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Fully Inorganic Ruddlesden-Popper Double Cl-I and Triple Cl-Br-I Lead Halide Perovskite Nanocrystals

Akkerman, Quinten A. ; Bladt, Eva ; Petralanda, Urko ; Dang, Zhiya ; Sartori, Emanuela ; Baranov, Dmitry LU orcid ; Abdelhady, Ahmed L. ; Infante, Ivan ; Bals, Sara and Manna, Liberato (2019) In Chemistry of Materials 31(6). p.2182-2190
Abstract

The vast majority of lead halide perovskite (LHP) nanocrystals (NCs) are currently based on either a single halide composition (CsPbCl3, CsPbBr3, and CsPbI3) or an alloyed mixture of bromide with either Cl- or I- [i.e., CsPb(Br:Cl)3 or CsPb(Br:I)3]. In this work, we present the synthesis as well as a detailed optical and structural study of two halide alloying cases that have not previously been reported for LHP NCs: Cs2PbI2Cl2 NCs and triple halide CsPb(Cl:Br:I)3 NCs. In the case of Cs2PbI2Cl2, we observe for the first time NCs with a fully inorganic Ruddlesden-Popper phase (RPP)... (More)

The vast majority of lead halide perovskite (LHP) nanocrystals (NCs) are currently based on either a single halide composition (CsPbCl3, CsPbBr3, and CsPbI3) or an alloyed mixture of bromide with either Cl- or I- [i.e., CsPb(Br:Cl)3 or CsPb(Br:I)3]. In this work, we present the synthesis as well as a detailed optical and structural study of two halide alloying cases that have not previously been reported for LHP NCs: Cs2PbI2Cl2 NCs and triple halide CsPb(Cl:Br:I)3 NCs. In the case of Cs2PbI2Cl2, we observe for the first time NCs with a fully inorganic Ruddlesden-Popper phase (RPP) crystal structure. Unlike the well-explored organic-inorganic RPP, here, the RPP formation is triggered by the size difference between the halide ions. These NCs exhibit a strong excitonic absorption, albeit with a weak photoluminescence quantum yield (PLQY). In the case of the triple halide CsPb(Cl:Br:I)3 composition, the NCs comprise a CsPbBr2Cl perovskite crystal lattice with only a small amount of incorporated iodide, which segregates at RPP planes' interfaces within the CsPb(Cl:Br:I)3 NCs. Supported by density functional theory calculations and postsynthetic surface treatments to enhance the PLQY, we show that the combination of iodide segregation and defective RPP interfaces are most likely linked to the strong PL quenching observed in these nanostructures. In summary, this work demonstrates the limits of halide alloying in LHP NCs because a mixture that contains halide ions of very different sizes leads to the formation of defective RPP interfaces and a severe quenching of LHP NC's optical properties.

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author
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publishing date
type
Contribution to journal
publication status
published
in
Chemistry of Materials
volume
31
issue
6
pages
9 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85063458568
ISSN
0897-4756
DOI
10.1021/acs.chemmater.9b00489
language
English
LU publication?
no
additional info
Publisher Copyright: © Copyright 2019 American Chemical Society.
id
3358a46e-4a3b-45f0-9556-f6925673815b
date added to LUP
2023-01-17 11:59:59
date last changed
2023-01-31 13:12:17
@article{3358a46e-4a3b-45f0-9556-f6925673815b,
  abstract     = {{<p>The vast majority of lead halide perovskite (LHP) nanocrystals (NCs) are currently based on either a single halide composition (CsPbCl<sub>3</sub>, CsPbBr<sub>3</sub>, and CsPbI<sub>3</sub>) or an alloyed mixture of bromide with either Cl<sup>-</sup> or I<sup>-</sup> [i.e., CsPb(Br:Cl)<sub>3</sub> or CsPb(Br:I)<sub>3</sub>]. In this work, we present the synthesis as well as a detailed optical and structural study of two halide alloying cases that have not previously been reported for LHP NCs: Cs<sub>2</sub>PbI<sub>2</sub>Cl<sub>2</sub> NCs and triple halide CsPb(Cl:Br:I)<sub>3</sub> NCs. In the case of Cs<sub>2</sub>PbI<sub>2</sub>Cl<sub>2</sub>, we observe for the first time NCs with a fully inorganic Ruddlesden-Popper phase (RPP) crystal structure. Unlike the well-explored organic-inorganic RPP, here, the RPP formation is triggered by the size difference between the halide ions. These NCs exhibit a strong excitonic absorption, albeit with a weak photoluminescence quantum yield (PLQY). In the case of the triple halide CsPb(Cl:Br:I)<sub>3</sub> composition, the NCs comprise a CsPbBr<sub>2</sub>Cl perovskite crystal lattice with only a small amount of incorporated iodide, which segregates at RPP planes' interfaces within the CsPb(Cl:Br:I)<sub>3</sub> NCs. Supported by density functional theory calculations and postsynthetic surface treatments to enhance the PLQY, we show that the combination of iodide segregation and defective RPP interfaces are most likely linked to the strong PL quenching observed in these nanostructures. In summary, this work demonstrates the limits of halide alloying in LHP NCs because a mixture that contains halide ions of very different sizes leads to the formation of defective RPP interfaces and a severe quenching of LHP NC's optical properties.</p>}},
  author       = {{Akkerman, Quinten A. and Bladt, Eva and Petralanda, Urko and Dang, Zhiya and Sartori, Emanuela and Baranov, Dmitry and Abdelhady, Ahmed L. and Infante, Ivan and Bals, Sara and Manna, Liberato}},
  issn         = {{0897-4756}},
  language     = {{eng}},
  month        = {{03}},
  number       = {{6}},
  pages        = {{2182--2190}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Chemistry of Materials}},
  title        = {{Fully Inorganic Ruddlesden-Popper Double Cl-I and Triple Cl-Br-I Lead Halide Perovskite Nanocrystals}},
  url          = {{http://dx.doi.org/10.1021/acs.chemmater.9b00489}},
  doi          = {{10.1021/acs.chemmater.9b00489}},
  volume       = {{31}},
  year         = {{2019}},
}