Materials Chemistry

Halide Perovskites as Disposable Epitaxial Templates for the Phase-Selective Synthesis of Lead Sulfochloride Nanocrystals

Authors

  • Stefano Toso Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy ,
  • Muhammad Imran Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy ,
  • Enrico Mugnaioli Istituto Italiano di Tecnologia, Viale Rinaldo Piaggio 34, 56025 Pontedera, Italy ,
  • Anna Moliterni Istituto Di Cristallografia – Consiglio Nazionale delle Ricerche (IC–CNR), I-70126 Bari, Italy ,
  • Rocco Caliandro Istituto Di Cristallografia – Consiglio Nazionale delle Ricerche (IC–CNR), I-70126 Bari, Italy ,
  • Nadine J. Schrenker Electron Microscopy for Materials Science (EMAT) and NANOlab Center of Excellence, University of Antwerp, 2020 Antwerp, Belgium ,
  • Andrea Pianetti Dipartimento di Scienza dei Materiali, Università degli Studi di Milano-Bicocca, 20125 Milano, Italy ,
  • Juliette Zito Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy & Dipartimento di Chimica e Chimica Industriale, Università degli Studi di Genova, Via Dodecaneso 31, 16146 Genova, Italy ,
  • Francesco Zaccaria Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy ,
  • Ye Wu Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy ,
  • Mauro Gemmi Istituto Italiano di Tecnologia, Viale Rinaldo Piaggio 34, 56025 Pontedera, Italy ,
  • Cinzia Giannini Istituto Di Cristallografia – Consiglio Nazionale delle Ricerche (IC–CNR), I-70126 Bari, Italy ,
  • Sergio Brovelli Dipartimento di Scienza dei Materiali, Università degli Studi di Milano-Bicocca, 20125 Milano, Italy ,
  • Ivan Infante Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy ,
  • Sara Bals Electron Microscopy for Materials Science (EMAT) and NANOlab Center of Excellence, University of Antwerp, 2020 Antwerp, Belgium ,
  • Liberato Manna Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy

Abstract

Colloidal chemistry grants access to a wealth of materials through simple and mild reactions. However, even few elements can combine in a variety of stoichiometries and structures, potentially resulting in impurities or even wrong products. Similar issues have been long addressed in organic chemistry by using reaction-directing groups, that are added to a substrate to promote a specific product and are later removed. Inspired by such approach, we demonstrate the use of CsPbCl3 perovskite nanocrystals to drive the phase-selective synthesis of two novel lead sulfochlorides: Pb3S2Cl2 and Pb4S3Cl2. When homogeneously nucleated in solution, lead sulfochlorides form Pb3S2Cl2 nanocrystals. Conversely, the presence of CsPbCl3 triggers the formation of Pb4S3Cl2/CsPbCl3 epitaxial heterostructures. The phase selectivity is guaranteed by the continuity of the cationic subnetwork across the interface, a condition not met in a hypothetical Pb3S2Cl2/CsPbCl3 heterostructure. The perovskite domain is then etched, delivering phase-pure Pb4S3Cl2 nanocrystals that could not be synthesized directly.

Content

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Supplementary material

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Supplementary Information
Synthesis of Sulfohalide nanocrystals (Pb3S2Cl2, Pb4S3Br2, Pb4S3I2), Structural characterization of Pb3S2Cl2 nanocrystals, Computational DFT modelling, Structure refinement of Pb3S2X2 nanocrystals and comparison with Pb3S2Cl2, Models of Pb4S3Cl2/Pb4S3Cl2 heterostructures, Synthesis and characterization of Pb4S3Cl2/CsPbCl3 heterostructures, Etching of heterostructures and characterization of Pb4S3Cl2 nanocrystals, Spectroscopic characterization
Thumbnail image of CIFs, Structures and Source Data.zip
CIFs, Structures and Source Data
Pb3S2Cl2_as_solved.cif and Pb3S2Cl2_standardized.cif files describe the structure of the Pb3S2Cl2 phase as solved and refined in this work. The Pb3S2Br2.cif and Pb3S2I.cif files describe the structure of the Pb4S3I2 and Pb4S3I2 phases as refined in this work. The file Heterostruc-ture.xzy contains an atomistic model of the Pb3S2Cl2/CsPbCl3 interface as represented in Figure 3a. Source Data.xlsx contains the source data for plots and charts.