Molecular Design of Electrode Surfaces and Interfaces: For Optimized Charge Transfer at Transparent Conducting Oxide Electrodes and Spectroelectrochemical Sensing
AuthorMarikkar, Fathima Saneeha
KeywordsElectrode Surface Modification & Sub-Micron Patterning
Optimizing Indium Tin Oxide Electrodes
Diffraction Based Sensors
Electron Transfer Enhancement at Partially Blocked Electrodes
AdvisorArmstrong, Neal R.
Committee ChairArmstrong, Neal R.
MetadataShow full item record
PublisherThe University of Arizona.
RightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
AbstractThis dissertation has focused on i) optimizing charge transfer rates at indium-tinoxide (ITO) electrodes, and ii) characterization of the supramolecular structure and properties of ultra thin surface modifier films on modified electrodes for various device applications. Commercial ITO surfaces were modified using conducting polymer thin film architectures with and without various chemical activation procedures. Ferrocene derivatives were used as redox probes, which showed dramatic changes in electron transfer rate as the SA-PANI/PAA layers were added to the ITO surface. Highest rates of electron transfer were observed for DMFc, whose oxidation potential coincides with the potential region where these SA-PANI/PAA films reach their optimal electroactivity. Apparent heterogeneous electron transfer rate constants, kS, measured voltammetrically, were ca.10 x higher for SA-PANI/PAA films on ITO, versus clean ITO substrates. These films also showed linear potentiometric responses with retention of the ITO transparency with the capability to create smoothest films using an aqueous deposition protocol, which proved important in other applications. ITO electrodes were also modified via chemisorption of carboxy functionalized EDOTCA and electropolymerization of PEDOTCA/PEDOT copolymers, when properly optimized for thickness and structure, enhance voltammetrically determined electron transfer rates (kS) to solution probe molecules, such as dimethylferrocene (DMFc). Values of kS ≥ 0.4 cm•sec⁻¹, were determined, approaching rates seen on clean gold surfaces. ITO activation combined with formation of these co-polymer films has the effect of enhancing the electroactive fraction of electrode surface, versus a non-activated, unmodified ITO electrode, which acts as a “blocked” electrode. The electroactivity and spectroelectrochemistry of these films helped to resolve the electron transfer rate mechanism and enabled the construction of models in combination with AFM, XPS, UPS and RAIRS studies. The surface topography, structure, composition, work function and contact angle, also revealed other desirable properties for molecular electronic devices. The carboxylic functionality of the EDOTCA molecule adds more desirable properties compared to normal PEDOT films, such as favoring the deposition of smooth films, increasing the optical contrast, participating in hydrogen-bonding, chemisorption to oxide surface, self-doping and providing a linker for incorporation of different functional groups, new molecules, or nanoparticles. Periodic sub-micron electrode arrays can be created using micro-contact printing and electropolymerization. The sinusoidal modulation of the refractive index of such confined conducting polymer nanostructures or nanoparticle stripes allows efficient visible light diffraction. The modulation of the diffraction efficiency at PANI and PEDOT gratings in the presence of an analytical stimulus such as pH or potential demonstrate the sensing capability at these surfaces. The template stripped gold surfaces that are being developed in our lab demonstrate several advantages over commercially available evaporated gold films especially for nanoscale surface modification.
Degree GrantorUniversity of Arizona
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Electrode material and geometry effects on the electrical properties of particle traps in a parallel plate plasma etch reactorCollins, Sean Michael, 1959- (The University of Arizona., 1993)A newly designed Langmuir probe has been evaluated and was used to map the plasma potential near the powered electrode of a plasma etch chamber in 2 dimensions. Various electrode materials and geometries were used in order to investigate the relationship between electrode design and the presence of localized regions of elevated plasma potential. These regions of elevated plasma potential were known to be responsible for the presence of particle clouds suspended in the plasma during operation. A relationship was established between sharp edges on the powered electrode, insulating materials on the electrode and localized elevation in plasma potential. A thin layer of raised plasma potential has also been discovered at the plasma-sheath boundary. Suggestions for electrode design to reduce the presence of particles suspended in the plasma are made.
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