Ligand-Controlled Growth of ZnSe Quantum Dots in Water during Ostwald Ripening


A strong ligand effect was observed for the aqueous-phase growth of ZnSe quantum dots (QDs) in the Ostwald ripening (OR) stage. The QDs were made by injecting Se monomer at room temperature followed by a ramp to 100 °C. The ramp produced a second, more gradual increase in the concentrations of both Zn and Se monomers fed by the dissolution of QDs below the critical size. The dissolution process was followed using measurements of the mass of Zn in QDs and in the supernatant by inductively coupled plasma optical emission spectroscopy (ICP-OES). Despite the flux of monomers, there was little growth in the QDs of average size based on UV–vis absorption spectra, until the temperature reached 100 °C, when there was a period of rapid growth followed by a period of linear growth. The linear growth stage is the result of OR as the total mass of Zn in QDs and in the solvent remained constant. The growth data were fit to a continuum model for the limiting case of surface reaction control. The rate is proportional to the equilibrium coefficient for ligand detachment from the QD surface. The ligand 3-mercaptopropionic acid (MPA) was the most tightly bound to the surface and produced the lowest growth rate of (1.5–2) × 10<sup>–3</sup> nm/min in the OR stage, whereas thiolactic acid (TLA) was the most labile and produced the highest growth rate of 3 × 10<sup>–3</sup> nm/min. Methyl thioglycolate (MTG) and thioglycolic acid (TGA) produced rates in between these values. Ligands containing electron-withdrawing groups closer to the S atom and branching promote growth, whereas longer, possibly bidendate, ligands retard it. Mixed ligand experiments confirmed that growth is determined by ligand bonding strength to the QD. Photoluminescence spectroscopy showed that the more labile the ligand, the more facile the repair of surface defects during the exposure of the QDs to room light

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