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Interplay of kinetic and thermodynamic reaction control explains incorporation of dimethylammonium iodide into CsPbI3
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Mishra, Aditya, Kubicki, Dominik, Boziki, Ariadni, Chavan, Rohit D., Dankl, Mathias, Mladenović, Marko, Prochowicz, Daniel, Grey, Clare P., Rothlisberger, Ursula and Emsley, Lyndon (2022) Interplay of kinetic and thermodynamic reaction control explains incorporation of dimethylammonium iodide into CsPbI3. ACS Energy Letters, 7 (8). pp. 2745-2752. doi:10.1021/acsenergylett.2c00877 ISSN 2380-8195.
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Official URL: https://doi.org/10.1021/acsenergylett.2c00877
Abstract
CsPbI3 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 DMAxCs1–xPbI3 perovskite solid solutions. Here, we use NMR of the 133Cs and 13C 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 DMAPbI3 phase and δ-CsPbI3. We show that mixed-cation DMAxCs1–xPbI3 perovskite phases only form when they are kinetically trapped by rapid antisolvent-induced crystallization. We explore the energetics of DMA incorporation into CsPbI3 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 CsPbI3 and shed new light on this deceptively simple material.
Item Type: | Journal Article | ||||||||||||||||||
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Subjects: | Q Science > QD Chemistry T Technology > TA Engineering (General). Civil engineering (General) |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Physics |
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SWORD Depositor: | Library Publications Router | ||||||||||||||||||
Library of Congress Subject Headings (LCSH): | Iodides, Optoelectronics, Thermodynamics, Perovskite materials | ||||||||||||||||||
Journal or Publication Title: | ACS Energy Letters | ||||||||||||||||||
Publisher: | American Chemical Society | ||||||||||||||||||
ISSN: | 2380-8195 | ||||||||||||||||||
Official Date: | 12 August 2022 | ||||||||||||||||||
Dates: |
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Volume: | 7 | ||||||||||||||||||
Number: | 8 | ||||||||||||||||||
Page Range: | pp. 2745-2752 | ||||||||||||||||||
DOI: | 10.1021/acsenergylett.2c00877 | ||||||||||||||||||
Status: | Peer Reviewed | ||||||||||||||||||
Publication Status: | Published | ||||||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||||||||||||
Date of first compliant deposit: | 17 October 2022 | ||||||||||||||||||
Date of first compliant Open Access: | 18 October 2022 | ||||||||||||||||||
RIOXX Funder/Project Grant: |
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