = 18 meV for Pt-silica. The proposed Ag-silica potential reproduces quantitatively the unexpected experimental observation of the variation of the aspect ratio for Ag nanoparticles larger than 5 nm, which has been interpreted as a consequence of the silica roughness. The nanoparticle orientation, structure, and disorder are also considered. This metal-silica potential for Ag and Pt should be helpful for further studies on pure metals as well as their alloys.