title: Surface-functionalization-dependent optical properties of II-VI semiconductor nanocrystals.
abstract: We report a study of the surface-functionalization-dependent optical properties of II-VI zinc-blende semiconductor nanocrystals on the basis of ligand-exchange chemistry, isomaterial core/shell growth, optical spectroscopy, transmission electron microscopy, and X-ray powder diffraction. Our results show that the transition energy and extinction coefficient of the 2S(h3/2)1S(e) excitonic band of these nanocrystals can be strongly modified by their surface ligands as well as ligand associated surface atomic arrangement. The oleylamine exchange of oleate-capped zinc-blende II-VI nanocrystals narrows the energy gap between their first and second excitonic absorption bands, and this narrowing effect is size-dependent. The oleylamine exchange results in the quenching, subsequent recovery, and even enhancing of the photoluminescence emission of these II-VI semiconductor nanocrystals. In addition, the results from our X-ray powder diffraction measurements and simulations completely rule out the possibility that oleate-capped zinc-blende CdSe nanocrystals can undergo zinc-blende-to-wurtzite crystal transformation upon ligand exchange with oleylamine. Moreover, our theoretical modeling results suggest that the surface-functionalization-dependent optical properties of these semiconductor nanocrystals can be caused by a thin type II isomaterial shell that is created by the negatively charged ligands (e.g., oleate and octadecyl phosphonate). Taking all these results together, we provide the unambiguous identification that II-VI semiconductor nanocrystals exhibit surface-functionalization-dependent excitonic absorption features.
authors.affiliation: Department of Chemistry, University of Florida, Gainesville, Florida 32611, USA.
authors.forename: Ou
authors.initials: O
authors.lastname: Chen
authors.forename: Yongan
authors.initials: Y
authors.lastname: Yang
authors.forename: Tie
authors.initials: T
authors.lastname: Wang
authors.forename: Huimeng
authors.initials: H
authors.lastname: Wu
authors.forename: Chenggang
authors.initials: C
authors.lastname: Niu
authors.forename: Jianhui
authors.initials: J
authors.lastname: Yang
authors.forename: Y Charles
authors.initials: YC
authors.lastname: Cao
mesh_terms: D053758:Nanoparticles / Q000737:chemistry*; D055095:Optics and Photonics; D012666:Semiconductors; D013499:Surface Properties