Automated wide-line nuclear quadrupole resonance of mixed-cation lead-halide perovskites

<p>Nuclear quadrupole resonance (NQR), a technique related to nuclear magnetic resonance, is extremely sensitive to local crystal composition and structure. Unfortunately, in disordered materials, this sensitivity also leads to very large linewidths, presenting a technical challenge and requir...

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Main Authors: J. W. Wolffs, J. S. Gómez, G. E. Janssen, G. A. de Wijs, A. P. M. Kentgens
Format: Article
Language:English
Published: Copernicus Publications 2025-07-01
Series:Magnetic Resonance
Online Access:https://mr.copernicus.org/articles/6/143/2025/mr-6-143-2025.pdf
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author J. W. Wolffs
J. S. Gómez
G. E. Janssen
G. A. de Wijs
A. P. M. Kentgens
author_facet J. W. Wolffs
J. S. Gómez
G. E. Janssen
G. A. de Wijs
A. P. M. Kentgens
author_sort J. W. Wolffs
collection DOAJ
description <p>Nuclear quadrupole resonance (NQR), a technique related to nuclear magnetic resonance, is extremely sensitive to local crystal composition and structure. Unfortunately, in disordered materials, this sensitivity also leads to very large linewidths, presenting a technical challenge and requiring a serious time investment to get a full spectrum. Here, we describe our newly developed, automated NQR set-up to acquire high-quality wide-line spectra. Using this set-up, we carried out <span class="inline-formula"><sup>127</sup></span>I NQR on three mixed-cation lead-halide perovskites (LHPs) of the form MA<span class="inline-formula"><sub><i>x</i></sub></span>FA<span class="inline-formula"><sub>1−<i>x</i></sub></span>PbI<span class="inline-formula"><sub>3</sub></span> (where MA denotes methylammonium; FA denotes formamidinium; and <span class="inline-formula"><i>x</i> =</span> 0.25, 0.50 and 0.75) at various temperatures. We achieve a signal-to-noise ratio of up to <span class="inline-formula">∼ 400</span> for lineshapes with a full width at half maximum of <span class="inline-formula">∼ 2.5 MHz</span> acquired with a spectral width of 20 MHz in the course of 2–3 d. The spectra, which at least partially exhibit features encoding structural information, are interpreted using a statistical model. This model finds a degree of MA–MA and FA–FA clustering (<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M8" display="inline" overflow="scroll" dspmath="mathml"><mrow><mn mathvariant="normal">0.2</mn><mspace linebreak="nobreak" width="0.125em"/><mo>≤</mo><mspace width="0.125em" linebreak="nobreak"/><mi>S</mi><mspace width="0.125em" linebreak="nobreak"/><mo>≤</mo><mspace linebreak="nobreak" width="0.125em"/><mn mathvariant="normal">0.35</mn></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="77pt" height="11pt" class="svg-formula" dspmath="mathimg" md5hash="3a87b1914cc7526b85faf97a713928fc"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="mr-6-143-2025-ie00001.svg" width="77pt" height="11pt" src="mr-6-143-2025-ie00001.png"/></svg:svg></span></span>). This proof-of-principle for both the wide-line NQR set-up and the statistical model widens the applicability of an underutilised avenue of non-invasive structural research.</p>
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spelling doaj-art-dbcefe91bfc84d41b7601c1cf4d5815f2025-08-20T03:50:49ZengCopernicus PublicationsMagnetic Resonance2699-00162025-07-01614315510.5194/mr-6-143-2025Automated wide-line nuclear quadrupole resonance of mixed-cation lead-halide perovskitesJ. W. Wolffs0J. S. Gómez1G. E. Janssen2G. A. de Wijs3A. P. M. Kentgens4Institute for Molecules and Materials, Radboud Universiteit, Heyendaalseweg 135, 6525 AJ Nijmegen, the NetherlandsInstitute for Molecules and Materials, Radboud Universiteit, Heyendaalseweg 135, 6525 AJ Nijmegen, the NetherlandsInstitute for Molecules and Materials, Radboud Universiteit, Heyendaalseweg 135, 6525 AJ Nijmegen, the NetherlandsInstitute for Molecules and Materials, Radboud Universiteit, Heyendaalseweg 135, 6525 AJ Nijmegen, the NetherlandsInstitute for Molecules and Materials, Radboud Universiteit, Heyendaalseweg 135, 6525 AJ Nijmegen, the Netherlands<p>Nuclear quadrupole resonance (NQR), a technique related to nuclear magnetic resonance, is extremely sensitive to local crystal composition and structure. Unfortunately, in disordered materials, this sensitivity also leads to very large linewidths, presenting a technical challenge and requiring a serious time investment to get a full spectrum. Here, we describe our newly developed, automated NQR set-up to acquire high-quality wide-line spectra. Using this set-up, we carried out <span class="inline-formula"><sup>127</sup></span>I NQR on three mixed-cation lead-halide perovskites (LHPs) of the form MA<span class="inline-formula"><sub><i>x</i></sub></span>FA<span class="inline-formula"><sub>1−<i>x</i></sub></span>PbI<span class="inline-formula"><sub>3</sub></span> (where MA denotes methylammonium; FA denotes formamidinium; and <span class="inline-formula"><i>x</i> =</span> 0.25, 0.50 and 0.75) at various temperatures. We achieve a signal-to-noise ratio of up to <span class="inline-formula">∼ 400</span> for lineshapes with a full width at half maximum of <span class="inline-formula">∼ 2.5 MHz</span> acquired with a spectral width of 20 MHz in the course of 2–3 d. The spectra, which at least partially exhibit features encoding structural information, are interpreted using a statistical model. This model finds a degree of MA–MA and FA–FA clustering (<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M8" display="inline" overflow="scroll" dspmath="mathml"><mrow><mn mathvariant="normal">0.2</mn><mspace linebreak="nobreak" width="0.125em"/><mo>≤</mo><mspace width="0.125em" linebreak="nobreak"/><mi>S</mi><mspace width="0.125em" linebreak="nobreak"/><mo>≤</mo><mspace linebreak="nobreak" width="0.125em"/><mn mathvariant="normal">0.35</mn></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="77pt" height="11pt" class="svg-formula" dspmath="mathimg" md5hash="3a87b1914cc7526b85faf97a713928fc"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="mr-6-143-2025-ie00001.svg" width="77pt" height="11pt" src="mr-6-143-2025-ie00001.png"/></svg:svg></span></span>). This proof-of-principle for both the wide-line NQR set-up and the statistical model widens the applicability of an underutilised avenue of non-invasive structural research.</p>https://mr.copernicus.org/articles/6/143/2025/mr-6-143-2025.pdf
spellingShingle J. W. Wolffs
J. S. Gómez
G. E. Janssen
G. A. de Wijs
A. P. M. Kentgens
Automated wide-line nuclear quadrupole resonance of mixed-cation lead-halide perovskites
Magnetic Resonance
title Automated wide-line nuclear quadrupole resonance of mixed-cation lead-halide perovskites
title_full Automated wide-line nuclear quadrupole resonance of mixed-cation lead-halide perovskites
title_fullStr Automated wide-line nuclear quadrupole resonance of mixed-cation lead-halide perovskites
title_full_unstemmed Automated wide-line nuclear quadrupole resonance of mixed-cation lead-halide perovskites
title_short Automated wide-line nuclear quadrupole resonance of mixed-cation lead-halide perovskites
title_sort automated wide line nuclear quadrupole resonance of mixed cation lead halide perovskites
url https://mr.copernicus.org/articles/6/143/2025/mr-6-143-2025.pdf
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AT gejanssen automatedwidelinenuclearquadrupoleresonanceofmixedcationleadhalideperovskites
AT gadewijs automatedwidelinenuclearquadrupoleresonanceofmixedcationleadhalideperovskites
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