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Bulk and Nanocrystalline Cesium Lead-Halide Perovskites as Seen by Halide Magnetic Resonance
[Image: see text] Lead-halide perovskites increasingly mesmerize researchers because they exhibit a high degree of structural defects and dynamics yet nonetheless offer an outstanding (opto)electronic performance on par with the best examples of structurally stable and defect-free semiconductors. Th...
Autores principales: | , , , , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2020
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7379391/ https://www.ncbi.nlm.nih.gov/pubmed/32724848 http://dx.doi.org/10.1021/acscentsci.0c00587 |
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author | Piveteau, Laura Aebli, Marcel Yazdani, Nuri Millen, Marthe Korosec, Lukas Krieg, Franziska Benin, Bogdan M. Morad, Viktoriia Piveteau, Christophe Shiroka, Toni Comas-Vives, Aleix Copéret, Christophe Lindenberg, Aaron M. Wood, Vanessa Verel, René Kovalenko, Maksym V. |
author_facet | Piveteau, Laura Aebli, Marcel Yazdani, Nuri Millen, Marthe Korosec, Lukas Krieg, Franziska Benin, Bogdan M. Morad, Viktoriia Piveteau, Christophe Shiroka, Toni Comas-Vives, Aleix Copéret, Christophe Lindenberg, Aaron M. Wood, Vanessa Verel, René Kovalenko, Maksym V. |
author_sort | Piveteau, Laura |
collection | PubMed |
description | [Image: see text] Lead-halide perovskites increasingly mesmerize researchers because they exhibit a high degree of structural defects and dynamics yet nonetheless offer an outstanding (opto)electronic performance on par with the best examples of structurally stable and defect-free semiconductors. This highly unusual feature necessitates the adoption of an experimental and theoretical mindset and the reexamination of techniques that may be uniquely suited to understand these materials. Surprisingly, the suite of methods for the structural characterization of these materials does not commonly include nuclear magnetic resonance (NMR) spectroscopy. The present study showcases both the utility and versatility of halide NMR and NQR (nuclear quadrupole resonance) for probing the structure and structural dynamics of CsPbX(3) (X = Cl, Br, I), in both bulk and nanocrystalline forms. The strong quadrupole couplings, which originate from the interaction between the large quadrupole moments of, e.g., the (35)Cl, (79)Br, and (127)I nuclei, and the local electric-field gradients, are highly sensitive to subtle structural variations, both static and dynamic. The quadrupole interaction can resolve structural changes with accuracies commensurate with synchrotron X-ray diffraction and scattering. It is shown that space-averaged site-disorder is greatly enhanced in the nanocrystals compared to the bulk, while the dynamics of nuclear spin relaxation indicates enhanced structural dynamics in the nanocrystals. The findings from NMR and NQR were corroborated by ab initio molecular dynamics, which point to the role of the surface in causing the radial strain distribution and disorder. These findings showcase a great synergy between solid-state NMR or NQR and molecular dynamics simulations in shedding light on the structure of soft lead-halide semiconductors. |
format | Online Article Text |
id | pubmed-7379391 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-73793912020-07-27 Bulk and Nanocrystalline Cesium Lead-Halide Perovskites as Seen by Halide Magnetic Resonance Piveteau, Laura Aebli, Marcel Yazdani, Nuri Millen, Marthe Korosec, Lukas Krieg, Franziska Benin, Bogdan M. Morad, Viktoriia Piveteau, Christophe Shiroka, Toni Comas-Vives, Aleix Copéret, Christophe Lindenberg, Aaron M. Wood, Vanessa Verel, René Kovalenko, Maksym V. ACS Cent Sci [Image: see text] Lead-halide perovskites increasingly mesmerize researchers because they exhibit a high degree of structural defects and dynamics yet nonetheless offer an outstanding (opto)electronic performance on par with the best examples of structurally stable and defect-free semiconductors. This highly unusual feature necessitates the adoption of an experimental and theoretical mindset and the reexamination of techniques that may be uniquely suited to understand these materials. Surprisingly, the suite of methods for the structural characterization of these materials does not commonly include nuclear magnetic resonance (NMR) spectroscopy. The present study showcases both the utility and versatility of halide NMR and NQR (nuclear quadrupole resonance) for probing the structure and structural dynamics of CsPbX(3) (X = Cl, Br, I), in both bulk and nanocrystalline forms. The strong quadrupole couplings, which originate from the interaction between the large quadrupole moments of, e.g., the (35)Cl, (79)Br, and (127)I nuclei, and the local electric-field gradients, are highly sensitive to subtle structural variations, both static and dynamic. The quadrupole interaction can resolve structural changes with accuracies commensurate with synchrotron X-ray diffraction and scattering. It is shown that space-averaged site-disorder is greatly enhanced in the nanocrystals compared to the bulk, while the dynamics of nuclear spin relaxation indicates enhanced structural dynamics in the nanocrystals. The findings from NMR and NQR were corroborated by ab initio molecular dynamics, which point to the role of the surface in causing the radial strain distribution and disorder. These findings showcase a great synergy between solid-state NMR or NQR and molecular dynamics simulations in shedding light on the structure of soft lead-halide semiconductors. American Chemical Society 2020-06-23 2020-07-22 /pmc/articles/PMC7379391/ /pubmed/32724848 http://dx.doi.org/10.1021/acscentsci.0c00587 Text en Copyright © 2020 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Piveteau, Laura Aebli, Marcel Yazdani, Nuri Millen, Marthe Korosec, Lukas Krieg, Franziska Benin, Bogdan M. Morad, Viktoriia Piveteau, Christophe Shiroka, Toni Comas-Vives, Aleix Copéret, Christophe Lindenberg, Aaron M. Wood, Vanessa Verel, René Kovalenko, Maksym V. Bulk and Nanocrystalline Cesium Lead-Halide Perovskites as Seen by Halide Magnetic Resonance |
title | Bulk and Nanocrystalline Cesium Lead-Halide Perovskites as Seen by
Halide Magnetic Resonance |
title_full | Bulk and Nanocrystalline Cesium Lead-Halide Perovskites as Seen by
Halide Magnetic Resonance |
title_fullStr | Bulk and Nanocrystalline Cesium Lead-Halide Perovskites as Seen by
Halide Magnetic Resonance |
title_full_unstemmed | Bulk and Nanocrystalline Cesium Lead-Halide Perovskites as Seen by
Halide Magnetic Resonance |
title_short | Bulk and Nanocrystalline Cesium Lead-Halide Perovskites as Seen by
Halide Magnetic Resonance |
title_sort | bulk and nanocrystalline cesium lead-halide perovskites as seen by
halide magnetic resonance |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7379391/ https://www.ncbi.nlm.nih.gov/pubmed/32724848 http://dx.doi.org/10.1021/acscentsci.0c00587 |
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