Surface effects on the crystallization kinetics of amorphous antimony

Elemental antimony (Sb) is regarded as a promising candidate to improve the programming consistency and cycling endurance of phase-change memory and neuro-inspired computing devices. Although bulk amorphous Sb crystallizes spontaneously, the stability of the amorphous form can be greatly increased by reducing the thickness of thin films down to several nanometers, either with or without capping layers. Computational and experimental studies have explained the depressed crystallization kinetics caused by capping and interfacial confinement; however, it is unclear why amorphous Sb thin films remain stable even in the absence of capping layers. In this work, we carry out thorough ab initio molecular dynamics (AIMD) simulations to investigate the effects of free surfaces on the crystallization kinetics of amorphous Sb. We reveal a stark contrast in the crystallization behavior between bulk and surface models at 450 K, which stems from deviations from the bulk structural features in the regions approaching the surfaces. The presence of free surfaces intrinsically tends to create a sub-nanometer region where crystallization is suppressed, which impedes the incubation process and thus constrains the nucleation in two dimensions, stabilizing the amorphous phase in thin-film Sb-based memory devices. We reveal how free surfaces effects suppress the crystallization kinetics of amorphous antimony thin film via ab initio molecular dynamics simulations, which could guide further optimization of device geometry for phase-change memory applications.