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Research Article

Post-synthesis phase and shape evolution of CsPbBr3 colloidal nanocrystals: The role of ligands

Elisabetta Fanizza1,2,§( ), Francesca Cascella1,†,§, Davide Altamura3, Cinzia Giannini3, Annamaria Panniello2, Leonardo Triggiani1,2, Francesca Panzarea1, Nicoletta Depalo2, Roberto Grisorio4,5, Gian Paolo Suranna4,5, Angela Agostiano1,2, M. Lucia Curri1,2, Marinella Striccoli2( )
Dipartimento di Chimica,Università degli Studi di Bari "A. Moro",Via Orabona 4,70126,Bari, Italy;
CNR-Istituto per i Processi Chimico Fisici,S. S. Bari,Via Orabona, 4,70126,Bari, Italy;
CNR-Istituto di Cristallografia,Via Amendola, 122/O,70126,Bari, Italy;
Dipartimento di Ingegneria Civile, Ambientale, del Territorio, Edile e di Chimica (DICATECh),Politecnico di Bari,Via Orabona 4,70125,Italy;
,CNR-NANOTEC-Istituto di Nanotecnologia,Via Monteroni,73100,Lecce, Italy;

§ Elisabetta Fanizza and Francesca Cascella contributed equally to this work.

† Present Address: Max Planck Institute for Dynamics of Complex Technical Systems, Physical and Chemical Foundations of Process Engineering, Sandtorstr.1, D-39106 Magdeburg, Germany

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Graphical Abstract

Abstract

The surface chemistry of colloidal cesium lead bromide (CsPbBr3) nanocrystals is decisive in determining the stability and the final morphology of this class of materials, characterized by ionic structure and a high defect tolerance factor. Here, the high sensitivity of purified colloidal nanocubes of CsPbBr3 to diverse environmental condition (solvent dilution, ageing, ligands post synthetic treatment) in ambient atmosphere is investigated by means of a comprehensive morphological (electron microscopy), structural (θ/2θ X-ray diffraction (XRD) and grazing incidence wide angle scattering (GIWAXS)), and spectroscopic chemical (1H nuclear magnetic resonance (NMR), nuclear Overhauser effect spectroscopy (NOESY), absorption and emission spectroscopy) characterization. The aging and solvent dilution contribute to modify the nanocrystal morphology, due to a modification of the ligand dynamic. Moreover, we establish the ability of aliphatic carboxylic acids and alkyl amines ligands to induce, even in a post preparative process at room temperature, structural, morphological and spectroscopic variations. Upon post synthesis alkyl amine addition, in particular of oleyl amine and octyl amine, the highly green emitting CsPbBr3 nanocubes effectively turn into one-dimensional (1D) thin tetragonal nanowires or lead halide deficient rhombohedral zero-dimensional (0D) Cs4PbBr6 structures with a complete loss of fluorescence. The addition of an alkyl carboxylic acid, as oleic and nonanoic acid, produces the transformation of nanocubes into still emitting orthorombic two-dimensional (2D) nanoplates. The acid/base equilibrium between the native and added ligands, the adsorbed/free ligands dynamic in solution and the ligand solubility in non-polar solvent contribute to render CsPbBr3 particularly sensitive to environmental and processing conditions and, therefore prone to undergo to structural, morphological and, hence spectroscopic, transformations.

Keywords

lead halide perovskite nanocrystalssurface chemistryligands equilibrialong term stability

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Nano Research
Volume 12 Issue 5,
May 2019
Pages 1155-1166
DOI: 10.1007/s12274-019-2371-2
Cite this article:
Fanizza E, Cascella F, Altamura D, et al. Post-synthesis phase and shape evolution of CsPbBr3 colloidal nanocrystals: The role of ligands. Nano Research, 2019, 12(5): 1155-1166. https://doi.org/10.1007/s12274-019-2371-2
Topics:
Absorption spectroscopyBromine compoundsCesium compoundsEmission spectroscopyLigands MorphologyNanocrystalsNuclear magnetic resonanceNuclear magnetic resonance spectroscopyPerovskiteSolsSolvents

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Received: 15 October 2018
Revised: 25 February 2019
Accepted: 05 March 2019
Published: 02 April 2019
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019
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