Colloidal Crystals of Charged-Polymer-Brush-Decorated Hybrid Particles in Low-Polarity Solvents.

Colloidal crystals are self-assembled systems that are suitable as models for studying crystallization; they are also attractive as nanostructures with a periodic arrangement of materials that have different refractive indices. Here, we present a method of constructing colloidal crystals in an organic solvent using charged-polymer-brush-decorated core-shell-type hybrid particles synthesized by surface-initiated living radical polymerization. The core-shell-type hybrid particles consisted of a silica particle core surrounded by a shell of polymer brushes obtained by the polymerization of methyl methacrylate and a small amount of a cationic monomer, [2-(methacryloyloxy)ethyl]trimethylammonium chloride. When the core-shell-type hybrid particles were dispersed in a low-polarity solvent with a dielectric constant of ∼11, colloidal crystals formed when the particle volume fraction exceeded a certain threshold, and remarkably, the interparticle distance in the colloidal crystal reached more than several micrometers under certain colloidal crystallization conditions. The colloidal crystallization behavior depended upon the surface charge density of the hybrid particles, ionic strength of the suspension, and dielectric constant of the solvent. The proposed method to construct colloidal crystals using electrostatic interactions between charged polymer brushes will promote the development of systems exhibiting particle self-assembly.