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Theses and Dissertations

Development of catalytic stamp lithography for nanoscale patterning of organic monolayers Open Access

Descriptions

Other title
Subject/Keyword
organic monolayer
catalytic
block copolymer
poly(dimethylsiloxane)
nanoscale patterning
Type of item
Thesis
Degree grantor
University of Alberta
Author or creator
Mizuno, Hidenori
Supervisor and department
Buriak, Jillian (Chemistry)
Examining committee member and department
Cadien, Kenneth (Chemical and Materials Engineering)
Gates, Byron (Chemistry)
Harrison, Jed (Chemistry)
Veinot, Jonathan (Chemistry)
Bergens, Steven (Chemistry)
Department
Department of Chemistry
Specialization

Date accepted
2010-03-24T19:41:23Z
Graduation date
2010-06
Degree
Doctor of Philosophy
Degree level
Doctoral
Abstract
Nanoscale patterning of organic molecules has received considerable attention in current nanoscience for a broad range of technological applications. In order to provide a viable approach, this thesis describes catalytic stamp lithography, a novel soft-lithographic process that can easily produce sub-100 nm patterns of organic monolayers on surfaces. Catalytic stamps were fabricated through a two-step procedure in which the nanoscale patterns of transition metal catalysts are first produced on SiOx/Si surfaces via the use of self-assembled block-copolymers, followed by the production of the poly(dimethylsiloxane) (PDMS) stamps on top of the as-patterned metals. Simply peeling off the as-formed PDMS stamps removes the metallic nanostructures, leading to the functional stamps. A number of different patterns with various metals were produced from a commercially available family of block copolymers, polystyrene-block-poly-2-vinylpyridine, by controlling the morphology of thin-film templates through the modulation of molecular weights of polymer blocks or solvent vapor annealing. Using these catalytic stamps, hydrosilylation-based catalytic stamp lithography was first demonstrated. When terminal alkenes, alkynes, or aldehydes were utilized as molecular inks, the metallic (Pt or Pd) nanopatterns on catalytic stamps were translated into corresponding molecular arrays on H-terminated Si(111) or Si(100) surfaces. Since localized catalytic hydrosilylations took place exclusively underneath the patterned metallic nanostructures, the pattern formations were not affected by ink diffusion and stamp deformation even at the sub-20 nm scale, while maintaining the advantages of the stamp-based patterning (i.e., large-area, high-throughput capabilities, and low-cost). The concept of catalytic stamp lithography was further extended with other catalytic reactions, and successful nanoscale patterning was performed using hydrogenation (on azide-terminated SiOx surfaces) and the Heck reaction (on alkene- or bromphenyl-terminated SiOx surfaces). A range of nanopatterned surfaces with different chemical functionalities, including thiol, amine, and acid, were created, and they were further modified through appropriate chemical reactions. The potential utility of this simple approach for the construction of a higher degree of nanoarchitectures was suggested.
Language
English
DOI
doi:10.7939/R3GS7S
Rights
Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.
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File size: 13773097
Last modified: 2015:10:12 13:05:06-06:00
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File title: 01_title.pdf
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File author: Hidenori Mizuno
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