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Realizing the Lowest Bandgap and Exciton Binding Energy in a Two-Dimensional Lead Halide System

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    Realizing the Lowest Bandgap and Exciton Binding Energy in a Two-Dimensional Lead Halide System
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 29, 15896–15905
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    https://doi.org/10.1021/jacs.3c03300
    Published July 13, 2023
    Copyright © 2023 American Chemical Society
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    Abstract

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    Finding stable analogues of three-dimensional (3D) lead halide perovskites has motivated the exploration of an ever-expanding repertoire of two-dimensional (2D) counterparts. However, the bandgap and exciton binding energy in these 2D systems are generally considerably higher than those in 3D analogues due to size and dielectric confinement. Such quantum confinements are most prominently manifested in the extreme 2D realization in (A)mPbI4 (m = 1 or 2) series of compounds with a single inorganic layer repeat unit. Here, we explore a new A-site cation, 4,4′-azopyridine (APD), whose size and hydrogen bonding properties endow the corresponding (APD)PbI4 2D compound with the lowest bandgap and exciton binding energy of all such compounds, 2.19 eV and 48 meV, respectively. (APD)PbI4 presents the first example of the ideal Pb–I–Pb bond angle of 180°, maximizing the valence and conduction bandwidths and minimizing the electron and hole effective masses. These effects coupled with a significant increase in the dielectric constant provide an explanation for the unique bandgap and exciton binding energies in this system. Our theoretical results further reveal that the requirement of optimizing the hydrogen bonding interactions between the organic and the inorganic units provides the driving force for achieving the structural uniqueness and the associated optoelectronic properties in this system. Our preliminary investigations in characterizing photovoltaic solar cells in the presence of APD show encouraging improvements in performances and stability.

    Copyright © 2023 American Chemical Society

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.3c03300.

    • Experimental section, synthesis procedure, material characterization, computational methods, powder X-ray diffraction, NMR, SEM, DSC, dielectric measurement, absorption spectra and associated analysis, Raman spectra, stability test studies, crystal data and comparison of bandgaps and exciton binding energies (PDF)

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    CCDC 2244358 and 2264398 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 29, 15896–15905
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.3c03300
    Published July 13, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

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