A Complicated Route from Disorder to Order in Antimony-Tellurium Binary Phase Change Materials.

The disorder-to-order (crystallization) process in phase-change materials determines the speed and storage polymorphism of phase-change memory devices. Only by clarifying the fine-structure variation can the devices be insightfully designed, and encode and store information. As essential phase-change parent materials, the crystallized Sb-Te binary system is generally considered to have the cationic/anionic site occupied by Sb/Te atoms. Here, direct atomic identification and simulation demonstrate that the ultrafast crystallization speed of Sb-Te materials is due to the random nature of lattice site occupation by different classes of atoms with the resulting octahedral motifs having high similarity to the amorphous state. It is further proved that after atomic ordering with disordered chemical occupation, chemical ordering takes place, which results in different storage states with different resistance values. These new insights into the complicated route from disorder to order will play an essential role in designing neuromorphic devices with varying polymorphisms.

Band Gap Engineering in Ultimately Thin Slabs of CdTe with Different Layer Stackings.

Ultrathin solid slabs often have properties different from those of the bulk phase. This effect can be observed both in traditional three-dimensional materials and in van der Waals (vdW) solids in the few monolayer limit. In the present work, the band gap variation of the CdTe slabs, induced by their thickness, was studied by the density functional theory (DFT) method for the sphalerite (zinc-blende) phase and for the recently proposed inverted phase. The sphalerite phase has the Te-Cd-Te-Cd atomic plane sequence, while in the inverted phase Cd atoms are sandwiched by Te planes forming vdW blocks with the sequence Te-Cd-Cd-Te. Based on these building blocks, a bulk vdW CdTe crystal was built, whose thermodynamical stability was verified by DFT calculations. Band structures and partial densities of states for sphalerite and inverted phases were calculated. It was demonstrated for both phases that using slabs with a thickness of one to several monolayers for sphalerite phase (vdW blocks for inverted phase), structures with band gaps varying in a wide range can be obtained. The presented results allow us to argue that ultrathin CdTe can be a promising electronic material.

Lone-Pair-Enabled Polymorphism and Photostructural Changes in Chalcogenide Glasses.

S- and Se-based chalcogenide glasses are intrinsically metastable and exhibit a number of photo-induced effects unique to this class of materials, reversible photostructural changes and photo-induced anisotropy being major examples. These effects are usually interpreted in terms of the formation of valence alternation pairs and 'wrong' bonds. In this work, using density functional theory simulations, we demonstrate for the case example of As2S3 that a strong decrease in the optical band gap can be achieved if a polymorphic transformation of the local structure from orpiment to that of tetradymite takes place. For the formation of the latter, the presence of lone-pair electrons in near-linear atomic configurations is crucial. Our results represent a novel approach to understanding the photo-induced structural changes in chalcogenide glasses as being due to the presence of polymorphism, and will lead to their wider use in various photonic devices.

Amorphous As2S3 Doped with Transition Metals: An Ab Initio Study of Electronic Structure and Magnetic Properties.

Crystalline transition-metal chalcogenides are the focus of solid state research. At the same time, very little is known about amorphous chalcogenides doped with transition metals. To close this gap, we have studied, using first principle simulations, the effect of doping the typical chalcogenide glass As2S3 with transition metals (Mo, W and V). While the undoped glass is a semiconductor with a density functional theory gap of about 1 eV, doping results in the formation of a finite density of states (semiconductor-to-metal transformation) at the Fermi level accompanied by an appearance of magnetic properties, the magnetic character depending on the nature of the dopant. Whilst the magnetic response is mainly associated with d-orbitals of the transition metal dopants, partial densities of spin-up and spin-down states associated with arsenic and sulphur also become slightly asymmetric. Our results demonstrate that chalcogenide glasses doped with transition metals may become a technologically important material.