Polymorphic crystalline wetting layers on crystal surfaces

Abstract Analogous to surface premelting, we propose that a crystal surface can undergo a pre-solid-solid transition, i.e. developing a thin polymorphic crystalline layer before reaching the solid-solid transition temperature if two crystals can form a low-energy coherent interface. We confirm this in simulations and colloid experiments at single-particle resolution. The power-law increase of surface layer thickness is analogous to premelting. Different kinetics and reversibilities of surface-crystal growth are observed in various systems. Surface crystals exist not only under thermal equilibrium, but also during melting, crystallization, and grain coarsening. Furthermore, the premelting and pre-solid-solid transition can coexist, resulting double surface wetting layers. We hypothesize that such surface phenomena exist in atomic and molecular crystals, which provide a novel way to tune material properties.