Tailoring CsPbBr₃ Growth via Non-Polar Solvent Choice and Heating Methods
2022
Zamani, Hediyeh | Chiang, Tsung-Hsing | Klotz, Kaylie R. | Hsu, Annie J. | Maye, Mathew M.
This study describes an investigation of the role of non-polar solvents on the growth of cesium lead halide (CsPbX₃ X = Br and I) nanoplatelets. We employed two solvents, benzyl ether (BE) and 1-octadecene (ODE), as well as two nucleation and growth mechanisms, one-pot, facilitated by microwave irradiation (MWI)-based heating, and hot-injection, using convection. Using BE and MWI, large mesoscale CsPbBr₃ nanoplatelets were produced, whereas use of ODE produced small crystallites. Differences between the products were observed by optical spectroscopies, which showed first band edge absorptions consistent with thicknesses of ∼9 nm [∼15 monolayer (ML)] for the BE-CsPbBr₃ and ∼5 nm (∼9 ML) for ODE-CsPbBr₃. Both products had orthorhombic crystal structures, with the BE-CsPbBr₃ revealing significant preferred orientation diffraction signals consistent with the asymmetric and two-dimensional platelet morphology. The differences in the final morphology were also observed for products formed via hot injection, with BE-CsPbBr₃ showing thinner square platelets with thicknesses of ∼2 ML and ODE-CsPbBr₃ showing similar morphologies and small crystallite sizes. To understand the role solvent plays in crystal growth, we studied lead plumbate precursor (PbBrₙ²–ⁿ) formation in both solvents, as well as solvent plus ligand solutions. The findings suggest that BE dissolves PbBr₂ salts to a higher degree than ODE, and that this BE to precursor affinity persists during growth.
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