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

Yujing Wei; Artem G. Volosniev; Dusan Lorenc; Ayan A. Zhumekenov; Osman M. Bakr; Mikhail Lemeshko; Zhanybek Alpichshev

doi:10.1021/acs.jpclett.3c01158

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

Yujing Wei, Artem G. Volosniev, Dusan Lorenc, Ayan A. Zhumekenov, Osman M. Bakr, Mikhail Lemeshko, Zhanybek Alpichshev^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	6309-6314
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	14
Issue number	27
DOIs	https://doi.org/10.1021/acs.jpclett.3c01158
State	Published - Jul 13 2023

Bibliographical note

Funding Information:
We thank Bingqing Cheng and Hong-Zhou Ye for valuable discussions; Y.W.’s work at IST Austria was supported through ISTernship summer internship program funded by OeAD-GmbH; D.L. and Z.A. acknowledge support by IST Austria (ISTA); M.L. acknowledges support by the European Research Council (ERC) Starting Grant No. 801770 (ANGULON). A.A.Z. and O.M.B. acknowledge support by KAUST.

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society

ASJC Scopus subject areas

General Materials Science
Physical and Theoretical Chemistry

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10.1021/acs.jpclett.3c01158

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title = "Bond Polarizability as a Probe of Local Crystal Fields in Hybrid Lead-Halide Perovskites",

abstract = "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.",

author = "Yujing Wei and Volosniev, {Artem G.} and Dusan Lorenc and Zhumekenov, {Ayan A.} and Bakr, {Osman M.} and Mikhail Lemeshko and Zhanybek Alpichshev",

note = "Funding Information: We thank Bingqing Cheng and Hong-Zhou Ye for valuable discussions; Y.W.{\textquoteright}s work at IST Austria was supported through ISTernship summer internship program funded by OeAD-GmbH; D.L. and Z.A. acknowledge support by IST Austria (ISTA); M.L. acknowledges support by the European Research Council (ERC) Starting Grant No. 801770 (ANGULON). A.A.Z. and O.M.B. acknowledge support by KAUST. Publisher Copyright: {\textcopyright} 2023 The Authors. Published by American Chemical Society",

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AU - Lemeshko, Mikhail

AU - Alpichshev, Zhanybek

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PY - 2023/7/13

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N2 - 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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Bond Polarizability as a Probe of Local Crystal Fields in Hybrid Lead-Halide Perovskites

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