Self-assembly of carbon nanodots induced by liquid-liquid phase separation in a surface microdroplet

Evaporating a sessile drop of ternary solutions containing one hydrotrope (such as ethanol) and two immiscible fluids exhibiting fascinating phase separation behaviours, has opened up a new pathway for controlled nanomaterial assembly. In this work, we studied the influence of liquid-liquid phase separation (LLPS) on the assembly of carbon nanodots (C-dots), 2 nm fluorescent carbon-based nanomaterials with high water solubility. Through self-evaporation of a micro-sized droplet containing ethanol, C-dot-water solution and different oils on a hydrophobic surface, C-dots rearranged into film, porous and granular structures by controlling the properties of oil component in the tenary droplet. Vapour pressure, solubility, surface tension and compositions of the oil components were investigated systematically for their impacts on the evaporation process of C-dot-laden droplets. By using confocal microscopy, we clearly revealed that C-dot assembly was triggered by LLPS in these four oil-water-ethanol ternary systems. The corresponding evaporation and assembly processes were unravelled to be determined by how the ternary solutions pass through the liquid-liquid equilibrium curves in the phase diagrams during evaporation. Our findings deepen the understanding of phase-separation behaviours for nanomaterial assembly as well as provide a novel, simple, and well-controlled approach for depositing different C-dot based nanostructures onto surfaces, which will benefit a wide range of practical applications in the fields of energy, environment and health.