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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Variable Temperature Rate Coefficient Studies through a Coaxial Molecular Beam Radiofrequency Ring Electrode Ion TrapYuan, Bing (The University of Arizona., 2012)The dissertation focuses on the temperature dependent rate coefficient measurement of reactions in the interstellar medium using a coaxial molecular beam ring electrode ion trap apparatus. The first chapter introduces the previous studies of ion-molecule reactions in the ISM, the types of instruments mainly used in the reaction rate coefficient study, the former research on the ring electrode ion trap and the gas phase reaction mechanisms. Compare to other instruments, our molecular beam - ring electrode ion trap is extremely good at ion cooling and temperature control for both ions and neutral molecules. Chapter two describes each part of the instrument used in detail. Ions produced by electron impact in the ion source chamber, are mass filtered and then reach the ring electrode ion trap. In the trap, ions collide with molecules in the molecular beam where reaction takes place. When the reaction is done, all the ions remained in the trap (the reactant and product ions) come out and move to the detector. The molecular beam terminates at residual gas analyzer which is used for the number density calibration. The third chapter shows how the temperature of ions and molecules are controlled separately in order to find the reaction mechanism. Ions are cooled by the pulsed He buffer in the ring electrode trap and a chopped beam is used to make sure the ions are cooled to the desired low temperature when the reaction takes place. Chapters four to six describe the three reactions being studied using this instrument: N₂⁺ + H₂O charge transfer reaction, H₃O⁺ + C₂H₄ proton transfer reaction and H3O⁺ + (C₂H₂)₂/C₂H₂ dimer reaction. The temperature dependent rate coefficient data of these reactions are explained by the average dipole orientation theory, statistical theory and Colussi's acetylene dimer model, respectively. Two temperatures are defined and applied in the experimental rate coefficients analysis: ion-molecule center of mass collision temperature and the reaction statistical temperature which is based on the numbers of degrees of freedom of both reactants.