Formability of ABS₃ Perovskites

In this study, the formability of ABS₃ sulfide perovskites is investigated based on the collection of 138 pseudobinary ABS₃ systems with tolerance factor-octahedral factor structural map (termed "<i>t</i> - <i>μ</i>" structural map) method. These 138 binary systems are denoted as A₂S-B₂S₅, AS-BS₂, or A₂S₃-B₂S₃, with 24 perovskite systems and the rest nonperovskite systems. It is found that almost all perovskite systems are localized in the upper right part of the <i>t</i> - <i>μ</i> map, while most nonperovskite systems are distributed in other locations. The formation rules for ABS₃ perovskites are identified with 96.38% accuracy, with only four systems being misclassified. These misclassified systems include four nonperovskite systems (PbS-HfS₂, PbS-ZrS₂, SnS-HfS₂, SnS-ZrS₂). The misclassification of these four systems may be due to the stereochemically active nature of the ns² lone pairs in Pb²⁺ and Sn²⁺ ions and the excessively small electronegativity of the A-site ion leading to an overtwisting of the corresponding octahedron. Based on these formation rules, 447 potential ABS₃ perovskites are proposed. This work will provide assistance and guidance for the development of novel sulfide perovskite materials.