The ground state crystal structure of GeTe–Sb₂Te₃ superlattices is actually a van der Waals heterostructure of Sb₂Te₃ and rhombohedral GeSbTe.

Phase Change Materials (PCMs) are unique compounds employed in non-volatile random access memory thanks to the rapid and reversible transformation between the amorphous and crystalline state that display large differences in electrical and optical properties. In addition to the amorphous-to-crystalline transition, experimental results on polycrystalline GeSbTe alloys (GST) films evidenced a Metal-Insulator Transition (MIT) attributed to disorder in the crystalline phase. Here we report on a fundamental advance in the fabrication of GST with out-of-plane stacking of ordered vacancy layers by means of three distinct methods: Molecular Beam Epitaxy, thermal annealing and application of femtosecond laser pulses. We assess the degree of vacancy ordering and explicitly correlate it with the MIT. We further tune the ordering in a controlled fashion attaining a large range of resistivity. Employing ordered GST might allow the realization of cells with larger programming windows.

Phase-change materials based on GeSbTe show unique switchable optoelectronic properties and are an important contender for next-generation non-volatile memories. Moreover, they recently received considerable scientific interest, because it is found that a vacancy ordering process is responsible for both an electronic metal–insulator transition and a structural cubic-to-trigonal transition. GeTe–Sb₂Te₃ based superlattices, or specifically their interfaces, provide an interesting platform for the study of GeSbTe alloys. In this work such superlattices have been grown with molecular beam epitaxy and they have been characterized extensively with transmission electron microscopy and X-ray diffraction. It is shown that the van der Waals gaps in these superlattices, which result from vacancy ordering, are mobile and reconfigure through the film using bi-layer defects and Ge diffusion upon annealing. Moreover, it is shown that for an average composition that is close to GeSb₂Te₄ a large portion of 9-layered van der Waals systems is formed, suggesting that still a substantial amount of random vacancies must be present within the trigonal GeSbTe layers. Overall these results illuminate the structural organization of van der Waals gaps commonly encountered in GeSbTe alloys, which are intimately related to their electronic properties and the metal–insulator transition.

The breaking of bulk inversion symmetry in ferroelectric semiconductors causes a Rashba-type spin splitting of electronic bulk bands. This is shown by a comprehensive mapping of the spin polarization of the electronic bands in ferroelectric $\alpha$-GeTe(111) films using a time-of-flight momentum microscope equipped with an imaging spin filter that enables a simultaneous measurement of more than 10 000 data points. The experiment reveals an opposite spin helicity of the inner and outer Rashba bands with a different spin polarization in agreement with theoretical predictions, confirming a complex spin texture of bulk Rashba states. The outer band has about twice larger spin polarization than the inner one, giving evidence of a spin-orbit effect being related to the orbital composition of the band states. The switchable inner electric field of GeTe implies new functionalities for spintronic devices.