Real-time observation of the isothermal crystallization kinetics in a deeply supercooled liquid

Below the melting temperature T_m, crystals are the stable phase of typical elemental or molecular systems. However, cooling down a liquid below T_m, crystallization is anything but inevitable. The liquid can be supercooled, eventually forming a glass below the glass transition temperature T_g. Despite their long lifetimes and the presence of strong barriers that produces an apparent stability, supercooled liquids and glasses remain intrinsically a metastable state and thermodynamically unstable towards the crystal. Here we investigated the isothermal crystallization kinetics of the prototypical strong glassformer GeO₂ in the deep supercooled liquid at 1100 K, about half-way between T_m and T_g. The crystallization process has been observed through time-resolved neutron diffraction for about three days. Data show a continuous reorganization of the amorphous structure towards the alpha-quartz phase with the final material composed by crystalline domains plunged into a low-density, residual amorphous matrix. A quantitative analysis of the diffraction patterns allows determining the time evolution of the relative fractions of crystal and amorphous, that was interpreted through an empirical model for the crystallization kinetics. This approach provides a very good description of the experimental data and identifies a predator-prey-like mechanism between crystal and amorphous, where the density variation acts as a blocking barrier.