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Nano Research 2020, 13(1): 282-291 https://doi.org/10.1007/s12274-019-2611-5
Research Article | Issue | Published: 27 December 2019

Synthesis and transformation of zero-dimensional Cs3BiX6 (X = Cl, Br) perovskite-analogue nanocrystals

Show Author's Information Hanjun Yang1,  Tong Cai1,  Exian Liu2,  Katie Hills-Kimball1,  Jianbo Gao2,  Ou Chen1( )
Department of Chemistry, Brown University, 324 Brook Street, Providence, Rhode Island 02912, USA
Ultrafast Photophysics of Quantum Devices Laboratory, Department of Physics and Astronomy, Clemson University, South Carolina 29634, USA
Keywords:
anion exchange, perovskite nanocrystals, zero-dimensional perovskite-analogue, bismuth-based perovskite, post-synthetic reactions
Topics:
Bromine compoundsChlorine compoundsIon exchangeMetal ionsMetalsNanocrystalsPerovskite
Cite this article:
Yang H, Cai T, Liu E, et al. Synthesis and transformation of zero-dimensional Cs3BiX6 (X = Cl, Br) perovskite-analogue nanocrystals. Nano Research, 2020, 13(1): 282-291. https://doi.org/10.1007/s12274-019-2611-5
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Abstract Full text Electronic supplementary material About this article

The unique structure of zero-dimensional (0D) perovskite-analogues has attracted a great amount of research interest in recent years. To date, the current compositional library of 0D perovskites is largely limited to the lead-based Cs4PbX6 (X = Cl, Br, and I) systems. In this work, we report a new synthesis of lead-free 0D Cs3BiX6 (X = Cl, Br) perovskite-analogue nanocrystals (NCs) with a uniform cubic shape. We observe a broad photoluminescence peak centered at 390 nm for the 0D Cs3BiCl6 NCs at low temperatures. This feature originates from a self-trapped exciton mechanism. In situ thermal stability studies show that Cs3BiX6 NCs remain stable upon heating up to 200 °C without crystal structural degradation. Moreover, we demonstrate that the Cs3BiX6 NCs can transform into other bismuth-based perovskite-analogues via facile anion exchange or metal ion insertion reactions. Our study presented here offers the opportunity for further understanding of the structure-property relationship of 0D perovskite-analogue materials, leading toward their future optoelectronic applications.


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Electronic supplementary material
About this article

Synthesis and transformation of zero-dimensional Cs3BiX6 (X = Cl, Br) perovskite-analogue nanocrystals

Show Author's information Hanjun Yang1, Tong Cai1, Exian Liu2, Katie Hills-Kimball1, Jianbo Gao2, Ou Chen1( )
Department of Chemistry, Brown University, 324 Brook Street, Providence, Rhode Island 02912, USA
Ultrafast Photophysics of Quantum Devices Laboratory, Department of Physics and Astronomy, Clemson University, South Carolina 29634, USA

Abstract

The unique structure of zero-dimensional (0D) perovskite-analogues has attracted a great amount of research interest in recent years. To date, the current compositional library of 0D perovskites is largely limited to the lead-based Cs4PbX6 (X = Cl, Br, and I) systems. In this work, we report a new synthesis of lead-free 0D Cs3BiX6 (X = Cl, Br) perovskite-analogue nanocrystals (NCs) with a uniform cubic shape. We observe a broad photoluminescence peak centered at 390 nm for the 0D Cs3BiCl6 NCs at low temperatures. This feature originates from a self-trapped exciton mechanism. In situ thermal stability studies show that Cs3BiX6 NCs remain stable upon heating up to 200 °C without crystal structural degradation. Moreover, we demonstrate that the Cs3BiX6 NCs can transform into other bismuth-based perovskite-analogues via facile anion exchange or metal ion insertion reactions. Our study presented here offers the opportunity for further understanding of the structure-property relationship of 0D perovskite-analogue materials, leading toward their future optoelectronic applications.

Keywords: anion exchange, perovskite nanocrystals, zero-dimensional perovskite-analogue, bismuth-based perovskite, post-synthetic reactions

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Publication history
Copyright
Acknowledgements

Publication history

Received: 29 October 2019
Revised: 15 December 2019
Accepted: 16 December 2019
Published: 27 December 2019
Issue date: January 2020

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Acknowledgements

O. C. acknowledges the support from Brown University startup funds and the National Science Foundation (OIA-1538893). K. H.-K. is supported by the U.S. Department of Education GAANN research fellowship (P200A150037). TEM, XRD, XPS and Raman measurements were performed at the Electron Microscopy Facility and NanoTools Facility in the Institute for Molecular and Nanoscale Innovation (IMNI) in Brown University. Part of the photoluminescence measurements was performed at Clemson University.

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