Sponsor
This work was supported by the U.S. National Science Foundation under Grant No. DMR-2532260. Materials characterization was conducted at the at the Integrated Macromolecular and Small Molecule X-ray Crystallography Facility, and the Materials Characterization Lab, both at Penn State. The authors would like to thank Hemant Yennawar for support with structural characterization and acknowledge support from the National Institutes of Health through Award Nos. 1S10OD028589-01 and 1S10RR023439-01 for X-ray instrumentation. H.L. and Y.X. acknowledge support from the U.S. National Science Foundation through award DMR-2532261. We acknowledge the computing resources provided by Bridges2 at Pittsburgh Supercomputing Center (PSC) through allocations mat220006p and mat220008p from the Advanced Cyber-infrastructure Coordination Ecosystem: Services & Support (ACCESS) program, which is supported by the National Science Foundation Grant Nos. 2138259, 2138286, 2138307, 2137603, and 2138296.
Published In
Chemistry of Materials
Document Type
Article
Publication Date
6-23-2026
Subjects
Chalcogenides, Optical properties
Abstract
Ten ACuHfQ3 (A = Na, K, Rb, Cs; Q = S, Se, Te) chalcogenides were prepared via high-temperature solid-state methods and structurally characterized using single-crystal X-ray diffraction. The type-I AMM′Q3 structures are defined by the arrangement of HfQ6 octahedra (O) and CuQ4 tetrahedra (T) in their layers, which adopt either OTOT (Cmcm, Pnma) or OOTT (Pnma, P21/m) connectivity. UV–vis absorption and photoluminescence spectra indicate optical band gaps ranging from 1.2 to 1.7 eV and reveal that OTOT and OOTT variants have direct and indirect band gaps, respectively. Density functional theory calculations corroborate these experimental observations, demonstrating that this structure–property relationship extends across the broader type-I AMM′Q3 family. A survey of reported compounds reveals trends linking ionic radii to structure, wherein systems with larger alkali (A+) cations and small chalcogen (Q2–) anions preferentially adopt OTOT connectivity. To formalize this trend, a machine learning model was trained on the expanded data set and used to classify compounds as either OTOT or OOTT based on ionic radii descriptors. From the model, we construct a two-dimensional structure–property map that provides a semiquantitative framework for predicting the phase and optical features in related quaternary systems. Together, these results establish a structure–property relationship in an important class of chalcogenides and demonstrate a strategy for targeting optical properties through integrated experiment and theory.
Rights
© 2026 The Authors. Published by American Chemical Society This publication is licensed under a Creative Commons Attribution 4.0 International License.
Locate the Document
DOI
10.1021/acs.chemmater.6c00212
Persistent Identifier
https://archives.pdx.edu/ds/psu/45179
Citation Details
Tassanov, A., Lee, H., Spainhour, D. W., Xia, Y., & Hodges, J. M. (2026). Structure–Optical Property Relationships in AMM′Q 3 Chalcogenides. Chemistry of Materials, 38(12), 5938–5946.