Atomic Mechanisms of Nanocrystallization via Cluster-Clouds in Solution Studied by Liquid-Phase Scanning Transmission Electron Microscopy.

The formation of nanocrystals is at the heart of various scientific disciplines, but the atomic mechanisms underlying the early stages of crystallization from supersaturated solutions are still rather unclear. Here, we used liquid-phase scanning transmission electron microscopy to study at the atomic level the very early stages of gold nanocrystal growth, and the evolution of its crystallinity. We found that the nucleation is initiated by the formation of poorly crystalline nanoparticles. These are transformed into monocrystals via nanocrystallization governed by a complex process of multiple out-and-in exchanges of matter between a crystalline-core and a disordered-shell, referred to as the cluster-cloud. Our observations at the crystal/cluster-cloud interface during growth demonstrate that the initially formed nanocrystals expel the poorly crystallized phases as nanoclusters into the cluster-cloud, then readsorb it by two distinct pathways, namely, by (i) monomer attachments and (ii) nanocluster coalescence. This growth process eventually leads to the formation of monocrystalline nanoparticles.