Computational models have been developed that can accurately predict the electronic structure and thus optical properties of a variety of quantum dot (QD) materials. However, the application of these models to core/shell and other heterostructured QDs has received less experimental corroboration owing to the difficulty in systematically synthesizing and characterizing large ranges of geometries. In the current work, we synthesized a library of core/shell CdSe/CdS QDs with varying core sizes and shell thicknesses, and have characterized their radiative recombination rates. We find that the core size has only a modest effect on the radiative recombination rates, far less than is predicted by conventional effective mass models. In order to theoretically describe the experimental data, we performed an empirical modification of an effective mass model. We find that the conduction band offset between CdSe and CdS must be empirically altered based on QD core size in order to match our experimental data. This is hypothesized to be a result of reduced interfacial strain in core/shell QDs with smaller cores. The resultant relationship between conduction band offset and core size is used to create a predictive map of radiative lifetime as a function of core size and shell thickness. This map will be useful to researchers implementing CdSe/CdS core/shell QDs for a variety of applications since it can provide geometry specific excited state lifetimes.
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