Phase Reentrances and Solid Deformations in Confined Colloidal Crystals

A simple geometric constraint often leads to novel, complex crystalline phases distinct from the bulk. Using thin-film charge colloidal crystals, a model system with tunable interactions, we study the effects of geometric constraints. Through a combination of experiments and simulations, we systematically explore phase reentrances and solid deformation modes concerning geometrical confinement strength, identifying two distinct categories of phase reentrances below a characteristic layer number, Nc: one for bcc bulk-stable and another for fcc bulk-stable systems. We further verify that the dominant thermodynamic origin is the nonmonotonic dependence of solids' free energy on the degree of spatial confinement. Moreover, we discover transitions in solid deformation modes between interface-energy and bulk-energy dominance: below a specific layer number, Nk, geometric constraints generate unique soft deformation modes adaptive to confinement. These findings on the N-dependent thermodynamic and kinetic behaviors offer fresh insights into understanding and manipulating thin-film crystal structures.