Thesis (M.S.)--University of Michigan, 1970.

Thesis (M.S.)--University of Michigan, 1970.

No description available.

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2007. / Committee Chair: Mizaikoff, Boris; Committee Member: Bottomley, Lawrence; Committee Member: Hunt, William; Committee Member: Janata, Jiri; Committee Member: Josowicz, Miroslawa.

The use of Attenuated Total Reflectance as an analytical technique in infrared spectroscopy has become increasingly important in the past few years. ATR (Attenuated Total Reflectance) is a relatively new analytical method. Producing spectra of compounds by this method requires no solvent for dissolving the sample and no salts for making pellets. The only requirements for spectra production, similar in quality to those produced by conventional methods, are that there is enough sample to cover both sides of the reflector be similar. The index of the sample is fixed; therefore, the index of the reflector is controlled by selecting a reflector with one similar to the sample. Reflectors with indices from 1.2 to 4.12 are commercially produced. Since no solvents or salts are used in ATR, this method allows complete recovery of the sample without using separation or abstraction processes. The elimination of solvents and salts should also lower the cost of spectra production. The ATR method eliminates the weighing and measuring of samples and salts and the time consuming process of pellet making; therefore, it should be a quicker method than any of the conventional methods. The principles of ATR have been applied to several fields of infrared analysis. Harris and Svoboda used ATR as a means of determination of Alkyl and Monomer Modified Resins; Katlaksky and Keller used ATR to study aqueous solutions. Ahliyah and MOoney used ATR in preparing spectra of Polyatomic Anions, and Deley and Liotti used ATR as a means of identifying coating on paper. Materials for which ATR has been useful in analysis include fabrics, polymers which cannot be easily prepared for other types of analysis, and surfaces of semiconductors. In this project, spectra of several pure barbiturates, drug compositions containing barbiturates, and several related compounds were prepared using ATR; these were compared to spectra produced by the conventional pellet method.

Structural changes of electroactive species during electrochemical reactions cannot be determined from the electroanalytical technique alone. By incorporating spectroscopic techniques with electrochemistry, additional information about analyte structure and composition of the double layer can be obtained during electrochemical processes. Several spectroscopic methodologies have been tailored for this purpose including electronic and vibrational spectroscopies. Mid-infrared ATR spectroscopy is especially interesting as it provides in-situ information about adsorbates at the electrode surface. Mass transport limitations present in mid-infrared (mid-IR) external reflection and transmission spectroelectrochemistry are circumvented with attenuated total reflectance (ATR) spectroelectrochemistry. However, limitations of appropriate electrode materials for internal reflection configurations have hindered widespread adoption of the technique. The work described in this thesis focuses on the development and coupling of electrically conducting DLC films with mid-IR transparent multi-reflection waveguides for ATR spectroelectrochemistry. Conducting diamondlike carbon (DLC) thin films were developed utilizing pulsed laser deposition systems in collaboration with Joanneum Research (Leoben, Austria) and at the University of North Carolina (Chapel Hill). Nitrogen doping and incorporation of noble metal nanoclusters were investigated as approaches aimed at improving the electrical conductivity of DLC. Detailed compositional studies of nitrogen-doped DLC layers showed that sp2-hybridized carbon is responsible for the observed electrochemical activity. Optical transparency of thin (~ 40 nm) DLC layers in the mid-IR regime was confirmed by transmission-absorption measurements upon deposition on zinc selenide ATR waveguides. Additionally, the first spectroelectrochemical application of conducting DLC films was demonstrated via the electropolymerization of polyaniline onto coated ATR elements. Metal-DLC nanocomposite layers were investigated with various analytical techniques obtaining detailed compositional information. Improved electrochemical activity of metal-DLC demonstrated their suitability as electrode materials. Sufficient mid-IR transmissivity of metal-DLC coated germanium waveguides was displayed to enable spectroelectrochemical application. Finally, electropolymerization of poly(4-vinylpyridine) in acetonitrile was pursued to produce highly cross-linked ion-exchange membranes for spectroelectrochemical sensing. The composition of the pre-polymerization mixture and deposition conditions were tailored to obtain uniform semipermeable membranes. Diffusion of cations to electrodes is restricted by performing the electropolymerization as established herein. By employing the described electropolymerization procedure at DLC-coated waveguides, spectroelectrochemical sensing strategies can now be extended into the mid-IR regime.

As the miniaturization of functional devices in integrated circuit (IC) continues to scale down to sub-nanometer size, the process complexity increases and makes materials characterization difficult. One of our research effort demonstrates the development and application of novel Multiple Internal Reflection Infrared Spectroscopy (MIR-IR) as a sensitive (sub-5 nm) metrology tool to provide precise chemical bonding information that can effectively guide through the development of more efficient process control. In this work, we investigated the chemical bonding structure of thin fluorocarbon polymer films deposited on low-k dielectric nanostructures, using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Complemented by functional group specific chemical derivatization reactions, fluorocarbon film was established to contain fluorinated alkenes and carbonyl moieties embedded in a highly cross-linked, branched fluorocarbon structure and a model bonding structure was proposed for the first time. In addition, plasma induced damage to high aspect ratio trench low-k structures especially on the trench sidewalls was evaluated both qualitatively and quantitatively. Damage from different plasma processing was correlated with Si-OH formation and breakage of Si-CH3 bonds with increase in C=O functionality. In another endeavor, TiN hard mask defect formation after fluorocarbon plasma etch was characterized and investigated. Finding suggest the presence of water soluble amines that could possibly trigger the formation of TiN surface defect. An effective post etch treatment (PET) methods were applied for etch residue defect removal/suppression.

No description available.