Abstract
We analyze the mechanism of seeded growth reactions used to synthesize colloidal core/shell nanocrystals. Looking at the formation of CdSe/CdS and CdSe/ZnSe using both zinc blende and wurtzite CdSe seeds with a different surface termination, we show that the formation rate of the shell material does not depend on the presence of the CdSe seed nanocrystals. This suggests that shells grow by inclusion of CdS or ZnSe initially formed in the reaction mixture, possibly under the form of reactive monomers, and not by successive adsorption and reaction of metal and chalcogen precursors. This insight makes balancing homogeneous nucleation and heterogeneous growth of the shell material key to suppressing spurious secondary nucleation. Through a combination of experimental work and reaction simulations, we show that this can be effectively achieved by raising the monomer solubility through the concentration of carboxylic acid used in the seeded growth reaction.