Stabilizing colloidal crystals by leveraging void distributions.

Colloids often crystallize into polymorphic structures, which are only separated by marginal differences in free energy. Due to this fact, the face-centred cubic and hexagonal close-packed hard-sphere morphologies, for example, usually crystallize simultaneously from a supersaturated solution. The resulting lack of long-range order in these polymorphic structures has been a significant barrier to the widespread application of these crystals in, for instance, photonic bandgap materials. Here, we report a simple method to stabilize one out of two competing polymorphs by exploiting the fact that they have significantly different spatial distributions of voids. We use a variety of polymeric additives whose geometries can be tuned such that their entropy loss, which is related to crystal void symmetries, is different in the two competing polymorphs. This, in turn, controls which polymorph is most thermodynamically stable, providing a generalizable means to stabilize a selected crystal polymorph from a suite of competing structures.