Crystal Patterning from Aqueous Solutions via Solutal Instabilities

Fluid instabilities can be harnessed for facile self-assembly of patterned structures on the nano- and microscale. Evaporative self-assembly from drops is one simple technique that enables a range of patterning behaviors due to the multitude of fluid instabilities that arise due to the simultaneous existence of temperature and solutal gradients. However, the method suffers from limited controllability over patterns that can arise and their morphology. Here, we demonstrate that a range of distinct crystalline patterns including hexagonal arrays, branches, and sawtooth structures emerge from evaporation of water drops containing calcium sulfate on hydrophilic and superhydrophilic substrates. Different pattern regimes emerge as a function of contact line dynamics and evaporation rates, which dictate which fluid instabilities are most likely to emerge. The underlying physical mechanisms behind instability for controlled self-assembly involve Marangoni flows and forced wetting/dewetting. We also demonstrate that these patterns composed of water-soluble inorganic crystals can serve as sustainable and easily removable masks for applications in microscale fabrication.