Nucleation and Growth of Monodisperse CdTe and CdTe/ZnSe Core/shell Nanocrystals: Roles of Cationic Precursors, Ligands, and Solvents

With CdTe nanocrystals as a model system, we discover a new synthetic strategy for control of size and size distribution of colloidal semiconductor nanocrystals in both nucleation and growth stages. Especially in the nucleation stage, an in situ-formed cadmium complex with approximately one alkanoate and one alkylphosphonate ligand enables both high-yield nucleation by reacting the reactive cadmium-carboxylate bond with Te precursors and efficient size control by immediate passivation with the close-proximity alkylphosphonate ligand from the same complex. Conversely, control on size distribution during either homoepitaxial or heteroepitaxial growth requires reactive cadmium (or zinc) alkanoates as the cationic precursors with a minimum concentration of alkylphosphonate ligands in the novel synergistic solvents. This new strategy not only yields monodisperse CdTe and CdTe/ZnSe core/shell nanocrystals with unprecedented optical quality but also provides a much-needed alternative route for synthesizing monodisperse semiconductor nanocrystals, which is commonly hindered by the growth barrier of the dense ligand monolayer.