In this paper we critically examine the literature and provide new data on fundamental optical properties of II–VI quantum dots (QDs). Specifically, we examine the integrated extinction coefficients and radiative lifetimes of different sizes of CdSe and CdTe QDs and different shell thicknesses in CdTe/CdSe core/shell QDs. We have synthesized particles having very high quantum yields and find that the measured radiative lifetimes are considerably longer and have a very different size dependence than what has been previously reported. In a simple two-level system the integrated extinction coefficients (or oscillator strengths) are related to the radiative lifetimes through the Einstein relations. The situation is more complicated in the case of II–VI QDs because of the thermal accessibility of dark states resulting from the valence band fine structure. There are significant but not equal populations in both bright and dark sublevels of the 1Se-1S3/2 exciton and in the dark 1Se-1P3/2 exciton. These Boltzmann populations depend on the QD size and shape. We find that in all three cases, quantitative or semiquantitative agreement between the measured radiative lifetimes and values calculated from the integrated extinction coefficients is obtained only if Boltzmann populations in all of the thermally accessible bright and dark states are considered. We also find that the shell thickness dependence of the radiative lifetimes of the CdTe/CdSe core/shell particles can be quantitatively understood in terms of overlap of calculated electron and hole wave functions. The results and analyses presented here clarify several discrepancies in the literature.

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One-photon excitation of CdSe/CdS quantum dots (QDs) in room-temperature chloroform results in a delayed and reversible photodarkening of the sample. There is little or no prompt loss of photoluminescence intensity and the subsequent photodarkening takes place on the tens of minutes time scale. The photodarkening kinetics have been studied as a function of the solvent, particle ligation, concentration, and shell thickness. The results indicate that the photochemistry is the result of a “hot” hole being transferred to a surface ligand, followed by dissociation to a QD–/L+ ion pair. The hot hole is generated by a trion Auger process through a surface charging mechanism. In this mechanism, the presence of unpassivated chalcogenide surface atoms in II–VI semiconductor QDs results in electrons that are in an equilibrium between the valence band and chalcogenide surface orbitals, that is, a surface cadmium vacancy has resulted in a p-type QD. The latter state corresponds to a surface-charged QD. Photoexcitation of a surface-charged QD produces a trion, which can undergo Auger recombination to produce an unrelaxed hole. Following QD to ligand hole transfer and ligand dissociation, the positively charged ligand can react with another QD in solution causing photodarkening. Charge recombination occurs on a slower time scale and reverses the loss of photoluminescence intensity.

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