First evidence of macroscale single crystal ion exchange found in lead halide perovskites

Ariel Efrati, Sigalit Aharon, Małgorzata Wierzbowska, Lioz Etgar*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


Ion exchange is classified as a reaction that may be performed among nanocrystals. Here, we discovered that methylammonium lead bromide macroscale perovskite single crystals may exchange ions with the environment while maintaining their original morphology. Iodide replaced bromide and was detected even in the very center of a previously pure macroscale MAPbBr3 single crystal. Additionally, the entrance of chloride into the crystal is energetically favorable and most bromides were exchanged, yet kinetic factors hindered Cs+ entry and Pb2+ by Sn2+ substitution. Furthermore, grinding different single crystals together revealed swift I/Br exchange. Clear differences in comparison with nanomaterials, along with density functional theory calculations, shed light on the nature of ion-exchange reactions in perovskite single crystals. This work provides first evidence of these halide exchange reactions in macroscale perovskite single crystals. These results offer a new perspective on ion-exchange reaction and pave a path toward synthesis of inhomogeneous single crystals. (Figure presented.).

Original languageAmerican English
Article numbere12016
Issue number1
StatePublished - Mar 2020

Bibliographical note

Funding Information:
Israel science foundation grant number 937/18; National Science Centre of Poland, Grant/Award Number: 2016/23/B/ST8/03480 Funding information

Funding Information:
The authors would like to acknowledge Dr. Vladimir Uvarov for assistance with powder XRD measurements, Evgenia Blayvas for SEM imaging, David Azulay and Bat‐El Cohen for professional photography, and Avi Schneider for reading the paper. L.E. acknowledges the Israel science foundation grant number 937/18 and the Israel ministry of defense. Calculations were performed in the Cyfronet Computer Centre using the Prometheus computer. This work has been supported by The National Science Centre of Poland (Project No. 2016/23/B/ST8/03480).

Publisher Copyright:
© 2020 The Authors. EcoMat published by John Wiley & Sons Australia, Ltd on behalf of The Hong Kong Polytechnic University.


  • energy materials
  • environmental science
  • ion-exchange reactions
  • perovskite
  • single crystals
  • solid-state chemistry


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