Sulfidation of Cadmium at the Nanoscale

We investigate the evolution of structures that result when spherical Cd nanoparticles of a few hundred nanometers in diameter react with dissolved molecular sulfur species in solution to form hollow CdS. Over a wide range of temperatures and concentrations, we find that rapid Cd diffusion through the growing CdS shell localizes the reaction front at the outermost CdS/S interface, leading to hollow particles when all the Cd is consumed. When we examine partially reacted particles, we find that this system differs significantly from others in which the nanoscale Kirkendall effect has been used to create hollow particles. In previously reported systems, partial reaction creates a hollow particle with a spherically symmetric metal core connected to the outer shell by filaments. In contrast, here we obtain a lower symmetry structure, in which the unreacted metal core and the coalesced vacancies separate into two distinct spherical caps, minimizing the metal/void interface. This pattern of void coalescence is likely to occur in situations where the metal/vacancy self-diffusivities in the core are greater than the diffusivity of the cations through the shell.