Multistep nucleation visualized during solid-state crystallization

Mechanisms of nucleation have been debated for more than a century, despite successes of classical nucleation theory. The nucleation process has been recently argued as involving a nonclassical mechanism (the two-step mechanism) in which an intermediate step occurs before the formation of a nascent ordered phase. However, a thorough understanding of this mechanism, in terms of both microscopic kinetics and thermodynamics, remains experimentally challenging. Here, in situ observations using transmission electron microscopy on a solid-state nucleation case indicate that early-stage crystallization can follow the non-classical pathway, yet proceed via a more complex manner in which multiple metastable states precede the emergence of a stable nucleus. The intermediate steps were sequentially isolated as spinodal decomposition of amorphous precursor, mass transport and structural oscillations between crystalline and amorphous states. Our experimental and theoretical analyses support the idea that the energetic favorability is the driving force for the observed sequence of events. Due to the broad applicability of solid-state crystallization, the findings of this study offer new insights into modern nucleation theory and a potential avenue for materials design.

Automated summary

This study provides insights into the nucleation process by observing solid-state nucleation in real time. The findings suggest that early-stage crystallization can follow a non-classical pathway and involve multiple intermediate steps. The driving force for these events is believed to be the energetic favorability.