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Bond Polarizability as a Probe of Local Crystal Fields in Hybrid Lead-Halide Perovskites

[Image: see text] A rotating organic cation and a dynamically disordered soft inorganic cage are the hallmark features of organic-inorganic lead-halide perovskites. Understanding the interplay between these two subsystems is a challenging problem, but it is this coupling that is widely conjectured t...

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Autores principales: Wei, Yujing, Volosniev, Artem G., Lorenc, Dusan, Zhumekenov, Ayan A., Bakr, Osman M., Lemeshko, Mikhail, Alpichshev, Zhanybek
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10350961/
https://www.ncbi.nlm.nih.gov/pubmed/37405449
http://dx.doi.org/10.1021/acs.jpclett.3c01158
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author Wei, Yujing
Volosniev, Artem G.
Lorenc, Dusan
Zhumekenov, Ayan A.
Bakr, Osman M.
Lemeshko, Mikhail
Alpichshev, Zhanybek
author_facet Wei, Yujing
Volosniev, Artem G.
Lorenc, Dusan
Zhumekenov, Ayan A.
Bakr, Osman M.
Lemeshko, Mikhail
Alpichshev, Zhanybek
author_sort Wei, Yujing
collection PubMed
description [Image: see text] A rotating organic cation and a dynamically disordered soft inorganic cage are the hallmark features of organic-inorganic lead-halide perovskites. Understanding the interplay between these two subsystems is a challenging problem, but it is this coupling that is widely conjectured to be responsible for the unique behavior of photocarriers in these materials. In this work, we use the fact that the polarizability of the organic cation strongly depends on the ambient electrostatic environment to put the molecule forward as a sensitive probe of the local crystal fields inside the lattice cell. We measure the average polarizability of the C/N–H bond stretching mode by means of infrared spectroscopy, which allows us to deduce the character of the motion of the cation molecule, find the magnitude of the local crystal field, and place an estimate on the strength of the hydrogen bond between the hydrogen and halide atoms. Our results pave the way for understanding electric fields in lead-halide perovskites using infrared bond spectroscopy.
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spelling pubmed-103509612023-07-18 Bond Polarizability as a Probe of Local Crystal Fields in Hybrid Lead-Halide Perovskites Wei, Yujing Volosniev, Artem G. Lorenc, Dusan Zhumekenov, Ayan A. Bakr, Osman M. Lemeshko, Mikhail Alpichshev, Zhanybek J Phys Chem Lett [Image: see text] A rotating organic cation and a dynamically disordered soft inorganic cage are the hallmark features of organic-inorganic lead-halide perovskites. Understanding the interplay between these two subsystems is a challenging problem, but it is this coupling that is widely conjectured to be responsible for the unique behavior of photocarriers in these materials. In this work, we use the fact that the polarizability of the organic cation strongly depends on the ambient electrostatic environment to put the molecule forward as a sensitive probe of the local crystal fields inside the lattice cell. We measure the average polarizability of the C/N–H bond stretching mode by means of infrared spectroscopy, which allows us to deduce the character of the motion of the cation molecule, find the magnitude of the local crystal field, and place an estimate on the strength of the hydrogen bond between the hydrogen and halide atoms. Our results pave the way for understanding electric fields in lead-halide perovskites using infrared bond spectroscopy. American Chemical Society 2023-07-05 /pmc/articles/PMC10350961/ /pubmed/37405449 http://dx.doi.org/10.1021/acs.jpclett.3c01158 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Wei, Yujing
Volosniev, Artem G.
Lorenc, Dusan
Zhumekenov, Ayan A.
Bakr, Osman M.
Lemeshko, Mikhail
Alpichshev, Zhanybek
Bond Polarizability as a Probe of Local Crystal Fields in Hybrid Lead-Halide Perovskites
title Bond Polarizability as a Probe of Local Crystal Fields in Hybrid Lead-Halide Perovskites
title_full Bond Polarizability as a Probe of Local Crystal Fields in Hybrid Lead-Halide Perovskites
title_fullStr Bond Polarizability as a Probe of Local Crystal Fields in Hybrid Lead-Halide Perovskites
title_full_unstemmed Bond Polarizability as a Probe of Local Crystal Fields in Hybrid Lead-Halide Perovskites
title_short Bond Polarizability as a Probe of Local Crystal Fields in Hybrid Lead-Halide Perovskites
title_sort bond polarizability as a probe of local crystal fields in hybrid lead-halide perovskites
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10350961/
https://www.ncbi.nlm.nih.gov/pubmed/37405449
http://dx.doi.org/10.1021/acs.jpclett.3c01158
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