4.8 Article

Ligands Mediate Anion Exchange between Colloidal Lead-Halide Perovskite Nanocrystals

Journal

NANO LETTERS
Volume 22, Issue 11, Pages 4340-4346

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.nanolett.2c00611

Keywords

perovskite nanocrystals; anion exchange; kinetics; surface ligands

Funding

  1. Israel Science Foundation-National Science Foundation China (ISF-NSFC) joint research program [2495/17]
  2. European Union through Horizon 2020 Research and Innovation Programme (ERC CoG Grant) [819740]
  3. Hebrew university center for nanoscience and nanotechnology
  4. European Research Council (ERC) [819740] Funding Source: European Research Council (ERC)

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This study investigates the effects of different stabilizing surface ligands on the kinetics of the cross-anion exchange reaction and finds that zwitterionic ligands can slow down the process, offering improved stability and enhanced solubility.
The soft lattice of lead-halide perovskite nanocrystals (NCs) allows tuning their optoelectronic characteristics via anion exchange by introducing halide salts to a solution of perovskite NCs. Similarly, cross-anion exchange can occur upon mixing NCs of different perovskite halides. This process, though, is detrimental for applications requiring perovskite NCs with different halides in close proximity. We study the effects of various stabilizing surface ligands on the kinetics of the cross-anion exchange reaction, comparing zwitterionic and ionic ligands. The kinetic analysis, inspired by the cage effect for solution reactions, showcases a mechanism where the surface capping ligands act as anion carriers that diffuse to the NC surface, forming an encounter pair enclosed by the surrounding ligands that initiates the anion exchange process. The zwitterionic ligands considerably slow down the cross-anion exchange process, and while they do not fully inhibit it, they confer improved stability alongside enhanced solubility relevant for various applications.

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