Simulation of crystallization in Ge2Sb2Te5: A memory effect in the canonical phase-change material

Crystallization of amorphous Ge2Sb2Te5 (GST) has been studied using four extensive (460 atoms, up to 4 ns) density functional/molecular dynamics simulations at 600 K. This phase change material is a rare system where crystallization can be simulated without adjustable parameters over the physical time scale, and the results could provide insight into order-disorder processes in general. Crystallization is accompanied by an increase in the number of ABAB squares (A: Ge, Sb; B: Te), percolation, and the occurrence of low-frequency localized vibration modes. A sample with a history of order crystallizes completely in 1.2 ns, but ordering in others was less complete, even after 4 ns. The amorphous starting structures without memory display phases (>1 ns) with subcritical nuclei (10-50 atoms) ranging from nearly cubical blocks to stringlike configurations of ABAB squares and AB bonds extending across the cell. Percolation initiates the rapid phase of crystallization and is coupled to the directional p-type bonding in metastable GST. Cavities play a crucial role, and the final ordered structure is distorted rock salt with a face-centered cubic sublattice containing predominantly Te atoms. We comment on earlier models based on smaller and much shorter simulations.