From Stacking Disorder to Cubic Order: Ice Crystallization from Deeply Supercooled Water

Abstract

Crystallization far from equilibrium can generate morphologies that defy classical crystal habits, yet the microscopic mechanisms linking atomic-scale disorder to emergent macroscopic order remain elusive. Here we use in situ cryogenic transmission electron microscopy with a membrane-encapsulated microdroplet platform to directly visualize the freezing of deeply supercooled water at molecular resolution. We show that homogeneous nucleation produces stacking-disordered ice composed of mixed hexagonal and cubic sequences, in which cubic ice initially exists only as isolated monolayers. The gradual thickening of these cubic layers constitutes the key kinetic mechanism that governs the entire crystallization pathway. As thickening proceeds, nanoscale, defect-free cubic ice germs nucleate on the basal planes of the disordered lattice. These faceted cubic germs act as facet-registered kinetic seeds that enforce cubic twinning and sequentially multiply growth branches. This kinetic pathway reproducibly generates robust eight-branched dendrites with global cubic (octahedral) symmetry, even though each branch remains highly stacking-disordered. At later stages, latent heat release drives a crossover to the thermodynamically favored hexagonal phase; remarkably, the pre-established global cubic symmetry is retained. These results reveal how strong kinetic driving forces convert microscopic disorder into emergent macroscopic symmetry, providing a general framework for understanding and controlling rapid crystallization far from equilibrium.