Proceedings of nanoGe Fall Meeting 2021 (NFM21)
DOI: https://doi.org/10.29363/nanoge.nfm.2021.165
Publication date: 23rd September 2021
Based on synthesis and the sample preparation procedure, the surface of colloidal nanocrystal is being covered by organic ligands on a regular manner. The ligand structure and the way of ligand-surface interaction can be crucial for the physicochemical and optical properties of nanocrystal as a system. In this work, we investigate the binding of zinc oleate to ZnSe nanocrystals from the perspective of its physicochemical properties. ZnSe nanocrystals have been used as narrow blue/violet emitters, as hosts for luminescent ions, or as large bandgap shell material, for example to form InP/ZnSe core/shell QDs [1]. In this study, we focus on neat ZnSe nanocrystals synthesized by injecting black selenium powder in a solution of zinc oleate in octadecene. By use of quantitative solution Nuclear Magnetic Resonance spectroscopy, we confirm that the ZnSe nanocrystals, obtained through described synthesis, are capped by zinc oleate. Following resembling work on CdSe quantum dots and nanoplatelets, we have shown that the addition of butylamine, an organic Lewis base or L-type ligands, leads to the displacement of zinc oleate from the ZnSe surface. By gradually increasing the concentration of butylamine, we record a displacement isotherm to represent the dynamic displacement equilibrium between bound zinc oleate and the desorbed zinc oleate butylamine complex. Going through quantitative analysis of these displacement isotherms and compare it with similar II-VI material we can conclude that zinc oleate is more prone to displacement from ZnSe as, for example, cadmium oleate ligand on the surface of CdSe quantum dots [2]. The estimation of the binding energy and the distribution of binding energies of zinc oleate over the surface of ZnSe nanocrystals can be done by using DFT-calculations on ZnSe model of the same crystal size.
(1) Tessier, M.D.; Dupont, D.; De Nolf, K.; De Roo, J.; and Hens, Z. Economic and Size-Tunable Synthesis of InP/ZnE (E = S, Se) Colloidal Quantum Dots. Chem. Mater. 2015, 27, 13, 4893–4898.
(2) Drijvers, E.; De Roo, J.; Martins, J.C.; Infante, I,; Hens, Z. Ligand Displacement Exposes Binding Site Heterogeneity on CdSe Nanocrystal Surfaces. Chem. Mater. 2018, 30, 3, 1178–1186.
Leila Mingabudinova thanks the SIM Flanders for the financial support and the Hercules foundation for funding the 500 MHz NMR equipment used in this work.
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