Size to density coupling of supported metallic clusters

Abstract

One of the difficulties in standard growth of metallic nano-clusters on oxide substrates as model catalysts is the strong coupling between clusters size and density. Employing multiple cycles, amorphous solid water–buffer layer assisted growth (ASW-BLAG) procedure, we demonstrate how the size to density coupling can be eliminated under certain conditions. In this study, gold clusters were deposited on a SiO₂/Si(100) substrate in UHV, using ASW as a buffer layer assisting aggregation and growth. The clusters were imaged ex situ by tapping mode atomic force microscope (AFM) and high-resolution scanning electron microscope (HR-SEM). In situAuger electron spectroscopy (AES) measurements have led to independent evaluation of the gold covered area. In order to increase the clusters density we have introduced a multiple BLAG procedure, in which, a BALG cycle is repeated up to 10 times. The cluster density can be increased this way by more than five fold without changing their size. Above a specific number of cycles, however, the cluster density reaches saturation and a gradual increase in clusters size is observed. Larger clusters correlate with lower saturation density following multiple BLAG cycles. This observation is explained in terms of long range cluster–cluster attraction between clusters already on the substrate and those approaching in the next BLAG cycle. This attraction is more pronounced as the clusters become larger. We have shown that at saturation density, inter-cluster distance can not be smaller than 20 nm for clusters 4 nm in diameter or larger. Employing two consecutive BLAG cycles, characterized by different parameters (metal dosage and buffer layer thickness) result in a bi-modal size distribution. Moreover, it is demonstrated that one can prepare this way co-adsorbed bi-metallic film of e.g.Au and Pd clusters, with specific density and size on the same substrate. The ASW-BLAG procedure is thus expected to introduce a new pathway for tailor made, versatile model catalysts.