title: Photostability of CdSe quantum dots functionalized with aromatic dithiocarbamate ligands.
abstract: Organic ligands are widely used to enhance the ability of CdSe quantum dots (QDs) to resist photodegradation processes such as photo-oxidation. Because long alkyl chains may adversely affect the performance of QD devices that require fast and efficient charge transfer, shorter aromatic ligands are of increasing interest. In this work, we characterize the formation of phenyl dithiocarbamate (DTC) adducts on CdSe surfaces and the relative effectiveness of different para-substituted phenyl dithiocarbamates to enhance the aqueous photostability of CdSe QDs on TiO2. Optical absorption and photoluminescence measurements show that phenyl DTC ligands can be highly effective at reducing QD photocorrosion in water, and that ligands bearing electron-donating substituents are the most effective. A comparison of the QD photostability resulting from use of ligands bearing DTC versus thiol surface-binding groups shows that the DTC group provides greater QD photostability. Density functional calculations with natural bond order analysis show that the effectiveness of substituted phenyl DTC results from the ability of these ligands to remove positive charge away from the CdSe and to delocalize positive charge on the ligand.
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison , Madison, Wisconsin 53706, United States.
authors.forename: Yizheng
authors.initials: Y
authors.lastname: Tan
authors.forename: Song
authors.initials: S
authors.lastname: Jin
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Hamers