Electron beam lithography of GeTe through polymorphic phase transformation†

We report two previously undiscovered phases of GeTe including the sphalerite (c-) phase and the hexagonal (h-) phase with interlayer van der Waals gaps. A polymorphic phase transformation from rhombohedral α-GeTe to c- and h-GeTe at near room temperature is first realized via electron beam irradiation. Their underlying thermodynamics and kinetics are illustrated using the in situ heating experiments and molecular dynamics simulations. Density-functional theory calculations indicate that c-GeTe exhibits typical metallic behavior and h-GeTe is a narrow-gap semiconductor with a strong spin–orbital coupling effect. Our findings shed light on a strategy for designing GeTe-based quantum devices compromising nanopillars and heterostructures via an atomic-scale electron beam lithography technique.