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

Abstract

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 (Δ Get = +2.24 eV), which is estimated electrochemically and from density functional theory calculations, is unfavorable for electron transfer from N, N-dimethylaniline to a quantum dot in the minimally excited (band-edge) state, electron transfer is obvious when a quantum dot is highly excited. Nonetheless, Δ Get crosses from the positive to negative scale as the solvent dielectric constant exceeds 5, favoring electron transfer from N, N-dimethylaniline to a quantum dot excited to the band-edge state. Based on single-molecule photoluminescence and ensemble electron transfer studies, we assign blinking suppression to the transfer of an electron from N, N-dimethylaniline to the hot hole state of a quantum dot. In addition to blinking suppression by electron transfer, complete removal of blinking is limited by short-living OFF states induced by the negative trion.