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In this Letter, we used fluorescence microscopy to image the reversible transformation of individual CsPbCl3 nanocrystals to CsPbBr3, which enables us to quantify heterogeneity in reactivity among hundreds of nanocrystals prepared within the same batch. We observed a wide distribution of waiting times for individual nanocrystals to react as has been seen previously for cation exchange and ion intercalation. However, a significant difference for this reaction is that the switching times for changes in fluorescence intensity are dependent on the concentration of substitutional halide ions in solution (i.e., Br– or Cl–). On the basis of the high solid-state miscibility between CsPbCl3 and CsPbBr3, we develop a model in which the activation energy for anion exchange depends on the density of exchanged ions in the nanocrystal. The heterogeneity in reaction kinetics observed among individual nanocrystals limits the compositional uniformity that can be achieved in luminescent CsPbCl3–xBrx nanocrystals prepared by anion exchange.
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Fluorescence Microscopy of Single Lead Bromide Nanocrystals Reveals Sharp Transitions during Their Transformation to Methylammonium Lead Bromide
Control over the nucleation and growth of lead-halide perovskite crystals is critical to obtain semiconductor films with high quantum yields in optoelectronic devices. In this report, we use the change in fluorescence brightness to image the transformation of individual lead bromide (PbBr 2 ) nanocrystals to methylammonium lead bromide (CH 3 NH 3 PbBr 3 ) via intercalation of CH 3 NH 3 Br. Analyzing this reaction one nanocrystal at a time reveals information that is masked when the fluorescence intensity is averaged over many particles. Sharp rises in the intensity of single nanocrystals indicate they transform much faster than the time it takes for the ensemble average to transform. While the ensemble reaction rate increases with increasing CH 3 NH 3 Br concentration, the intensity rises for individual nanocrystals are insensitive to the CH 3 NH 3 Br concentration. To explain these observations, we propose a phase-transformation model in which the reconstructive transitions necessary to convert a PbBr 2 nanocrystal into CH 3 NH 3 PbBr 3 initially create a high energy barrier for ion intercalation. A critical point in the transformation occurs when the crystal adopts the perovskite phase, at which point the activation energy for further ion intercalation becomes progressively smaller. Monte Carlo simulations that incorporate this change in activation barrier into the likelihood of reaction events reproduce key experimental observations for the intensity trajectories of individual particles. The insights gained from this study may be used to further control the crystallization of CH 3 NH 3 PbBr 3 and other solution-processed semiconductors.
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- PAR ID:
- 10086875
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- ISSN:
- 2050-7526
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C8TC06470A
