Skip navigation
Please use this identifier to cite or link to this item:
Title: Self-Assembled Monolayers at the Solid-Liquid Interface: Design, Post-Modification and Effects of Molecular Variations as Compared to Homogenous Systems
Authors: Frederick, Esther Frederick
Advisors: Bernasek, Steven L
Contributors: Chemistry Department
Keywords: heterogenous chemistry
solid-liquid interface
Subjects: Chemistry
Materials Science
Issue Date: 2016
Publisher: Princeton, NJ : Princeton University
Abstract: Since the dawn of chemistry, the study of reactions has taken place in homogenous systems. There is a wealth of knowledge relating to the kinetics and thermodynamics of such reactions. However, the increasingly smaller materials used in today’s advancing technology requires novel heterogeneous chemistries at solid-liquid interfaces. Control over surface chemistry has numerous applications, including increasing biocompatibility for medical use, catalysis, improving cosmetic products and developing novel electronic devices. As we move toward a world with self-healing materials, single molecule circuits and nanoscale machines, the ability to attach molecules to a surface in a well-organized fashion is increasingly important. Astoundingly, under appropriate conditions, single molecules self-arrange into highly ordered nanomaterials using guidelines internally coded by its elements and their arrangement in the molecule. Being able to exploit self-assembly is invaluable to successful fast-paced engineering of nanomaterials. However, quantifying the interplay between forces and developing a predictive model for 2D self-assembly is to date unsolved. An additional question that largely remains unanswered is, to what extent can relationships known from homogenous chemistry aid in understanding the self-assembly of heterogeneous systems? The work in thesis was motivated by these fundamental problems. This thesis includes studies of both physisorbed and chemisorbed systems. Chapters 3 and 4 explore the effect of H-bonding and van der Waals interactions on physisorbed self-assembled monolayer (SAM) morphology using a series of 5-alkoxyisophthalamides and 5-alkoxyisophthalic acids on HOPG. The relationship between self-assembly in heterogeneous versus homogenous phases was examined in Chapter 3 and continued in chemisorbed systems in Chapter 5. The results of substituent effects on formation kinetic studies of chemisorbed styrene SAMs on H-Si fit to equations quantifying substituent effects in homogenous reactions. These studies provide evidence for the success in applying well quantified homogeneous relationships to lesser explored chemistry at a solid-liquid interface. As interest in unique surface functionalization grew, this thesis expanded to include collaborations requiring surfaces exhibiting specific properties. These projects, described in Chapter 6 and 7, include surface assemblies for fullerene bombardment and SAMs for quantum control experiments. The design, post-modification and characterization of Si-phosphonate and Au-carbene linked SAMs for designated applications are presented.
Alternate format: The Mudd Manuscript Library retains one bound copy of each dissertation. Search for these copies in the library's main catalog:
Type of Material: Academic dissertations (Ph.D.)
Language: en
Appears in Collections:Chemistry

Files in This Item:
File Description SizeFormat 
Frederick_princeton_0181D_11773.pdf3.91 MBAdobe PDFView/Download

Items in Dataspace are protected by copyright, with all rights reserved, unless otherwise indicated.