Observing in space and time the ephemeral nucleation of liquid-to-crystal phase transitions

The phase transition of crystalline ordering is a general phenomenon, but its evolution in space and time requires microscopic probes for visualization. Here we report direct imaging of the transformation of amorphous titanium dioxide nanofilm, from the liquid state, passing through the nucleation step and finally to the ordered crystal phase. Single-pulse transient diffraction profiles at different times provide the structural transformation and the specific degree of crystallinity (η) in the evolution process. It is found that the temporal behaviour of η exhibits unique ‘two-step' dynamics, with a robust ‘plateau' that extends over a microsecond; the rate constants vary by two orders of magnitude. Such behaviour reflects the presence of intermediate structure(s) that are the precursor of the ordered crystal state. Theoretically, we extend the well-known Johnson–Mehl–Avrami–Kolmogorov equation, which describes the isothermal process with a stretched-exponential function, but here over the range of times covering the melt-to-crystal transformation.