Year: 2026
Type: article
Abstract: Hexagonal perovskites with face-sharing octahedral connectivity are an underexplored class of materials. We propose quantitative design principles for stabilizing face-sharing ABX 3 hexagonal perovskites based on a comparative analysis of oxides and sulfides. By mapping structural preferences across a phase space defined by an electronegativity-corrected tolerance factor and the Shannon radius of the A -site cations, we identify distinct thresholds that separate hexagonal phases from competing cubic polymorphs having corner-sharing octahedral connectivity. Our analysis reveals that sulfides differ significantly from oxides due to the increased covalency of the transition metal–sulfur bonds, which enables broader compositional flexibility. Applying these principles, we predict a set of thermodynamically formable AB O 3 and AB S 3 compounds that are likely to adopt face-sharing octahedral connectivity. These findings establish a predictive framework for designing hexagonal perovskites, highlighting sulfides as promising candidates for obtaining quasi-one-dimensional materials having transition-metal cations for novel ferroic phenomena.
Source: Chemistry of Materials
Institution: Washington University in St. Louis
Language: English
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: green
Funder: Division of Materials Research
Awards: G2022785388, G6371783279, G8012535901
OpenAlex ID: W7128744120