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[×ÊÔ´] Structural Investigations of Surfaces in Nanocrystals and Their Assemblies

Title:Structural Investigations of Surfaces and Orientation-Specific Phenomena in Nanocrystals and Their Assemblies
Creator/Author:Aruguete, Deborah Michiko  
Publication Date :2006 Jun 17
Resource Type:Thesis/Dissertation
Research Org Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)
Description/Abstract :
Studies of colloidal nanocrystals and their assemblies are presented. Two of these studies concern the atomic-level structural characterization of the surfaces, interfaces, and interiors present in II-VI semiconductor nanorods. The third study investigates the crystallographic arrangement of cobalt nanocrystals in self-assembled aggregates.
Crystallographically-aligned assemblies of colloidal CdSe nanorods are examined with linearly-polarized Se-EXAFS spectroscopy, which probes bonding along different directions in the nanorod. This orientation-specific probe is used, because it is expected that the presence of specific surfaces in a nanorod might cause bond relaxations specific to different crystallographic directions. Se-Se distances are found to be contracted along the long axis of the nanorod, while Cd-Se distances display no angular dependence, which is different from the bulk. Ab-initio density functional theory calculations upon CdSe nanowires indicate that relaxations on the rod surfaces cause these changes.
ZnS/CdS-CdSe core-shell nanorods are studied with Se, Zn, Cd, and S X-ray absorption spectroscopy (XAS). It is hypothesized that there are two major factors influencing the core and shell structures of the nanorods: the large surface area-to-volume
2 ratio, and epitaxial strain. The presence of the surface may induce bond rearrangements or relaxations to minimize surface energy; epitaxial strain might cause the core and shell lattices to contract or expand to minimize strain energy. A marked contraction of Zn-S bonds is observed in the core-shell nanorods, indicating that surface relaxations may dominate the structure of the nanorod (strain might otherwise drive the Zn-S lattice to accommodate the larger CdS or CdSe lattices via bond expansion). EXAFS and X-ray diffraction (XRD) indicate that Cd-Se bond relaxations might be anisotropic, an expected phenomenon for a rod-shaped nanocrystal...
http://www.osti.gov/bridge/servlets/purl/901229-NLaxyV/
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