Photoluminescence of charged CdSe/ZnS quantum dots in the gas phase: effects of charge and heating on absorption and emission probabilities.

Abstract

Gas phase spectral measurements for CdSe/ZnS core/shell nanocrystal quantum dots (QDs) before and after heating with both infrared (CO2) and visible lasers are reported. As-trapped QDs are spectrally similar to the same QDs in solution; however their photoluminescence (PL) intensities are very low, at least partly due to low absorption cross sections. After heating, the PL intensities brighten by factors ranging from ∼4 to 1800 depending on the QD size and pump laser wavelength. The emission spectra no longer resemble solution spectra and are similar, regardless of the QD diameter. Emission extends from the pump laser wavelength into the near-IR, with strong emission features above the band gap energy, between 645 and 775 nm, and in the near-infrared. Emission spectra from brightened QD ensembles, single QD aggregates, and single QD monomers are similar, showing that even single QDs support PL from a wide variety of states. The heating and cooling processes for QDs in this environment are analyzed, providing limits on the magnitudes of the absorption cross sections before and after thermal brightening. A model, based on absorption bleaching by extra electrons in the conduction band, appears to account for the changes in absorption and emission behavior induced by charging and heating.