Two-fluid wetting behavior of a hydrophobic silicon nanowire array

The two-fluid wetting behavior of surfaces textured by an array of silicon nanowires is investigated systematically. The Si nanowire array is produced by a combination of colloidal patterning and metal-catalyzed etching, with control over its roughness depending upon the wire length. The nanowires are made hydrophobic and oleophobic by treatment with hydrocarbon and fluorinated self-assembled monolayers, respectively. Static, advancing, and receding contact angles are measured with water, hexadecane, and perfluorotripentylamine in both single-fluid (droplet on solid in an air environment) and two-fluid (droplet on solid in a liquid environment) configurations. The single-fluid measurements show wetting behavior similar to that expected by the Wenzel and Cassie-Baxter models, where the wetting or non-wetting behaviors are amplified with increasing roughness. The two-fluid systems on the rough surface exhibit more complex configurations because either the droplet or the environment fluid can penetrate the asperities depending upon the wettability of each fluid. It is observed that, when the Young contact angles are significantly increased or reduced from single-liquid to two-liquid systems, the effect of roughness is relatively minimal. However, when the Young contact angles are similar, roughness has almost identical influence on apparent contact angles in single- and two-liquid systems. The Wenzel and Cassie-Baxter models are modified to describe various two-fluid wetting states. In cases where metastable behavior is observed for the droplet, advancing and receding measurements are performed to suggest the equilibrium state of the droplet.