Rich Polymorphism of Layered NbS3

Abstract

Layered group V transition-metal trichalcogenides are paradigmatic low-dimensional materials providing an ever increasing series of unusual properties. They are all based on the same basic building units, one-dimensional MX3 (M = Nb, Ta; X = S, Se) trigonal-prismatic chains that condense into layers, but their electronic structures exhibit significant differences leading to a broad spectrum of transport properties, ranging from metals with one, two, or three charge density wave instabilities to semimetals with potential topological properties or semiconductors. The different physical and chemical properties are shown to be related with subtle structural differences within the layers that result in half-, third-, or quarter-filled quasi-one-dimensional Nb dz2-type bands, providing a clear-cut illustration of the intimate link between structural and electronic features within a family of solids. An interesting yet not sufficiently explored feature of these solids is the polymorphism. Based on both experimental and new theoretical results, we examine this aspect for NbS3 and show that at least seven different polymorphs with a stability compatible with the presently known phases of this compound are possible. We discuss a simple rationale for the physical properties of the presently known polymorphs as well as predictions for those that have still not been characterized or prepared. It is argued that some of the presently unknown polymorphs may have been prepared in an uncontrolled way as mixtures of different phases which could not be structurally characterized. The rich landscape of structures and properties found for this van der Waals material is suggested to represent an ideal platform for the preparation of flakes with fine-tuned properties for applications in new electronic and optoelectronic devices.