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Green-Emitting Powders of Zero-Dimensional Cs4PbBr6 : Delineating the Intricacies of the Synthesis and the Origin of Photoluminescence

Ray, Aniruddha ; Maggioni, Daniela ; Baranov, Dmitry LU orcid ; Dang, Zhiya ; Prato, Mirko ; Akkerman, Quinten A. ; Goldoni, Luca ; Caneva, Enrico ; Manna, Liberato and Abdelhady, Ahmed L. (2019) In Chemistry of Materials 31(18). p.7761-7769
Abstract

A detailed investigation into the synthesis of green-emitting powders of Cs4PbBr6 and CsPbBr3 materials by antisolvent precipitation from CsBr-PbBr2 precursor solutions in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is reported. Various solvated lead bromide and polybromide species (PbBr2, [PbBr3]-, [PbBr4]2-, and possibly [PbBr5]3- or [PbBr6]4-) are detected in the precursor solutions by optical absorbance and emission spectroscopies. The solvodynamic size of the species in solution is strongly solvent-dependent: ∼1 nm species were detected in DMSO, while significantly larger species... (More)

A detailed investigation into the synthesis of green-emitting powders of Cs4PbBr6 and CsPbBr3 materials by antisolvent precipitation from CsBr-PbBr2 precursor solutions in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is reported. Various solvated lead bromide and polybromide species (PbBr2, [PbBr3]-, [PbBr4]2-, and possibly [PbBr5]3- or [PbBr6]4-) are detected in the precursor solutions by optical absorbance and emission spectroscopies. The solvodynamic size of the species in solution is strongly solvent-dependent: ∼1 nm species were detected in DMSO, while significantly larger species were observed in DMF by dynamic light scattering. The solvodynamic size of the lead bromide species plays a critical role in determining the Cs-Pb-Br composition of the precipitated powders: smaller species favor the precipitation of Cs4PbBr6, while larger species template the formation of CsPbBr3 under identical experimental conditions. The powders have been characterized by 133Cs and 207Pb solid-state nuclear magnetic resonance, and 133Cs sensitivity toward the different Cs environments within Cs4PbBr6 is demonstrated. Finally, the possible origins of green emission in Cs4PbBr6 samples are discussed. It is proposed that a two-dimensional Cs2PbBr4 inclusion may be responsible for green emission at ∼520 nm in addition to the widely acknowledged CsPbBr3 impurity, although we found no conclusive experimental evidence supporting such claims.

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publishing date
type
Contribution to journal
publication status
published
in
Chemistry of Materials
volume
31
issue
18
pages
9 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85072881677
ISSN
0897-4756
DOI
10.1021/acs.chemmater.9b02944
language
English
LU publication?
no
additional info
Publisher Copyright: © 2019 American Chemical Society.
id
1c19a549-8510-4b5b-a11e-ef02d27dc0f3
date added to LUP
2023-01-17 11:59:37
date last changed
2023-01-31 13:04:24
@article{1c19a549-8510-4b5b-a11e-ef02d27dc0f3,
  abstract     = {{<p>A detailed investigation into the synthesis of green-emitting powders of Cs<sub>4</sub>PbBr<sub>6</sub> and CsPbBr<sub>3</sub> materials by antisolvent precipitation from CsBr-PbBr<sub>2</sub> precursor solutions in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is reported. Various solvated lead bromide and polybromide species (PbBr<sub>2</sub>, [PbBr<sub>3</sub>]<sup>-</sup>, [PbBr<sub>4</sub>]<sup>2-</sup>, and possibly [PbBr<sub>5</sub>]<sup>3-</sup> or [PbBr<sub>6</sub>]<sup>4-</sup>) are detected in the precursor solutions by optical absorbance and emission spectroscopies. The solvodynamic size of the species in solution is strongly solvent-dependent: ∼1 nm species were detected in DMSO, while significantly larger species were observed in DMF by dynamic light scattering. The solvodynamic size of the lead bromide species plays a critical role in determining the Cs-Pb-Br composition of the precipitated powders: smaller species favor the precipitation of Cs<sub>4</sub>PbBr<sub>6</sub>, while larger species template the formation of CsPbBr<sub>3</sub> under identical experimental conditions. The powders have been characterized by <sup>133</sup>Cs and <sup>207</sup>Pb solid-state nuclear magnetic resonance, and <sup>133</sup>Cs sensitivity toward the different Cs environments within Cs<sub>4</sub>PbBr<sub>6</sub> is demonstrated. Finally, the possible origins of green emission in Cs<sub>4</sub>PbBr<sub>6</sub> samples are discussed. It is proposed that a two-dimensional Cs<sub>2</sub>PbBr<sub>4</sub> inclusion may be responsible for green emission at ∼520 nm in addition to the widely acknowledged CsPbBr<sub>3</sub> impurity, although we found no conclusive experimental evidence supporting such claims.</p>}},
  author       = {{Ray, Aniruddha and Maggioni, Daniela and Baranov, Dmitry and Dang, Zhiya and Prato, Mirko and Akkerman, Quinten A. and Goldoni, Luca and Caneva, Enrico and Manna, Liberato and Abdelhady, Ahmed L.}},
  issn         = {{0897-4756}},
  language     = {{eng}},
  month        = {{09}},
  number       = {{18}},
  pages        = {{7761--7769}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Chemistry of Materials}},
  title        = {{Green-Emitting Powders of Zero-Dimensional Cs<sub>4</sub>PbBr<sub>6</sub> : Delineating the Intricacies of the Synthesis and the Origin of Photoluminescence}},
  url          = {{http://dx.doi.org/10.1021/acs.chemmater.9b02944}},
  doi          = {{10.1021/acs.chemmater.9b02944}},
  volume       = {{31}},
  year         = {{2019}},
}