Modeling Shell Formation in Core-Shell Nanocrystals in Reverse Micelle Systems

The mechanisms responsible for the formation of the shell in core−shell nanocrystals are ion-displacement and heterogeneous nucleation. In the ion-displacement mechanism, the shell is formed by the displacement reaction at the surface of the core nanoparticle whereas in heterogeneous nucleation the core particle induces the nucleation (or direct deposition) of shell material on its surface. The formation of core−shell nanocrystals via the post-core route has been examined in the current investigation. A purely probabilistic Monte Carlo scheme for the formation of the shell has been developed to predict the experimental results of Hota et al. (Hota, G.; Jain, S.; Khilar, K. C. Colloids Surf., A 2004, 232, 119) for the precipitation of Ag₂S-coated CdS (Ag₂S@CdS) nanoparticles. The simulation procedure involves two stages. In the first stage, shell formation takes place as a result of the consumption of supersaturation, ion displacement, and reaction between Ag⁺and excess sulfide ions. The growth in the second stage is driven by the coagulation of nanoparticles. The results indicate that the fraction of shell deposited by the ion-displacement mechanism increases with increasing ion ratio and decreases with increasing water-to-surfactant molar ratio.