The Impact of Core/Shell Sizes on the Optical Gain Characteristics of CdSe/CdS Quantum Dots

Colloidal quantum dots (QDs) are highly attractive as the active material for optical amplifiers and lasers. Here, we address the relation between the structure of CdSe/CdS core/shell QDs, the material gain they can deliver, and the threshold needed to attain net stimulated emission by optical pumping. On the basis of an initial gain model, we predict that reducing the thickness of the CdS shell grown around a given CdSe core will increase the maximal material gain, while increasing the shell thickness will lower the gain threshold. We assess this trade-off by means of transient absorption spectroscopy. Our results confirm that thin-shell QDs exhibit the highest material gain. In quantitative agreement with the model, core and shell sizes hugely impact on the material gain, which ranges from 2800 cm^-1 for large core/thin shell QDs to less than 250 cm^-1 for small core/thick shell QDs. On the other hand, the significant threshold reduction expected for thick-shell QDs is absent. We relate this discrepancy between model and experiment to a transition from attractive to repulsive exciton-exciton interactions with increasing shell thickness. The spectral blue-shift that comes with exciton-exciton repulsion leads to competition between stimulated emission and higher energy absorbing transitions, which raises the gain threshold. As a result, small-core/thick-shell QDs need up to 3.7 excitations per QD to reach transparency, whereas large-core/thin shell QDs only need 1.0, a number often seen as a hard limit for biexciton-mediated optical gain. This makes large-core/thin-shell QDs that feature attractive exciton-exciton interactions the overall champion core/shell configuration in view of highest material gain, lowest threshold exciton occupation, and longest gain lifetime.