Inorganic Cluster Syntheses of TM²⁺-Doped Quantum Dots (CdSe, CdS, CdSe/CdS):  Physical Property Dependence on Dopant Locale

A series of colloidal transition-metal-doped chalcogenide semiconductor nanocrystals (TM2+:CdSe, TM2+:CdS, etc.) has been prepared by thermal decomposition of inorganic cluster precursors. It is shown through extensive spectroscopic and structural characterization that the nanocrystals prepared following literature procedures for synthesis of TM2+:CdSe nanocrystals actually possess an unintended CdSe/TM2+:CdS core/shell morphology. The conditions required for successful formation of TM2+:CdSe and TM2+:CdS by cluster decomposition have been determined. Magneto-optical and photoluminescence spectroscopic results for this series of doped nanocrystals reveal major physical consequences of dopant localization within the shell and demonstrate the capacity to engineer dopant-carrier exchange interactions via core/shell doping strategies. The results presented here illustrate some of the remarkable and unexpected complexities that can arise in nanocrystal doping chemistries and emphasize the need for meticulous characterization to avoid false positives.