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Area selective atomic layer deposition (ASALD) is demonstrated to be a promising route to perform direct patterned deposition. In particular, methods to modify (or mask) the surface and process parameters to perform selective deposition of titanium dioxide have been developed and investigated in detail. Results indicated that self assembled monolayer based masking methodology posses significant limitations due to challenges associated with obtaining defect free monolayer and absence of traditional patterning techniques. On the other hand, polymer films based masking methodology offer a better alternative to perform ASALD. A number of factors that must be considered in designing a successful ASALD process based on polymer films were identified. These include: reactivity of polymer with ALD precursor, diffusion of ALD precursors through polymer mask and remnant precursor content in the polymer film during ALD cycling. Investigations suggested that ALD nucleation can be successfully blocked on polymer films that do not contain direct OH sites in their backbone. It was observed that sorption of water in the polymer film does not pose a serious limitation however; metal precursor diffusion through the polymer mask was identified as a critical parameter in determining the minimum required masking layer thickness for a successful ASALD process. In addition, a novel ASALD-based top surface imaging (TSI) technique has been developed. The ASALD-TSI process has demonstrated sharp contrast (etch barrier deposition vs exposure dose) and therefore offers the potential to overcome many of the challenges experienced with conventional TSI schemes.

This dissertation describes a theoretical and experimental study on coherent thermal emission from thin-film multilayer structures. A novel multilayer structure consisting of a one-dimensional photonic crystal and a polar material (or a metal) is proposed as a coherent thermal-emission source. Surface electromagnetic waves can be excited at the edge of photonic crystal, enabling coherent emission characteristics (i.e., spectral- and directional-selectivity in the emissivity). A near-infrared coherent emission source is designed and fabricated using vacuum deposition and chemical vapor deposition techniques. Measurements were performed using a Fourier-transform infrared spectrometer and a laser scatterometer. The agreement between the resonance conditions obtained from experiments and the calculated dispersion relation confirms that surface waves at the photonic crystal-metal interface can be utilized to build coherent thermal-emission sources. The second part of this dissertation focuses on the energy propagation direction in near-field thermal radiation. The energy streamline method based on the Poynting vector is applied to near-field thermal radiation by incorporating the fluctuational electrodynamics, in which thermal emission is viewed as originated from random motion of electric dipoles at temperatures above absolute zero. It is shown that the Poynting vector is decoupled for each parallel wavevector component due to the randomness of thermal emission. The spectral radiative energy travels in infinite directions along curved lines; this is a fundamental characteristic of near-field thermal radiation. The findings in this dissertation are important for the design of near-field optical sensors and energy conversion devices.

Understanding the mechanisms for fatigue crack initiation and propagation in micron-scale silicon (Si) is of great importance to assess and improve the reliability of Si based microelectromechanical systems (MEMS) in harsh environments. Accordingly, this investigation studies the fatigue properties of 10-micron-thick single-crystal Si (SCSi) films using kHz-frequency resonating structures under fully-reversed loading. Overall, the stress plays a major role on the fatigue properties: decreasing the stress amplitude from ~3-3.5 GPa to ~1.5-2 GPa results in an increase in lifetime from 10² to 10¹⁰ cycles, and a decrease in degradation rate by 4-5 orders of magnitude. In addition to stress, the influences of resonant frequency (4 vs. 40 kHz) and environment (30°C, 50%RH vs. 80°C, 30%RH and 80°C, 90%RH) on the resulting S-N curves and resonant frequency evolution are thoroughly investigated. In the high- to very high-cycle fatigue (HCF/VHCF) regime, both the frequency and environment strongly affect the fatigue properties. Damage accumulation rates are significantly higher in harsh environments. In 80°C, 90%RH the rates exceed by one to two orders of magnitude the values at 30°C, 50%RH for similar stress amplitudes. The separate influence of humidity, affecting the adsorbed water layer thickness, is also highlighted at 80°C: the decrease rates are measured up to one order of magnitude lower at 30%RH than at 90%RH. Moreover, a strong influence of frequency is detected. These observations bring further evidence supporting reaction-layer fatigue as a viable description of the HCF/VHCF behavior of micron-scale Si.

This work targeted the growth of gadolinium (Gd)-doped gallium nitride (GaN) thin films (Ga₁₋ₓGdₓN) by metal organic chemical vapor deposition (MOCVD). Characterization and evaluation of these Ga₁₋ₓGdₓN thin films for application in spintronics/optoelectronics devices also formed part of this work. This work presents: (1) the first report of stable, reproducible n- and p-type Ga₁₋ₓGdₓN thin films by MOCVD; (2) the first Ga₁₋ₓGdₓN p-n diode structure; and (3) the first report of a room temperature spin-polarized LED using a Ga₁₋ₓGdₓN spin injection layer. The Ga₁₋ₓGdₓN thin films grown in this work were electrically conductive, and co-doping them with Silicon (Si) or Magnesium (Mg) resulted in n-type and p-type materials, respectively. All the materials and structures grown in this work, including the Ga₁₋ₓGdₓN-based p-n diode and spin polarized LED, were characterized for their structural, optical, electrical and magnetic properties. The spin-polarized LED gave spin polarization ratio of 22% and systematic variation of this ratio at room temperature with external magnetic field was observed.

The spectral and directional control of radiative properties by utilizing engineered micro/nanostructures has enormous applications in photonics, microelectronics, and energy conversion systems. The present dissertation aims at: (1) design and analysis of micro/nanostructures based on wave interference and magnetic resonance effects to achieve tunable coherent thermal emission or enhanced optical transmission; (2) microfabrication of the designed structures; and (3) development of a high-temperature emissometer to experimental demonstrate coherent thermal emission from fabricated samples at temperatures from 300 K to 800 K. Asymmetric Fabry-Perot resonant cavities were studied as a potential coherent emission source. The reflectance was measured at room temperature using a Fourier-transform infrared spectrometer, and the emittance can be indirectly obtained from Kirchhoff's law. A high-temperature emissometer was built to measure the thermal emission of fabricated samples, and the temperature effect on the emission peaks was discussed. The direct and indirect approaches were unified and a generalized Kirchhoff's law was deduced to calculate thermal emission from layered structures with nonuniform temperatures. Magnetic polaritons were identified as a mechanism for achieving extraordinary optical transmission/absorption, through the comparison between equivalent capacitor-inductor models and the rigorous coupled-wave analysis. With carefully tuned geometric parameters, the resonance frequencies can be tailored for specific applications. A coherent emission source was designed with grating structures by excitation of magnetic polaritons, and is well suitable for thermophotovoltaic applications, thanks to the spectral selectivity and directional insensitivity of magnetic polaritons. Test samples were fabricated, and coherent thermal emission was experimentally observed at room temperatures up to 800 K. The results obtained in this dissertation will facilitate the design and application of micro/nanostructures in energy-harvesting systems.

Thesis (Ph. D.)--University of Canterbury, 2009. / Typescript (photocopy). Includes bibliographical references (p. 241-266). Also available via the World Wide Web.

Thesis (Ph. D.)--University of Alabama at Birmingham, 2007. / Title from PDF t.p. (viewed Feb. 3, 2010). Additional advisors: Derrick R. Dean, Sergey B. Mirov, Sergey Vyazovkin, Mary Ellen Zvanut. Includes bibliographical references (p. 122-145).

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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.