Charge competition with oxygen molecules determines the growth of gold particles on doped CaO films

Abstract

The influence of gas-phase oxygen on the growth of Au nanoparticles on Mo-doped CaO films has been investigated by means of low temperature scanning tunnelling microscopy and X-ray photoelectron spectroscopy. Whereas at ideal vacuum conditions, only 2D Au islands develop on the oxide surface, the fraction of 3D deposits increases with increasing O₂ pressure until they become the dominant species in 10⁻⁶ mbar oxygen. The morphology crossover arises from changes in the interfacial electron flow between Mo donors in the CaO lattice and different ad-species on the oxide surface. In the absence of O₂ molecules, the donor electrons are predominately transferred to the Au ad-atoms, which consequently experience enhanced binding to the oxide surface and agglomerate into 2D islands. In an oxygen atmosphere, on the other hand, a substantial fraction of the excess electrons is trapped by adsorbed O₂ molecules, while the Au atoms remain neutral and assemble into tall 3D particles that are typical for non-doped oxides. Our experiments demonstrate how the competition for charge between different adsorbates governs the physical and chemical properties of doped oxides, so widely used in heterogeneous catalysis.