Detection of Pb2+ traces in dispersion of Cs4PbBr6 nanocrystals by in situ liquid cell transmission electron microscopy

The Cs4PbBr6 nanocrystals are often used as a starting material for the preparation of green-emitting CsPbBr3 perovskite nanocrystals by means of chemical and physical transformations. Herein, we probe the Cs4PbBr6 nanocrystals dispersed in a solvent by liquid cell transmission electron microscopy (LCTEM). The nanocrystal dispersion in toluene is placed between two electron-transparent membranes separated by a gold spacer in a liquid cell and studied in a high angular annular dark-field scanning TEM mode with a fixed electron dose rate. We observe the spontaneous nucleation and growth of round and dendrite-shaped nanoparticles under electron beam illumination in the areas of solution where no Cs4PbBr6 nanocrystals are seen. These newly-formed nanoparticles show high contrast and contain Pb as the only heavy element, suggesting that they are made from metallic lead and indicating Pb2+-containing species in solution as their precursor. Also, a small amount of Au-0 nanoparticles are formed, most likely due to the dissolution of the gold spacer by free Br-containing species in the nanocrystal dispersion and a subsequent reduction of the leached species under the electron beam. The analysis of the UV-Vis absorption spectra of Cs4PbBr6 nanocrystals and the supernatant isolated from the synthesis points to mixed lead(ii) oleate/bromide species as the likely residue, corroborating LCTEM results. The identification of the residual precursors in Cs4PbBr6 nanocrystal samples after the post-synthetic isolation is an important task because the residues may alter the subsequent reactivity of the nanocrystals.

Automated summary

Cs4PbBr6 nanocrystals are commonly used for the synthesis of CsPbBr3 perovskite nanocrystals. In this study, liquid cell transmission electron microscopy (LCTEM) was used to observe spontaneous nucleation and growth of nanoparticles, mainly containing Pb, under electron beam illumination in a toluene solution. The identification of residual precursors in Cs4PbBr6 nanocrystal samples is important to understand and control the reactivity of the nanocrystals in subsequent reactions.