Spontaneous Formation of Cluster Array of Gold Particles by Convective Self-Assembly

Cluster arrays composed of metal nanoparticles are promising for application in sensing devices because of their interesting surface plasmon characteristics. Herein, we report the spontaneous formation of cluster arrays of gold colloids on flat substrates by vertical-deposition convective self-assembly. In this technique, under controlled temperature, a hydrophilic substrate is vertically immersed in a colloid suspension. Cluster arrays form when the particle concentration is extremely low (in the order of 10<sup>–6</sup>–10<sup>–8</sup> v/v). These arrays are arranged in a hierarchically ordered structure, where the particles form clusters that are deposited at a certain separation distance from each other, to form “dotted” lines that are in turn aligned with a constant spacing. The size of the cluster can be controlled by varying the particle concentration and temperature while an equal separation distance is maintained between the lines formed by the clusters. Our technique thus demonstrates a one-step, template-free fabrication method for cluster arrays. In addition, through the direct observation of the assembly process, the spacing between the dotted lines is found to result from the “stick-and-slip” behavior of the meniscus tip, which is entirely different from the formation processes observed for the striped patterns, which we reported previously at higher particle concentrations. The difference in the meniscus behavior possibly comes from the difference in colloidal morphology at the meniscus tip. These results demonstrate the self-regulating characteristics of the convective self-assembly process to produce colloidal patterns, whose structure depends on particle concentration and temperature.