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Interplay of Kinetic and Thermodynamic Reaction Control Explains Incorporation of Dimethylammonium Iodide into CsPbI(3)
[Image: see text] CsPbI(3) is a promising material for optoelectronics owing to its thermal robustness and favorable bandgap. However, its fabrication is challenging because its photoactive phase is thermodynamically unstable at room temperature. Adding dimethylammonium (DMA) alleviates this instabi...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9380017/ https://www.ncbi.nlm.nih.gov/pubmed/35990415 http://dx.doi.org/10.1021/acsenergylett.2c00877 |
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author | Mishra, Aditya Kubicki, Dominik J. Boziki, Ariadni Chavan, Rohit D. Dankl, Mathias Mladenović, Marko Prochowicz, Daniel Grey, Clare P. Rothlisberger, Ursula Emsley, Lyndon |
author_facet | Mishra, Aditya Kubicki, Dominik J. Boziki, Ariadni Chavan, Rohit D. Dankl, Mathias Mladenović, Marko Prochowicz, Daniel Grey, Clare P. Rothlisberger, Ursula Emsley, Lyndon |
author_sort | Mishra, Aditya |
collection | PubMed |
description | [Image: see text] CsPbI(3) is a promising material for optoelectronics owing to its thermal robustness and favorable bandgap. However, its fabrication is challenging because its photoactive phase is thermodynamically unstable at room temperature. Adding dimethylammonium (DMA) alleviates this instability and is currently understood to result in the formation of DMA(x)Cs(1–x)PbI(3) perovskite solid solutions. Here, we use NMR of the (133)Cs and (13)C local structural probes to show that these solid solutions are not thermodynamically stable, and their synthesis under thermodynamic control leads to a segregated mixture of yellow one-dimensional DMAPbI(3) phase and δ-CsPbI(3). We show that mixed-cation DMA(x)Cs(1–x)PbI(3) perovskite phases only form when they are kinetically trapped by rapid antisolvent-induced crystallization. We explore the energetics of DMA incorporation into CsPbI(3) using first-principles calculations and molecular dynamics simulations and find that this process is energetically unfavorable. Our results provide a complete atomic-level picture of the mechanism of DMA-induced stabilization of the black perovskite phase of CsPbI(3) and shed new light on this deceptively simple material. |
format | Online Article Text |
id | pubmed-9380017 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-93800172022-08-17 Interplay of Kinetic and Thermodynamic Reaction Control Explains Incorporation of Dimethylammonium Iodide into CsPbI(3) Mishra, Aditya Kubicki, Dominik J. Boziki, Ariadni Chavan, Rohit D. Dankl, Mathias Mladenović, Marko Prochowicz, Daniel Grey, Clare P. Rothlisberger, Ursula Emsley, Lyndon ACS Energy Lett [Image: see text] CsPbI(3) is a promising material for optoelectronics owing to its thermal robustness and favorable bandgap. However, its fabrication is challenging because its photoactive phase is thermodynamically unstable at room temperature. Adding dimethylammonium (DMA) alleviates this instability and is currently understood to result in the formation of DMA(x)Cs(1–x)PbI(3) perovskite solid solutions. Here, we use NMR of the (133)Cs and (13)C local structural probes to show that these solid solutions are not thermodynamically stable, and their synthesis under thermodynamic control leads to a segregated mixture of yellow one-dimensional DMAPbI(3) phase and δ-CsPbI(3). We show that mixed-cation DMA(x)Cs(1–x)PbI(3) perovskite phases only form when they are kinetically trapped by rapid antisolvent-induced crystallization. We explore the energetics of DMA incorporation into CsPbI(3) using first-principles calculations and molecular dynamics simulations and find that this process is energetically unfavorable. Our results provide a complete atomic-level picture of the mechanism of DMA-induced stabilization of the black perovskite phase of CsPbI(3) and shed new light on this deceptively simple material. American Chemical Society 2022-07-26 2022-08-12 /pmc/articles/PMC9380017/ /pubmed/35990415 http://dx.doi.org/10.1021/acsenergylett.2c00877 Text en © 2022 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 | Mishra, Aditya Kubicki, Dominik J. Boziki, Ariadni Chavan, Rohit D. Dankl, Mathias Mladenović, Marko Prochowicz, Daniel Grey, Clare P. Rothlisberger, Ursula Emsley, Lyndon Interplay of Kinetic and Thermodynamic Reaction Control Explains Incorporation of Dimethylammonium Iodide into CsPbI(3) |
title | Interplay
of Kinetic and Thermodynamic Reaction Control
Explains Incorporation of Dimethylammonium Iodide into CsPbI(3) |
title_full | Interplay
of Kinetic and Thermodynamic Reaction Control
Explains Incorporation of Dimethylammonium Iodide into CsPbI(3) |
title_fullStr | Interplay
of Kinetic and Thermodynamic Reaction Control
Explains Incorporation of Dimethylammonium Iodide into CsPbI(3) |
title_full_unstemmed | Interplay
of Kinetic and Thermodynamic Reaction Control
Explains Incorporation of Dimethylammonium Iodide into CsPbI(3) |
title_short | Interplay
of Kinetic and Thermodynamic Reaction Control
Explains Incorporation of Dimethylammonium Iodide into CsPbI(3) |
title_sort | interplay
of kinetic and thermodynamic reaction control
explains incorporation of dimethylammonium iodide into cspbi(3) |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9380017/ https://www.ncbi.nlm.nih.gov/pubmed/35990415 http://dx.doi.org/10.1021/acsenergylett.2c00877 |
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