We report on the fabrication of colloidal clusters through the combination of spherical particles. Polystyrene latex particles bearing amino groups on their surface were used as building blocks of the clusters. Packing of these particles with diameters of 91 and 154 nm into assemblies with defined configurations was accomplished using narrow dispersed emulsion droplets as templates. The building blocks of the clusters adhered to the oil-water interphase due to the Pickering effect. Subsequent evaporation of the dispersed phase forced them to pack into small clusters. Addition of the particles via the dispersed phase led to higher yields of clusters than if the building blocks were added via the continuous phase. All clusters had well-defined configurations. Because the dimensions of these clusters were below 400 nm, the colloidal assemblies underlay Brownian motion which resulted in stable suspensions. The number and yields of different species could be controlled via the concentration of the building blocks and surfactant within the emulsions. Moreover, the nature of the dispersed phase itself had a strong impact on the cluster formation. When cyclohexane was used as the dispersed phase, predominately particle doublets and triplets were obtained. The use of toluene-in-water emulsions resulted into a broader spectrum of clusters of up to 12 constituents. Such clusters could satisfy the demand for particles with complex but defined shapes and special symmetries for the fabrication of novel hierarchically organized materials.

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