Near surface nucleation and particle mediated growth of colloidal Au nanocrystals.

During non-classical growth of nanostructures via assembly of primary nuclei, nucleation and assembly are assumed to be distinct processes: nanoparticles nucleate randomly and aggregate to form extended structures through Brownian motion in the presence of long-range attractive interactions. Here we investigate the relationship between these two processes by using in situ AFM, in situ, ex situ and cryo TEM and UV-Vis spectroscopy to observe growth of colloidal gold and simulations to develop a mechanistic model of the process. Our results reveal an inexorable link between nucleation and assembly with nuclei forming almost exclusively within a ∼1 nm interfacial region of existing particles. The new particles immediately close the gap either through a diffusive jump or via growth of a neck between the seed and new particle, generating aggregates exhibiting features commonly attributed to oriented attachment of independently nucleated particles. The results demonstrate that creation of initial particle interfaces leads to local environments that redirect growth towards non-classical processes.