The precise control over the location of targeted dopants using expensive and time-consuming vacuum deposition techniques revolutionized the semiconductor industry. However, the analogous level of precision has not been attained in the solution-based syntheses of semiconductor nanostructures. The nucleation and growth kinetics of nanocrystals from monomeric precursors strongly favors the nucleation of undoped cores with dopants only incorporated during growth. As an alternative strategy to introduce dopants in the critical nucleus, we have focused our studies on a class of discrete molecular clusters that possess a framework similar to zincblende CdS. In this talk, we will present recent studies on the controlled speciation of transition metal ions into the core or surface cation sites of both [Cd10S4(SPh)16]4– and [Cd17S4(SPh)28]2– clusters. Confirmation of cluster location in the cluster is deduced from electrospray ionization mass spectrometry and various spectroscopies including electronic absorption and photoluminescence. These results provide insight into how the cluster dynamics and cluster-to-cluster equilibria can be exploited to introduce and trap impurities in the cluster core.

Controlled dopant speciation of dopants in CdS-based nanoclusters

256th National Meeting (2018)

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