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Exogenous Metal Cations in the Synthesis of CsPbBr3 Nanocrystals and Their Interplay with Tertiary Amines

Li, Zhanzhao ; Goldoni, Luca ; Wu, Ye ; Imran, Muhammad ; Ivanov, Yurii P. ; Divitini, Giorgio ; Zito, Juliette ; Panneerselvam, Iyyappa Rajan ; Baranov, Dmitry LU orcid and Infante, Ivan , et al. (2024) In Journal of the American Chemical Society 146(30). p.20636-20648
Abstract

Current syntheses of CsPbBr3 halide perovskite nanocrystals (NCs) rely on overstoichiometric amounts of Pb2+ precursors, resulting in unreacted lead ions at the end of the process. In our synthesis scheme of CsPbBr3 NCs, we replaced excess Pb2+ with different exogenous metal cations (M) and investigated their effect on the synthesis products. These cations can be divided into two groups: group 1 delivers monodisperse CsPbBr3 cubes capped with oleate species (as for the case when Pb2+ is used in excess) and with a photoluminescence quantum yield (PLQY) as high as 90% with some cations (for example with M = In3+); group 2 yields irregularly shaped... (More)

Current syntheses of CsPbBr3 halide perovskite nanocrystals (NCs) rely on overstoichiometric amounts of Pb2+ precursors, resulting in unreacted lead ions at the end of the process. In our synthesis scheme of CsPbBr3 NCs, we replaced excess Pb2+ with different exogenous metal cations (M) and investigated their effect on the synthesis products. These cations can be divided into two groups: group 1 delivers monodisperse CsPbBr3 cubes capped with oleate species (as for the case when Pb2+ is used in excess) and with a photoluminescence quantum yield (PLQY) as high as 90% with some cations (for example with M = In3+); group 2 yields irregularly shaped CsPbBr3 NCs with broad size distributions. In both cases, the addition of a tertiary ammonium cation (didodecylmethylammonium, DDMA+) during the synthesis, after the nucleation of the NCs, reshapes the NCs to monodisperse truncated cubes. Such NCs feature a mixed oleate/DDMA+ surface termination with PLQY values of up to 97%. For group 1 cations this happens only if the ammonium cation is directly added as a salt (DDMA-Br), while for group 2 cations this happens even if the corresponding tertiary amine (DDMA) is added, instead of DDMA-Br. This is attributed to the fact that only group 2 cations can facilitate the protonation of DDMA by the excess oleic acid present in the reaction environment. In all cases studied, the incorporation of M cations is marginal, and the reshaping of the NCs is only transient: if the reactions are run for a long time, the truncated cubes evolve to cubes.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the American Chemical Society
volume
146
issue
30
pages
13 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:39018374
  • scopus:85198956095
ISSN
0002-7863
DOI
10.1021/jacs.4c03084
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2024 American Chemical Society.
id
f34b3687-edf0-4ba2-8b21-c7dd1410417e
date added to LUP
2024-08-24 16:43:19
date last changed
2025-01-26 09:10:58
@article{f34b3687-edf0-4ba2-8b21-c7dd1410417e,
  abstract     = {{<p>Current syntheses of CsPbBr<sub>3</sub> halide perovskite nanocrystals (NCs) rely on overstoichiometric amounts of Pb<sup>2+</sup> precursors, resulting in unreacted lead ions at the end of the process. In our synthesis scheme of CsPbBr<sub>3</sub> NCs, we replaced excess Pb<sup>2+</sup> with different exogenous metal cations (M) and investigated their effect on the synthesis products. These cations can be divided into two groups: group 1 delivers monodisperse CsPbBr<sub>3</sub> cubes capped with oleate species (as for the case when Pb<sup>2+</sup> is used in excess) and with a photoluminescence quantum yield (PLQY) as high as 90% with some cations (for example with M = In<sup>3+</sup>); group 2 yields irregularly shaped CsPbBr<sub>3</sub> NCs with broad size distributions. In both cases, the addition of a tertiary ammonium cation (didodecylmethylammonium, DDMA<sup>+</sup>) during the synthesis, after the nucleation of the NCs, reshapes the NCs to monodisperse truncated cubes. Such NCs feature a mixed oleate/DDMA<sup>+</sup> surface termination with PLQY values of up to 97%. For group 1 cations this happens only if the ammonium cation is directly added as a salt (DDMA-Br), while for group 2 cations this happens even if the corresponding tertiary amine (DDMA) is added, instead of DDMA-Br. This is attributed to the fact that only group 2 cations can facilitate the protonation of DDMA by the excess oleic acid present in the reaction environment. In all cases studied, the incorporation of M cations is marginal, and the reshaping of the NCs is only transient: if the reactions are run for a long time, the truncated cubes evolve to cubes.</p>}},
  author       = {{Li, Zhanzhao and Goldoni, Luca and Wu, Ye and Imran, Muhammad and Ivanov, Yurii P. and Divitini, Giorgio and Zito, Juliette and Panneerselvam, Iyyappa Rajan and Baranov, Dmitry and Infante, Ivan and De Trizio, Luca and Manna, Liberato}},
  issn         = {{0002-7863}},
  language     = {{eng}},
  month        = {{07}},
  number       = {{30}},
  pages        = {{20636--20648}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of the American Chemical Society}},
  title        = {{Exogenous Metal Cations in the Synthesis of CsPbBr<sub>3</sub> Nanocrystals and Their Interplay with Tertiary Amines}},
  url          = {{http://dx.doi.org/10.1021/jacs.4c03084}},
  doi          = {{10.1021/jacs.4c03084}},
  volume       = {{146}},
  year         = {{2024}},
}