Highly tunable β-relaxation enables the tailoring of crystallization in phase-change materials

In glasses, secondary (β-) relaxations are the predominant source of atomic dynamics. Recently, they have been discovered in covalently bonded glasses, i.e., amorphous phase-change materials (PCMs). However, it is unclear what the mechanism of β-relaxations is in covalent systems and how they are related to crystallization behaviors of PCMs that are crucial properties for non-volatile memories and neuromorphic applications. Here we show direct evidence that crystallization is strongly linked to β-relaxations. We find that the β-relaxation in Ge₁₅Sb₈₅ possesses a high tunability, which enables a manipulation of crystallization kinetics by an order of magnitude. In-situ synchrotron X-ray scattering, dielectric functions, and ab-initio calculations indicate that the weakened β-relaxation intensity stems from a local reinforcement of Peierls-like distortions, which increases the rigidity of the bonding network and decreases the dynamic heterogeneity. Our findings offer a conceptually new approach to tuning the crystallization of PCMs based on manipulating the β-relaxations.