Revealing roles of competing local structural orderings in crystallization of polymorphic systems

Most systems have more than two stable crystalline states in the phase diagram, which is known as polymorphism. Crystallization in such a system is often under strong influence of competing orderings linked to those crystals. However, how such competition affects crystal nucleation and ordering toward the final crystalline state is largely unknown. This is primarily because the competition takes place locally and thus is masked by large positional fluctuations. We develop a unique method to correctly identify local symmetries by removing their distortions due to positional fluctuations. This allows us to experimentally access the spatiotemporal fluctuations of local symmetries at a single-particle level in crystallization of a charged colloidal system near the body-centered cubic–face-centered cubic border. Thus, we successfully reveal the crucial roles of competing ordering in the initial selection of polymorphs and the final grain boundary motion toward the most stable state from a microscopic perspective.