Cinematographic Recording of a Metastable Floating Island in Two- and Three-Dimensional Crystal Growth

Many chemical reactions go through a cascade of events in which a series of metastable intermediates appear, and crystal nucleation is no exception. Although the consensus on the energetics of nucleation suggests the formation of metastable states preceding the crystal growth, little experimental evidence has been reported for their dynamics at an atomistic level. Operando imaging of two-dimensional nucleation on a defect-free NaCl nanocrystal in carbon nanotubes using a millisecond angstrom-resolution transmission electron microscope revealed the formation of a metastable "floating island" (FI) that migrates thermally on the (100) facet of NaCl as the first intermediate of epitaxy. The speed of the migration at 298 K is estimated to be larger than 0.3 nm ms^-1. When a crystal tumbles in a container, a space repeatedly forms between the crystal and the container wall that hosts the FI. Tumbling changes the surface energy repeatedly and promotes the conversion of the FI into a new epitaxial layer. We anticipate that this surface catalysis mechanism found on the nanoscale also operates in bulk heterogeneous nucleation where agitation and attrition accelerate crystallization.