Blinking Suppression in Highly Excited CdSe/ZnS Quantum Dots by Electron Transfer under Large Positive Gibbs (Free) Energy Change

Semiconductor quantum dots with stable photoluminescence are necessary for next generation optoelectronic and photovoltaic devices. Photoluminescence intensity fluctuations of cadmium and lead chalcogenide quantum dots have been extensively investigated since the first observation of blinking in CdSe nanocrystals in 1996. In a quantum dot, blinking originates from stochastic photocharging, nonradiative Auger recombination, and delayed neutralization. So far, blinking is suppressed by defect passivation, electron transfer, and shell preparation, but without any deep insight into free energy change of electron transfer. We report real-time detection of significant blinking suppression for CdSe/ZnS quantum dots exposed to N,N-dimethylaniline, which is accompanied by a considerable increase in the time-averaged photoluminescence intensity of quantum dots. Although the Gibbs (free) energy change (ΔGet = +2.24 eV), which is estimated electrochemically and from density functional theory calculations, is unfavora...