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Microscopic (Dis)order and Dynamics of Cations in Mixed FA/MA Lead Halide Perovskites
[Image: see text] Recent developments in the field of high efficiency perovskite solar cells are based on stabilization of the perovskite crystal structure of FAPbI(3) while preserving its excellent optoelectronic properties. Compositional engineering of, for example, MA or Br mixed into FAPbI(3) re...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7848893/ https://www.ncbi.nlm.nih.gov/pubmed/33542781 http://dx.doi.org/10.1021/acs.jpcc.0c10042 |
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author | Grüninger, Helen Bokdam, Menno Leupold, Nico Tinnemans, Paul Moos, Ralf De Wijs, Gilles A. Panzer, Fabian Kentgens, Arno P. M. |
author_facet | Grüninger, Helen Bokdam, Menno Leupold, Nico Tinnemans, Paul Moos, Ralf De Wijs, Gilles A. Panzer, Fabian Kentgens, Arno P. M. |
author_sort | Grüninger, Helen |
collection | PubMed |
description | [Image: see text] Recent developments in the field of high efficiency perovskite solar cells are based on stabilization of the perovskite crystal structure of FAPbI(3) while preserving its excellent optoelectronic properties. Compositional engineering of, for example, MA or Br mixed into FAPbI(3) results in the desired effects, but detailed knowledge of local structural features, such as local (dis)order or cation interactions of formamidinium (FA) and methylammonium (MA), is still limited. This knowledge is, however, crucial for their further development. Here, we shed light on the microscopic distribution of MA and FA in mixed perovskites MA(1–x)FA(x)PbI(3) and MA(0.15)FA(0.85)PbI(2.55)Br(0.45) by combining high-resolution double-quantum (1)H solid-state nuclear magnetic resonance (NMR) spectroscopy with state-of-the-art near-first-principles accuracy molecular dynamics (MD) simulations using machine-learning force-fields (MLFFs). We show that on a small local scale, partial MA and FA clustering takes place over the whole MA/FA compositional range. A reasonable driving force for the clustering might be an increase of the dynamical freedom of FA cations in FA-rich regions. While MA(0.15)FA(0.85)PbI(2.55)Br(0.45) displays similar MA and FA ordering as the MA(1–x)FA(x)PbI(3) systems, the average cation–cation interaction strength increased significantly in this double mixed material, indicating a restriction of the space accessible to the cations or their partial immobilization upon Br(–) incorporation. Our results shed light on the heterogeneities in cation composition of mixed halide perovskites, helping to exploit their full optoelectronic potential. |
format | Online Article Text |
id | pubmed-7848893 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-78488932021-02-02 Microscopic (Dis)order and Dynamics of Cations in Mixed FA/MA Lead Halide Perovskites Grüninger, Helen Bokdam, Menno Leupold, Nico Tinnemans, Paul Moos, Ralf De Wijs, Gilles A. Panzer, Fabian Kentgens, Arno P. M. J Phys Chem C Nanomater Interfaces [Image: see text] Recent developments in the field of high efficiency perovskite solar cells are based on stabilization of the perovskite crystal structure of FAPbI(3) while preserving its excellent optoelectronic properties. Compositional engineering of, for example, MA or Br mixed into FAPbI(3) results in the desired effects, but detailed knowledge of local structural features, such as local (dis)order or cation interactions of formamidinium (FA) and methylammonium (MA), is still limited. This knowledge is, however, crucial for their further development. Here, we shed light on the microscopic distribution of MA and FA in mixed perovskites MA(1–x)FA(x)PbI(3) and MA(0.15)FA(0.85)PbI(2.55)Br(0.45) by combining high-resolution double-quantum (1)H solid-state nuclear magnetic resonance (NMR) spectroscopy with state-of-the-art near-first-principles accuracy molecular dynamics (MD) simulations using machine-learning force-fields (MLFFs). We show that on a small local scale, partial MA and FA clustering takes place over the whole MA/FA compositional range. A reasonable driving force for the clustering might be an increase of the dynamical freedom of FA cations in FA-rich regions. While MA(0.15)FA(0.85)PbI(2.55)Br(0.45) displays similar MA and FA ordering as the MA(1–x)FA(x)PbI(3) systems, the average cation–cation interaction strength increased significantly in this double mixed material, indicating a restriction of the space accessible to the cations or their partial immobilization upon Br(–) incorporation. Our results shed light on the heterogeneities in cation composition of mixed halide perovskites, helping to exploit their full optoelectronic potential. American Chemical Society 2021-01-15 2021-01-28 /pmc/articles/PMC7848893/ /pubmed/33542781 http://dx.doi.org/10.1021/acs.jpcc.0c10042 Text en © 2021 The Authors. Published by American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Grüninger, Helen Bokdam, Menno Leupold, Nico Tinnemans, Paul Moos, Ralf De Wijs, Gilles A. Panzer, Fabian Kentgens, Arno P. M. Microscopic (Dis)order and Dynamics of Cations in Mixed FA/MA Lead Halide Perovskites |
title | Microscopic (Dis)order and Dynamics of Cations in
Mixed FA/MA Lead Halide Perovskites |
title_full | Microscopic (Dis)order and Dynamics of Cations in
Mixed FA/MA Lead Halide Perovskites |
title_fullStr | Microscopic (Dis)order and Dynamics of Cations in
Mixed FA/MA Lead Halide Perovskites |
title_full_unstemmed | Microscopic (Dis)order and Dynamics of Cations in
Mixed FA/MA Lead Halide Perovskites |
title_short | Microscopic (Dis)order and Dynamics of Cations in
Mixed FA/MA Lead Halide Perovskites |
title_sort | microscopic (dis)order and dynamics of cations in
mixed fa/ma lead halide perovskites |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7848893/ https://www.ncbi.nlm.nih.gov/pubmed/33542781 http://dx.doi.org/10.1021/acs.jpcc.0c10042 |
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