First-Principles Thermodynamic Analysis of Ternary Chalcogenide Phase Change Materials

Abstract: Chalcogenide phase-change materials (PCMs) are important for nonvolatile memory and reconfigurable photonic technologies. The GeTe-Sb2Te3 mixture system, commonly referred to as GST, is the most well-known PCM family, but new PCMs are needed to broaden the accessible property space while retaining fast switching. Here, we propose a thermodynamic framework, motivated by Ostwald's rule, for understanding and identifying PCM materials. Since direct modeling of phase-transition dynamics is computationally expensive, Using first-principles calculations, we systematically evaluate the energetics of ternary chalcogenide mixtures along binary-binary tie lines and their polymorphs. By comparing ground-state and metastable structures, we assess phase stability, miscibility, and the likelihood of GST-like polymorph-mediated crystallization pathways across a broad composition space. The calculations reproduce known behavior in GST and related systems and identify several promising candidate mixtures with similar features. These results provide insight into why some PCM systems are more favorable than others and establish thermodynamic polymorph screening as a practical route for future PCM discovery.