Capillary Assembly of Liquid Particles

Abstract Capillary assembly is a versatile method for depositing colloidal particles within templates, resulting in nano/microarrays and colloidal superstructures for optical, plasmonic, and sensory applications. Liquid particles (LPs), comprised of oligomerized 3‐(trimethoxysilyl)propyl methacrylate, are herein shown to deposit into patterned cavities via capillary assembly. In contrast to solid colloids, LPs coalesce upon solvent evaporation and assume the geometry of the template. Incorporating small molecules such as dyes followed by LP solidification generates fluorescent polymer microarrays of any geometry. The LP size is inversely proportional to the quantity of deposited material and the convexity of the final polymer array. Cavity filling can be tuned by increasing the assembly temperature. Extraction of the polymerized regions produces solidified particles with faceted shapes including square prisms, trapezoids, and ellipsoids with sizes up to 14 µm that retain the shape of the cavity in which they are initially held. LP deposition thus presents a highly controllable fabrication scheme for geometrically diverse polymer microarrays and anisotropic colloids of any conceivable polygonal shape due to space filling of the template. The extension of capillary assembly to LPs that can be doped with small molecule dyes and analytes invaluably expands the synthetic toolbox for top‐down, scalable, hierarchically engineered materials.