Induced transition of CdSe nanoparticle superstructures by controlling the internal flow of colloidal solution

The self-assembly behaviors of flow-enhanced CdSe nanoparticle (NP) colloidal systems were investigated, which were systemically prepared by adding ethylene glycol (EG) or acetic acid (AA) to NP suspensions with deionized water (DI water) base. The additive solvents, which had higher boiling points and lower surface tensions than those of the DI water, modified the internal flow of the NP colloidal system, consequently affecting the morphologies of the generated NP superstructures after the full evaporation of their droplets. In flow-enhanced systems, NPs were formed into highly elongated dendrites that stretched from the center region to the edges along the direction of convective flow inside the droplet, while NPs in random drift system were easily aggregated to form cluster-shaped thick dendritic structures. When the volume fraction of EG was increased, the dominant superstructures were changed from dendrites to clusters, which can be mainly attributed to the changes in the dielectric properties of the NP droplets as evaporation proceeded because of the large discrepancy in the vapor pressures of EG and DI water. The balance between the interparticle potentials of electrostatic repulsion and van der Waals attraction was continuously altered, resulting in the formation of clusters with increasing EG ratio. Contrastively, the transition of superstructures could not be observed in the case of colloidal system prepared by mixing DI water and AA, which can be ascribed to the similar vapor pressures of the two solvents; the dielectric properties of the solution mixture was barely changed throughout the steady evaporation process, which resulted in the formation of uniformly distributed highly elongated dendrites. Polarization-dependent imaging experiments and photoluminescence measurements revealed that the stretched dendrites formed under the flow-enhanced conditions showed higher crystallinity than that of the clusters.