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

Abstract

A combination of experimental and numerical calculations on metallic silver and platinum nanoparticles deposited on silica substrates is presented, with a focus on the metal-substrate interactions. Experimentally, the nanoparticles are elaborated under ultra-high vacuum and characterized by Grazing-Incidence Small-Angle X-ray Scattering (GISAXS) and High Resolution Transmission Electronic Microscopy (HRTEM) to determine their structure and morphology, and in particular their aspect ratio (height/diameter) which quantifies the metal-substrate interaction. 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: {\sigma}_{Ag-O} = 0.278 nm, {\sigma}_{Ag-Si} = 0.329 nm, {\epsilon}_{Ag-O} = 75 meV, and {\epsilon}_{Ag-Si} = 13 meV for Ag-silica and {\sigma}_{Pt-O} = 0.273 nm, {\sigma}_{Pt-Si} = 0.324 nm, {\epsilon}_{Pt-O} = 110 meV, and {\epsilon}_{Pt-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.