No abstract

CdSe x S y nanocrystals were synthesized in eight solvents that have different coordinating properties, trioctylphosphine oxide, trioctylphosphine, triphenylphosphine, oleylamine, hexadecylamine, dioctylamine, trioctylamine, and 1-octadecene at 230−300 °C. These nanocrystals exhibited high photoluminescence, which could be tuned over most of the visible region by changing the Se/S ratio or the solvent. The nanocrystals were characterized using UV−vis and IR spectroscopy, TEM, EDS, XRD, and NMR. 31P NMR and IR studies provided vital information about the nanocrystal surface capping ligands, indicating that those prepared in noncoordinating solvents were stabilized in solution mainly by oleic acid while those prepared in the coordinating solvents were stabilized mainly by solvent, phosphine and phosphine sulfide ligands, and some oleic acid. The hexagonal or cubic phase of these nanocrystals can be selectively prepared at temperatures as high as 300 °C by choosing the appropriate solvent.

Ligand exchange reactions at the surface of oleate- and trioctylphosphine oxide (TOPO)-capped CdS quantum dots have been studied with attenuated total reflection infrared (ATR-IR) spectroscopy, using thin films deposited from organic solvent suspensions. The oleate and trioctylphosphine capping ligands were found to form highly ordered and densely packed monolayers on the CdS surface. Adsorbed oleate is coordinated to CdS in a chelating bidentate manner through the carboxylate functional group, while adsorbed trioctylphosphine oxide is coordinated though the P=O functional group and appears to have numerous adsorption environments on the CdS surface. Exposure of such films to aqueous solution was found to cause partial delamination of the films from the ATR prism interface which was reversible upon redrying. Ligand exchange reactions on the oleate- and trioctylphosphine-capped CdS films were studied in situ at room temperature by allowing the films to be exposed to dilute aqueous solutions of thiol-containing ligands. Oleate and trioctylphosphine oxide are both strongly adsorbed to the CdS surface, and ligand exchange with monothiol-containing ligands has been found to be highly dependent upon experimental conditions, in particular pH, where exchange is only observed at solution pH where the exchanging ligand is uncharged. This is attributed to the inability of a charged ligand to penetrate the hydrophobic polymethylene layer on the CdS surface.