Mechanistic insight into the formation of colloidal WS₂ nanoflakes in hot alkylamine media

Developing convenient and reliable synthetic methodologies for solution processable 2D layered ultrathin nanostructures with lateral size control is one of the major challenges for practical applications. In this study, a rational understanding a long-chain amphiphilic surfactant assisted non-hydrolytic synthesis that is able to generate dimension-controllable 2D-WS₂ nanocrystal flakes in a single-step protocol is proposed. The evolution of the starting soft organic-inorganic lamellar template into ultrathin few-layer 2D-WS₂ nanostructures with lateral size modulation over a range between 3 and 30 nm is monitored. The initial formation of WS₂ nanoseeds occurs in a self-assembled sacrificial precursor source, acting as a template, where larger two-dimensional nanostructures can grow without undergoing significant thickness variation. Overall, the chemical nature and steric hindrance of the alkylamines are essential to modulate the reactivity of such WS₂ nanoclusters, which correlate with the lateral size of the resulting nanoflakes.