Radial-position-controlled doping of CdS/ZnS core/shell nanocrystals: surface effects and position-dependent...

Energy transfer in doped semiconductor nanocrystals: Mn-doped CdS/ZnS nanocrystals show interesting photoluminescence and EPR properties that are strongly dependent on the radial position of Mn dopants inside nanocrystals (see graphic). Furthermore, the results suggest a two-step mechanism for the energy transfer inside the doped nanocrystals.This paper reports a study of the surface effects and position-dependent properties of Mn-doped CdS/ZnS core/shell nanocrystals, which were prepared by using a three-step synthesis method. The Mn-doping level of these nanocrystals was determined by a combination of electron paramagnetic resonance spectroscopy and inductively coupled plasma atomic emission spectroscopy. These nanocrystals were further characterized by using transmission electron microscopy and fluorescence spectroscopy. First, we found that injecting a large excess of zinc stearate at the end of nanocrystal synthesis can sufficiently eliminate the surface-trap states from the doped CdS/ZnS core/shell nanocrystals and enhance their photoluminescence (PL) quantum yield (QY). Second, our results demonstrate that the Mn-PL QY is determined by the product of the efficiency of energy transfer from an exciton inside the CdS core to a Mn ion (Phi(ET)) and the efficiency of the emission from the Mn ion (Phi(Mn)). Third, Phi(Mn) strongly depends on the radial position of Mn ions in the doped core/shell nanocrystals. The position-dependent changes of Phi(Mn) nearly perfectly correlate to those of the linewidth of Mn EPR peaks: the higher the Phi(Mn), the narrower the linewidth of the Mn EPR peak. Fourth, the results demonstrate that Phi(ET) depends on the Mn-doping level as well as the inverse sixth power of the distance between a Mn ion and the center of its host nanocrystal. Accordingly, we propose a two-step mechanism for the energy transfer: 1) the energy transfer from an exciton inside the CdS core to a bound exciton around a Mn center, which is the rate-determining step and follows the Förster mechanism, and 2) the energy transfer from the bound exciton to the Mn center, which might follow a mechanism such as dark exciton (triplet exciton) or Auger transfer.