Two-Photon Photochemistry of CdSe Quantum Dots.

Zeng, Youhong; Kelley, David F · ACS Nano · 2015

basic_science · Level V

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Abstract

The two-photon photochemistry of CdSe quantum dots (QDs) has been systematically studied. We find that upon intense irradiation CdSe quantum dots that absorb two or more visible photons undergo photodarkening. The quantum yield for this process is on the order of 6% in chloroform and much smaller in nonpolar solvents, such as octane. An analysis of the energetics indicates that, following two-photon excitation, the biexciton undergoes an Auger process producing a hot hole. This hot hole is ejected to a surface-bound TOP ligand, forming a QD(-)/TOP(+) contact ion pair that separates in chloroform, but not in octane. The charged and deligated QD is dark, resulting in the overall photodarkening. This photodarkening reaction may or may not be reversible, depending on what other chemical components are in the irradiated solution. The quantum dot concentration dependence and PL decay kinetics indicate that charge recombination occurs rapidly, followed by ligand reattachment and reorganization on a longer (tens of minutes) time scale. The relation of this mechanism to one-photon photochemistry is also discussed.