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Exploiting the Transformative Features of Metal Halides for the Synthesis of CsPbBr3@SiO2 Core-Shell Nanocrystals

Rossi, Christian ; Scarfiello, Riccardo ; Brescia, Rosaria ; Goldoni, Luca ; Caputo, Gianvito ; Carbone, Luigi ; Colombara, Diego ; De Trizio, Luca ; Manna, Liberato and Baranov, Dmitry LU orcid (2022) In Chemistry of Materials 34(1). p.405-413
Abstract
The encapsulation of colloidal lead halide perovskite nanocrystals within silica (SiO2)
is one of the strategies to protect them from polar solvents and other
external factors. Here, we demonstrate the overcoating of CsPbBr3 perovskite nanocrystals with silica by exploiting the anhydride-induced transformation of Cs4PbBr6 nanocrystals. CsPbBr3@SiO2 core–shell nanocrystals are obtained after (i) a reaction between colloidal Cs4PbBr6 nanocrystals and maleic anhydride in toluene that yields CsPbBr3 nanocrystals and maleamic acid and (ii) a silica-shell growth around CsPbBr3 nanocrystals via hydrolysis of added alkoxysilanes.... (More)
The encapsulation of colloidal lead halide perovskite nanocrystals within silica (SiO2)
is one of the strategies to protect them from polar solvents and other
external factors. Here, we demonstrate the overcoating of CsPbBr3 perovskite nanocrystals with silica by exploiting the anhydride-induced transformation of Cs4PbBr6 nanocrystals. CsPbBr3@SiO2 core–shell nanocrystals are obtained after (i) a reaction between colloidal Cs4PbBr6 nanocrystals and maleic anhydride in toluene that yields CsPbBr3 nanocrystals and maleamic acid and (ii) a silica-shell growth around CsPbBr3 nanocrystals via hydrolysis of added alkoxysilanes. The reaction between Cs4PbBr6
nanocrystals and maleic anhydride is necessary to promote shell
formation from alkoxysilanes, as demonstrated in control experiments.
The best samples of as-prepared CsPbBr3@SiO2 nanocrystals consist of ∼10 nm single-crystal CsPbBr3
cores surrounded by ∼5–7 nm amorphous silica shell. Despite their
core–shell structure, such nanostructures are poor emitters and degrade
within minutes of exposure to ethanol. The photoluminescence intensity
of the core–shell nanocrystals is improved by the treatment with a
solution of PbBr2 and ligands, and their stability in ethanol
is extended to several days after applying an additional silica growth
step. Overall, the investigated approach outlines a strategy for making
colloidal core–shell nanocrystals utilizing the transformative chemistry
of metal halides and reveals interesting insights regarding the
conditions required for CsPbBr3@SiO2 nanocrystal formation. (Less)
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author
; ; ; ; ; ; ; ; and
publishing date
type
Contribution to journal
publication status
published
in
Chemistry of Materials
volume
34
issue
1
pages
9 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85122818175
ISSN
0897-4756
DOI
10.1021/acs.chemmater.1c03749
language
English
LU publication?
no
additional info
Publisher Copyright: © 2021 The Authors. Published by American Chemical Society.
id
2be35365-6541-413b-b1ce-e82666e9708f
date added to LUP
2023-01-17 11:52:16
date last changed
2023-01-27 02:50:00
@article{2be35365-6541-413b-b1ce-e82666e9708f,
  abstract     = {{The encapsulation of colloidal lead halide perovskite nanocrystals within silica (SiO<sub>2</sub>)<br>
 is one of the strategies to protect them from polar solvents and other <br>
external factors. Here, we demonstrate the overcoating of CsPbBr<sub>3</sub> perovskite nanocrystals with silica by exploiting the anhydride-induced transformation of Cs<sub>4</sub>PbBr<sub>6</sub> nanocrystals. CsPbBr<sub>3</sub>@SiO<sub>2</sub> core–shell nanocrystals are obtained after (i) a reaction between colloidal Cs<sub>4</sub>PbBr<sub>6</sub> nanocrystals and maleic anhydride in toluene that yields CsPbBr<sub>3</sub> nanocrystals and maleamic acid and (ii) a silica-shell growth around CsPbBr<sub>3</sub> nanocrystals via hydrolysis of added alkoxysilanes. The reaction between Cs<sub>4</sub>PbBr<sub>6</sub><br>
 nanocrystals and maleic anhydride is necessary to promote shell <br>
formation from alkoxysilanes, as demonstrated in control experiments. <br>
The best samples of as-prepared CsPbBr<sub>3</sub>@SiO<sub>2</sub> nanocrystals consist of ∼10 nm single-crystal CsPbBr<sub>3</sub><br>
 cores surrounded by ∼5–7 nm amorphous silica shell. Despite their <br>
core–shell structure, such nanostructures are poor emitters and degrade <br>
within minutes of exposure to ethanol. The photoluminescence intensity <br>
of the core–shell nanocrystals is improved by the treatment with a <br>
solution of PbBr<sub>2</sub> and ligands, and their stability in ethanol<br>
 is extended to several days after applying an additional silica growth <br>
step. Overall, the investigated approach outlines a strategy for making <br>
colloidal core–shell nanocrystals utilizing the transformative chemistry<br>
 of metal halides and reveals interesting insights regarding the <br>
conditions required for CsPbBr<sub>3</sub>@SiO<sub>2</sub> nanocrystal formation.}},
  author       = {{Rossi, Christian and Scarfiello, Riccardo and Brescia, Rosaria and Goldoni, Luca and Caputo, Gianvito and Carbone, Luigi and Colombara, Diego and De Trizio, Luca and Manna, Liberato and Baranov, Dmitry}},
  issn         = {{0897-4756}},
  language     = {{eng}},
  month        = {{01}},
  number       = {{1}},
  pages        = {{405--413}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Chemistry of Materials}},
  title        = {{Exploiting the Transformative Features of Metal Halides for the Synthesis of CsPbBr<sub>3</sub>@SiO<sub>2</sub> Core-Shell Nanocrystals}},
  url          = {{http://dx.doi.org/10.1021/acs.chemmater.1c03749}},
  doi          = {{10.1021/acs.chemmater.1c03749}},
  volume       = {{34}},
  year         = {{2022}},
}