X-RAY PHOTOELECTRON-SPECTROSCOPY OF CDSE NANOCRYSTALS WITH APPLICATIONS TO STUDIES OF THE NANOCRYSTAL SURFACE

We report the use of X-ray photoelectron spectroscopy (XPS) to determine the surface composition of semiconductor nanocrystals. Crystalline, nearly monodisperse CdSe nanocrystals ranging in radius from 9 to 30 Angstrom were chemically synthesized and covalently bound to Au and Si surfaces for study. XPS core level peak positions for Cd and Se were in agreement with those of bulk CdSe. We have determined that the majority of Se atoms on the surface are unbonded as prepared and that Cd atoms are bonded to the surface ligand, tri-n-octylphosphine oxide, to the extent that such bonding is sterically allowed. We have determined that the total ligand saturation of the nanocrystal surface varies from 60% in the smaller nanocrystals to 30% in the larger nanocrystals. In addition, we have determined that upon exposure of the nanocrystals to air Se surface sites are oxidized, forming a SeO2 surface film which causes the nanocrystals to degrade over time. The nanocrystal surface can be modified by dispersing the crystals in pyridine. Nearly all of the P ligands are removed in this case, leaving behind primarily unsaturated Cd and Se surface atoms. In this case, both Cd and Se oxidize upon exposure to air.