Lead chalcogenide colloidal quantum dots are attractive candidates for applications operating in the near infrared spectral range. However, their function is forestalled by limited stability under ambient conditions. Prolonged temperature-activated cation-exchange of Cd(2+) for Pb(2+) forms PbSe/CdSe core/shell heterostructures, unveiling a promising surface passivation route and a method to modify the dots' electronic properties. Here, we follow early stages of an-exchange process, using spectroscopic and structural characterization tools, as well as numerical calculations. We illustrate that preliminary-exchange stages involve the formation of nonconcentric heterostructures, presumably due to a facet selective reaction, showing a pronounced change in the optical properties upon the increase of the degree of nonconcentricity or/and plausible creation of core/shell interfacial alloying. However, progressive-exchange stages lead to rearrangement of the shell segment into uniform coverage, providing tolerance to oxygen exposure with a spectral steadiness already on the formation of a monolayer shell.
Keywords: cation-exchange; colloidal quantum dots; effective mass approximation; nonconcentric core/shell.