Solution-Phase Synthesis and Photoluminescence of Quaternary Chalcohalide Semiconductors

• Published in: Chemistry of materials 2023-03, Vol.35 (5), p.2165-2172
• Main Authors: Roth, Alison N., Opare-Addo, Jemima, Gi, Eunbyeol, Mena, Silvia, Guirado, Gonzalo, Schaller, Richard D., Smith, Emily A., Vela, Javier
• Format: Article
• Language: English
• Subjects: Chemical synthesis; Diffraction; Electrical conductivity; Energy; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Semiconductors
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/acs.chemmater.3c00011

Mixed-metal chalcohalide semiconductors have emerged as promising candidates for photovoltaic applications. However, preparation of these multinary compounds using solution-phase techniques remains particularly challenging compared to traditional solid-state methods. To fully harness their potential, it is desirable to develop synthetic methods that enable control over both the phase purity and dimensionality of chalcohalides. Here, we report the solution-phase synthesis of Pb2SbS2I3 and Pb2BiS2I3 quaternary chalcohalides using readily available precursors. Fine tuning of reaction parameters allows for the isolation of rod-like morphologies with tunable diameters and aspect ratios. The quaternary chalcohalides display photoluminescence as an ensemble as well as at the single particle level, as demonstrated using fluorescence microscopy. We further evaluate the relative stability and band gap of Pb2SbS2I3 polymorphs and their coloring patterns using electronic structure calculations. The synthetic methods developed here will motivate the study of ever more complex chalcohalides and other multinary semiconductors for new technological applications.