Studies of Structure and Reactivity in Monolayer Assemblies: 1. Ozonolysis of Alkanethiolate Self Assembled Monolayers on Au. 2. In-Plane Resistivity of Ultrathin Gold Films as a High Sensitivity, Molecularly Differentiated Probe of Chemisorption at the Liquid-Metal Interface
Zhang, Yumo
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https://hdl.handle.net/2142/84462
Description
Title
Studies of Structure and Reactivity in Monolayer Assemblies: 1. Ozonolysis of Alkanethiolate Self Assembled Monolayers on Au. 2. In-Plane Resistivity of Ultrathin Gold Films as a High Sensitivity, Molecularly Differentiated Probe of Chemisorption at the Liquid-Metal Interface
Author(s)
Zhang, Yumo
Issue Date
1999
Doctoral Committee Chair(s)
Bohn, Paul W.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Analytical
Language
eng
Abstract
Ultrathin gold films, with thicknesses between the onset of conductivity (d ∼ 5 nm) and the electron mean free path ( d ∼ 80 nm), display surface-sensitive resistivities, which have been exploited to follow the adsorption and desorption of molecular monolayers at the metal solution interface with high precision. For nominal Au film thicknesses (d ∼ 40 nm), strongly chemisorbed thiolate monolayers increase the resistivity of the thin Au films by ca. 4%, but weakly adsorbed species, such as pyridine or phenolate at open circuit, induce no observable change in the Au film resistance. Resistivity measurements implemented with a high stability current source and high-precision digital voltmeter sampling at 1 Hz resulted in 3 sigma uncertainties in alkanethiolate coverage of 1.4 x 10--4 monolayer. Correlating chemical manipulations with changes in surface morphology as characterized by AFM indicates a significant morphology-related contribution to resistivity which must be controlled to extract meaningful information related to the electronic interaction of adsorbate and substrate.
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