Top-Down Heterogeneous Colloidal Engineering Using Capillary Assembly of Liquid Particles

Capillary assembly of liquid particles (CALP) is a microfabrication strategy for engineering arbitrarily shaped polymer colloids. The method entails depositing emulsion particles into patterned microarrays within a fluidic cell: coalescence, polymerization, and extraction of the deposited material engender faceted colloids. Herein, the versatility of CALP is demonstrated by using both consecutive assembly and heterogeneous coassembly to engineer geometrically diverse Janus and patchy colloids. Liquid particles (LPs) can be patterned laterally across the plane of the template by manipulating the capillary immersion force, liquid particle hardness, and rate of coalescence. Bilayers of different polymeric LPs and patchy microarrays are fabricated, comprising solid colloids made from various materials including poly(styrene), p-styryltrimethoxysilane, and iron oxide. Eleven different structures including concentric Janus squares, triblock ellipsoids, and planar tetramer and pentagonal patchy particles are described. All particles are fluorescently labeled, resist flocculation, withstand extended heating, and endure dispersion in organic solvent. Further crystallization and processing into colloid-based microscale devices is therefore anticipated. Heterogeneous CALP combines top-down microfabrication with bottom-up synthesis to engineer nonequilibrium particle structures that cannot be made with wet chemistry. CALP enables the design and fabrication of colloids with complex internal construction to target hierarchical functional materials. Ultimately, the integration of colloidal building blocks comprising multiple components that are independently addressable is crucial for the development of nano/micromaterials such as filtration devices, sensors, diagnostics, solid-state catalysts, and optical electronics.