Preparation of Doublet, Triangular, and Tetrahedral Colloidal Clusters by Controlled Emulsification

We describe a six-step method for making colloidal clusters of 2, 3, or 4 silica particles with a radius of 1.2 microm. This method, originally described by Manoharan et al. (Manoharan, V. N.; Elsesser, M. T.; Pine, D. J. Science 2003, 301, 483), is based on the encapsulation of silica spheres in emulsion droplets. The originality of our work lies in the preparation of monodisperse emulsions, which allows us to obtain some high yields of small aggregates over a wide range of conditions. Using optical microscopy and disk centrifugation, we show that the relative fractions of 2, 3, and 4 particle aggregates are controlled by the emulsification conditions, particularly the concentration of silica in the dispersed phase. Our best yields are obtained using low to moderate shear rates, a highly viscous continuous phase, and intermediate amounts of silica. The sedimentation of the colloidal solution into a gradient of concentration leads to aqueous suspensions of identical clusters. Since the overall process can easily be scaled up, large quantities of identical clusters may be prepared, which should allow the thermodynamic properties of these new colloidal objects to be measured for the first time. These nonspherical particles could serve as building blocks for more complex assemblies, such as colloidal crystals which could find applications as photonic materials.