Systematic Bandgap Engineering of a 2D Organic–Inorganic Chalcogenide Semiconductor via Ligand Modification
Name
sakurada-et-al-2025-systematic-bandgap-engineering-of-a-2d-organic-inorganic-chalcogenide-semiconductor-via-ligand.pdf
Description
Published version
Size
5.68 MB
Format
Adobe PDF
Checksum (MD5)
9735c234e1376198874cb222fd537b4a
Author(s)
Sakurada, Tomoaki
Paritmongkol, Watcharaphol
Cho, Yeongsu
Lee, Woo Seok
Chatsiri, Petcharaphorn
Oppenheim, Julius J
Wan, Ruomeng
Su, Annlin
Samulewicz, Nicholas
Wannakan, Khemika
Date Issued
August 19, 2025
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Citation
Sakurada, Tomoaki, Paritmongkol, Watcharaphol, Cho, Yeongsu, Lee, Woo Seok, Chatsiri, Petcharaphorn et al. 2025. "Systematic Bandgap Engineering of a 2D Organic–Inorganic Chalcogenide Semiconductor via Ligand Modification." Journal of the American Chemical Society.
Version
Final published version
Abstract
Hybrid organic–inorganic semiconductors present new opportunities for optoelectronic materials design not available in all-organic or all-inorganic materials. One example is silver phenylselenide (AgSePh) – or “mithrene” – a blue-emitting 2D organic–inorganic semiconductor exhibiting strong optical and electronic anisotropy. Here, we show that the bandgap of mithrene can be systematically tuned by introducing electron-donating and electron-withdrawing groups to the phenyl ligands. We synthesized nine mithrene variants, eight of which formed 2D van der Waals crystals analogous to those of AgSePh. Density functional theory calculations reveal that these 2D mithrene variants are direct-gap or nearly direct gap semiconductors. Furthermore, we identify correlations between the optical gap and three experimental observables – the Hammett constant, 77Se chemical shift, and selenium partial charge – offering predictive power for bandgap tuning. These findings highlight new opportunities for applying the tools of chemical synthesis to semiconductor materials design.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution
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DOI of Published Version
https://doi.org/10.1021/jacs.5c07989
