Directing the Growth of Semiconductor Nanocrystals in Aqueous Solution: Role of Electrostatics

In this study, we demonstrate a new insight into the growth stage of aqueous semiconductor nanocrystals (NCs); namely, that the experimental variable‐dependent growth rate and photoluminescence quantum yields (PLQYs) are understandable according to electrostatics. In this context, the aqueous NCs possess (from core outwards) an inorganic core, ligand layer, adsorbed layer, and a diffuse layer. The presence of an electric double‐layer not only makes the NCs dispersible in the colloidal solution, but also governs the migration of monomers and monomer adsorption on the NC surface. To maintain NC growth, monomers need to migrate through the double‐layer. Consequently, the nature of the diffuse layer influences the ability of monomer diffusion and hence the growth rate of NCs. Systematic studies reveal that the experimental variables, including precursor concentrations, pH of the solution, additional NaCl concentrations, ratio of Cd to ligand, and the nature of the ligands significantly govern the nature of the NC electric double‐layer. The experimental variables, which reduce the thickness of the diffuse layer, benefit from monomer diffusion and a rapid growth of NCs. However, on the other hand, the diffuse layer also presents a charge‐selective transfer of Cd monomers. The neutral monomers, such as the complex of Cd²⁺ and 3‐mercaptopropionic acid (MPA) with 1:1 molar ratio Cd(MPA)], migrate through the diffuse layer more easily than the charged ones Cd(MPA)₂^2? or Cd(MPA)₃^4?], thus facilitating the growth of NCs. The nature of the adsorbed layer inside the diffuse layer, defined as the assumed interface of solid NCs and the liquid environment, also affects the growth rate and especially the PLQYs of NCs through the adsorption and coalescence of monomers on this interface. Strong interaction between the adsorbed layer and Cd monomers provides the opportunity to accelerate NC growth and to obtain NCs with high PLQYs.