Effects of Chemical and Geometric Microstructures on the Crystallization of Surface Droplets during Solvent Exchange

In this work, we investigate the crystallization of droplets formed on micropatterned surfaces. By solvent exchange in a microchamber, a ternary solution consisting of a model compound β-alanine, water, and isopropanol was displaced by a flow of isopropanol. In the process, oiling-out droplets formed and crystallized. Our results showed that the shape and size of the crystals on surfaces with chemical micropatterns could be simply mediated by the flow conditions of solvent exchange. More uniform crystals formed on hydrophilic microdomains compared to hydrophobic microdomains or homogeneous surfaces. Varying flow rates or channel heights led to the formation of thin films with microholes, connected networks of crystals, or small diamond-shaped crystals. Physical microstructures (represented by microlenses) on the surface allowed the easy detachment of crystals from the surface. Beyond oiling-out crystallization, we demonstrated that the crystal formation of another solute dissolved in the droplets could be triggered by solvent exchange. The length of crystal fibers after the solvent-exchange process was shorter at a faster flow rate. This study may provide further understanding to effectively obtain the crystallization of surface droplets through the solvent-exchange approach.