Electron Stability and Negative-Tetron Luminescence in Free-Standing Colloidal n-Type CdSe/CdS Quantum Dots

We examine the effects of CdS shell growth on photochemical reduction of colloidal CdSe quantum dots (QDs) and describe the spectroscopic properties of the resulting n-type CdSe/CdS QDs. CdS shell growth greatly slows electron trapping. Because of this improvement, complete two-electron occupancy of the 1S e conduction-band orbital is achieved in CdSe/CdS QDs and found to be much more stable than in past experiments. Simultaneous photoluminescence at two different energies is now observed from QDs possessing two excess conduction-band electrons, reflecting competing recombination of discretized 1S e and 1P e conduction-band electrons within photogenerated four-carrier negative tetrons (three electrons and one hole). Stable occupancy of the 1P e level is not achievable under these conditions, and possible reasons are discussed. The stability and accessibility of these multielectron configurations, and the facile spectroscopic detection of negative tetrons, both make photodoped core/shell QDs attractive for exploring the physical properties of free-standing heavily n-doped colloidal CdSe-based QDs.