Sessile Liquid Features as Molds for Silicone Elastomers

Liquid applied to a chemically patterned (wetting/nonwetting, lyophilic/lyophobic) substrate forms a 3-dimensional contoured surface, the shape of which depends on the volume of liquid applied and the shape of the three-phase contact lines of air (or other phase in contact), liquid, and the wetted pattern. The resulting binary contoured interface with air, which consists of flat unwetted regions of the substrate and the mean curvature liquid-vapor interfaces of the sessile structures, can be used as a mold for imprinting solid polymers by curing liquid resins in contact. The success, flexibility with regard to shape, and reproducibility of this molding process depend on numerous issues. These include the substrate surface chemistry, the liquid application method, properties of the liquid (vapor pressure, surface tension, viscosity, and permeability in the resin), the contact angles of the liquid on the patterned substrate, and the resin curing chemistry and conditions. We investigate the room temperature platinum(0)-catalyzed curing of the most commonly studied commercial silicone elastomer, Sylgard 184, using molds composed of sessile drops of liquids on circular wetting features (bare silicon wafer) patterned on covalently attached fluoroalkylsilyl monolayers. Liquids reported are water, glycerol, an ethylene glycol oligomer, and an ionic liquid. The vapor pressure of water and its permeability in dimethyl silicone were important (and problematic) issues that could be controlled by adjusting humidity. The ionic liquid N-ethyl-N'-methylimidazolium methanesulfonate poisoned/inhibited the curing chemistry and affected silicone cross-link density and the resulting feature shape, but its lack of vapor pressure was useful in studying flow coating as a scalable liquid application method. The ethylene glycol oligomer exhibited compatibility with (and diffusion into) the silicone. Glycerol proved to be the most well-behaved and controllable liquid studied and was used to demonstrate that condensation/evaporation can be used to adjust feature shape.