Crystalline-to-Crystalline Phase Transition between Germanium Selenide Polymorphs with High Resistance Contrast

Understanding phase transitions between crystalline phases of a material is crucial for both fundamental research and potential applications such as phase-change memory. In this study, we investigate the phase transition between GeSe crystalline polymorphs induced by either global annealing at moderate temperatures or localized laser-induced heating. The highly conductive γ-GeSe transforms into semiconducting, single-crystalline α-GeSe while preserving a well-aligned crystal orientation. The distinct structural and electronic properties at the γ-GeSe/α-GeSe interface were investigated by transmission electron microscopy analysis. We propose that the clustering of Ge vacancies in the γ-GeSe phase at elevated temperatures is a key mechanism driving the transition, leading to the formation of α-GeSe through the segregation of a minor GeSe₂ phase. Furthermore, we observe a high electrical resistance contrast of approximately 10⁷ between γ-GeSe and α-GeSe, underscoring the potential of GeSe as a model polymorphic system for electronic applications, including phase-change memory.