Breakdown of the Stokes-Einstein relation above the melting temperature in a liquid phase-change material.

Abstract

The dynamic properties of liquid phase-change materials (PCMs), such as viscosity η and the atomic self-diffusion coefficient <i>D</i>, play an essential role in the ultrafast phase switching behavior of novel nonvolatile phase-change memory applications. To connect η to <i>D</i>, the Stokes-Einstein relation (SER) is commonly assumed to be valid at high temperatures near or above the melting temperature <i>T</i> _m and is often used for assessing liquid fragility (or crystal growth velocity) of technologically important PCMs. However, using quasi-elastic neutron scattering, we provide experimental evidence for a breakdown of the SER even at temperatures above <i>T</i> _m in the high-atomic mobility state of a PCM, Ge₁Sb₂Te₄. This implies that although viscosity may have strongly increased during cooling, diffusivity can remain high owing to early decoupling, being a favorable feature for the fast phase switching behavior of the high-fluidity PCM. We discuss the origin of the observation and propose the possible connection to a metal-semiconductor and fragile-strong transition hidden below <i>T</i> _m.