On the polytypism of layered $\textit{MX}_2$ materials

TL;DR

This paper develops a new labeling scheme for stacking arrangements in layered MX2 materials, creating a comprehensive phase space model that explains structural variations and suggests ways to control material properties through composition and temperature changes.

Contribution

It introduces a compact labeling system for MX2 stacking sequences and constructs a phase space model that captures all possible polytypes, enhancing understanding of structural evolution.

Findings

Most common structures are limiting cases in the phase space

Structural evolution aligns with temperature and composition changes

Potential for new control strategies in material design

Abstract

We revisit the problem of polytypism in layered $\textit{MX}_2$ materials, with a view to reinterpreting the phase space accessible to this family. Our starting point is to develop a simple, constructive and compact label for the most commonly observed stacking arrangements that is similar to the Glazer notation used to label tilt systems in perovskites. The key advantage of this label in the context of $\textit{MX}_2$ systems is that it contains sufficient information to generate the corresponding stacking sequences uniquely. Using a related approach, we generate a Cartesian representation of the phase space containing all possible $\textit{MX}_2$ polytypes, with the most common structures appearing as limiting cases. We argue that variation in (e.g. composition, or temperature, or pressure) may allow navigation of this phase space along continuous paths. This interpretation is shown to be consistent with the structural evolution of stacking-faulted $\textit{MX}_2$ systems as a function of temperature and composition. Our study highlights the potential for controlling composition/structure/property relationships amongst layered $\textit{MX}_2$ materials in ways that might not previously have been obvious.