Morphology-Controlled Coating of Colloidal Particles with Silica: Influence of Particle Surface Functionalization

We present a general, convenient, and efficient synthetic concept for the coating of colloidal particles with a silica (SiO₂) shell of well-defined and precisely controlled morphology and porosity. Monodisperse submicroscopic polystyrene (PS) particles were synthesized via two-stage emulsifier-free emulsion polymerization and subsequent swelling polymerization, enabling selective particle surface modification by the incorporation of ionic (methacrylic acid, MAA) or nonionic (hydroxyethyl methacrylate, HEMA or methacrylamide, MAAm) comonomers, which could be proven by zeta potential measurements as well as by determining the three-phase contact angle of the colloidal particles adsorbed at the air-water and n-decane-water interface. The functionalized particles could be directly coated with silica shells of variable thickness, porosity, and controlled surface roughness in a seeded sol-gel process from tetraethoxysilane (TEOS), leading to hybrid PS@silica particles with morphologies ranging from core-shell (CS) to raspberry-type architectures. The experimental results demonstrated that the silica coating could be precisely tailored by the type of surface functionalization, which strongly influences the surface properties of the colloidal particles and thus the morphology of the final silica shell. Furthermore, the PS cores could be easily removed by thermal treatment, yielding extremely uniform hollow silica particles, while maintaining their initial shell architecture. These particles are highly stable against irreversible aggregation and could be readily dried, purified, and redispersed in various solvents. Herein we show a first example of coating semiconducting CdSe/ZnS nanocrystals with smooth and spherical silica shells by applying the presented method that are expected to be suitable systems for applications as markers in biology and life science by using fluorescence microscopy methods, which are also briefly discussed.