Anomalous photo-induced spectral changes in CdSe/ZnS quantum dots

We study photo-induced static and dynamic spectral changes in self-assembled CdSe/ZnS quantum dot (QD) thin films with varying QD concentrations under ambient conditions. Using spatially resolved scanning photoluminescence microscopy in conjunction with spectrally resolved time-correlated photon counting, we measure the variations in spectral intensity, emission wavelength, and recombination lifetimes as functions of photo-exposure time. We find that at low concentrations photo-darkening and photo-oxidation rates slow down with increasing QD density, but in the high concentration limit these rates are strongly enhanced. Our measurements lead us to conclude that the interplay of photo-induced surface trap discharging with preferential photo-oxidation of smaller QDs is further modulated by resonant energy transfer driven by strong inter-dot interactions in highly concentrated samples. Our results would imply that the efficiency and longevity of semiconducting nanoparticle based opto-electronic devices will be limited by the concentration of the active material (C) 2011 American Institute of Physics. [doi: 10.1063/1.3630977]