The Underlying Chemical Mechanism of Selective Chemical Etching in CsPbBr₃ Nanocrystals for Reliably Accessing Near-Unity Emitters

Journal Article · Wed Sep 25 00:00:00 EDT 2019 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.9b05782· OSTI ID:1619131

Koscher, Brent A. ^[1]; Nett, Zachary ^[1]; Alivisatos, A. Paul ^[1]

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1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)

Reliably accessing nanocrystal luminophores with near-unity efficiencies aids in the ability to understand the upper performance limits in optoelectronic applications that require minimal nonradiative losses. Constructing structure-function relationships at the atomic level, while accounting for inevitable defects, allows for the development of robust strategies to achieve near-unity quantum yield luminophores. For CsPbBr₃ perovskite nanocrystals, bromine vacancies leave behind undercoordinated lead atoms that act as traps, limiting the achievable optical performance of the material. Here, we show that selective etching represents a promising path for mitigating the consequences of optical defects in CsPbBr₃ nanocrystals. A mechanistic understanding of the etching reaction is essential for developing strategies to finely control the reaction. We report a study of the selective etching mechanism of CsPbBr3 nanocrystal cubes by controlling the etchant chemical potential. We observe optical absorption and luminescence trajectories while varying the extent and rate of lead removal, removing in some cases up to 75% of the lead from the original nanocrystal ensemble. At modest etchant chemical potentials, the size and shape uniformity of the nanocrystal ensemble improves in addition to the quantum yield, proceeding through a layer-by-layer etching mechanism. Operating with excessively high etchant chemical potentials is detrimental to the overall optical performance as the etching transitions to nonselective, while too low of a chemical potential results in incomplete etching. Through this general approach, we show how to finely control selective etching to consistently access a steady state or chemical stability zone of near-unity quantum yield CsPbBr₃ nanocrystals postsynthetically, suggesting a practical framework to extend this treatment to other perovskite compositions and sizes.

• Research Organization: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
• Grant/Contract Number: AC02-05CH11231
• OSTI ID: 1619131
• Journal Information: ACS Nano, Journal Name: ACS Nano Journal Issue: 10 Vol. 13; ISSN 1936-0851
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CsPbBr3
colloidal nanocrystals
lead halide perovskites
photoluminescence quantum yield
selective etching