Breaking the Boundaries of the Goldschmidt Tolerance Factor with Ethylammonium Lead Iodide Perovskite Nanocrystals

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Auteurs principaux: Guvenc, C. Meric, Toso, Stefano, Ivanov, Yurii P., Saleh, Gabriele, Balci, Sinan, Divitini, Giorgio, Manna, Liberato
Format: Preprint
Publié: 2025
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author Guvenc, C. Meric
Toso, Stefano
Ivanov, Yurii P.
Saleh, Gabriele
Balci, Sinan
Divitini, Giorgio
Manna, Liberato
author_facet Guvenc, C. Meric
Toso, Stefano
Ivanov, Yurii P.
Saleh, Gabriele
Balci, Sinan
Divitini, Giorgio
Manna, Liberato
contents We report the synthesis of ethylammonium lead iodide (EAPbI3) colloidal nanocrystals as another member of the lead halide perovskites family. The insertion of an unusually large A-cation (274 pm in diameter) in the perovskite structure, hitherto considered unlikely due to the unfavorable Goldschmidt tolerance factor, results in a significantly larger lattice parameter compared to the Cs-, methylammonium- and formamidinium-based lead halide perovskite homologues. As a consequence, EAPbI3 nanocrystals are highly unstable, evolving to a non-perovskite delta-EAPbI3 polymorph within one day. Also, EAPbI3 nanocrystals are very sensitive to electron irradiation and quickly degrade to PbI2 upon exposure to the electron beam, following a mechanism similar to that of other hybrid lead iodide perovskites (although degradation can be reduced by partially replacing the EA+ ions with Cs+ ions). Interestingly, in some cases during this degradation the formation of an epitaxial interface between (EAxCs1-x)PbI3 and PbI2 is observed. The photoluminescence emission of the EAPbI3 perovskite nanocrystals, albeit being characterized by a low quantum yield (around 1%), can be tuned in the 664-690 nm range by regulating their size during the synthesis. The emission efficiency can be improved upon partial alloying at the A site with Cs+ or formamidinium cations. Furthermore, the morphology of the EAPbI3 nanocrystals can be chosen to be either nanocube or nanoplatelet, depending on the synthesis conditions.
format Preprint
id arxiv_https___arxiv_org_abs_2512_06788
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Breaking the Boundaries of the Goldschmidt Tolerance Factor with Ethylammonium Lead Iodide Perovskite Nanocrystals
Guvenc, C. Meric
Toso, Stefano
Ivanov, Yurii P.
Saleh, Gabriele
Balci, Sinan
Divitini, Giorgio
Manna, Liberato
Materials Science
We report the synthesis of ethylammonium lead iodide (EAPbI3) colloidal nanocrystals as another member of the lead halide perovskites family. The insertion of an unusually large A-cation (274 pm in diameter) in the perovskite structure, hitherto considered unlikely due to the unfavorable Goldschmidt tolerance factor, results in a significantly larger lattice parameter compared to the Cs-, methylammonium- and formamidinium-based lead halide perovskite homologues. As a consequence, EAPbI3 nanocrystals are highly unstable, evolving to a non-perovskite delta-EAPbI3 polymorph within one day. Also, EAPbI3 nanocrystals are very sensitive to electron irradiation and quickly degrade to PbI2 upon exposure to the electron beam, following a mechanism similar to that of other hybrid lead iodide perovskites (although degradation can be reduced by partially replacing the EA+ ions with Cs+ ions). Interestingly, in some cases during this degradation the formation of an epitaxial interface between (EAxCs1-x)PbI3 and PbI2 is observed. The photoluminescence emission of the EAPbI3 perovskite nanocrystals, albeit being characterized by a low quantum yield (around 1%), can be tuned in the 664-690 nm range by regulating their size during the synthesis. The emission efficiency can be improved upon partial alloying at the A site with Cs+ or formamidinium cations. Furthermore, the morphology of the EAPbI3 nanocrystals can be chosen to be either nanocube or nanoplatelet, depending on the synthesis conditions.
title Breaking the Boundaries of the Goldschmidt Tolerance Factor with Ethylammonium Lead Iodide Perovskite Nanocrystals
topic Materials Science
url https://arxiv.org/abs/2512.06788