Doctor of Philosophy / Department of Physics / Jingyu Lin / Time-resolved deep ultraviolet (DUV) Photoluminescence (PL) spectroscopy system has been employed to systematically monitor crystalline quality, identify the defects and impurities, and investigate the light emission mechanism in III-nitride semiconducting materials and photonic structures. A time correlated single photon counting system and streak camera with corresponding time resolutions of 20 and 2 ps, respectively, were utilized to study the carrier excitation and recombination dynamics. A closed cycle He-flow cryogenic system was employed for temperature dependent measurements. This system is able to handle sample temperatures in a wide range (from 10 to 900 K). Structural, electrical, and morphological properties of the material were monitored by x-ray diffraction (XRD), Hall-effect measurement, and atomic force microscopy (AFM), respectively. Most of the samples studied here were synthesized in our laboratory by metal organic chemical vapor deposition (MOCVD). Some samples were bulk AlN synthesized by our collaborators, which were also employed as substrates for homoepilayer growth. High quality AlN epilayers with (0002) XRD linewidth as narrow as 50 arcsec and screw type dislocation density as low as 5x10[superscript]6 cm[superscript]-2 were grown on sapphire substrates. Free exciton transitions related to all valence bands (A, B, and C) were observed in AlN directly by PL, which allowed the evaluation of crystal field (Δ[subscript]CF) and spin-orbit (Δ[subscript]SO) splitting parameters exerimentally. Large negative Δ[subscript]CF and, consequently, the difficulties of light extraction from AlN and Al-rich AlGaN based emitters due to their unique optical polarization properties have been further confirmed with these new experimental data. Due to the ionic nature of III-nitrides, exciton-LO phonon Frohlich interaction is strong in these materials, which is manifested by the appearance of phonon replicas accompanying the excitonic emission lines in their PL spectra. The strength of the exciton-phonon interactions in AlN has been investigated by measuring the Huang-Rhys factor. It compares the intensity of the zero phonon (exciton emission) line relative to its phonon replica. AlN bulk single crystals, being promising native substrate for growing nitride based high quality device structures with much lower dislocation densities (<10[superscript]4 cm[superscript]-2), are also expected to be transparent in visible to UV region. However, available bulk AlN crystals always appear with an undesirable yellow or dark color. The mechanism of such undesired coloration has been investigated. MOCVD was utilized to deposit ~0.5 μm thick AlN layer on top of bulk crystal. The band gap of strain free AlN homoepilayers was 6.100 eV, which is ~30 meV lower compared to hetero-epitaxial layers on sapphire possessing compressive strain. Impurity incorporation was much lower in non-polar m-plane growth mode and the detected PL signal at 10 K was about an order of magnitude higher from a-plane homo-epilayers compared to that from polar c-plane epilayers. The feasibility of using Be as an alternate p-type dopant in AlN has been studied. Preliminary studies indicate that the Be acceptor level in AlN is ~330 meV, which is about 200 meV shallower than the Mg level in AlN. Understanding the optical and electronic properties of native point defects is the key to achieving good quality material and improving overall device performance. A more complete picture of optical transitions in AlN and GaN has been reported, which supplements the understanding of impurity transitions in AlGaN alloys described in previous reports.

Doctor of Philosophy / Department of Chemical Engineering / Vikas Berry / Graphene - a single atom thick two dimensional sheet of sp[superscript]2 bonded carbon atoms arranged in a honeycomb lattice - has shown great promise for both fundamental research & applications because of its unique electrical, optical, thermal, mechanical and chemical properties. Derivatization of graphene unlocks a plethora of novel properties unavailable to their pristine parent “graphene”. In this dissertation we have synthesized various structural and chemical derivatives of graphene; characterized them in detail; and leveraged their exotic properties for diverse applications. We have synthesized protein/DNA/ethylenediamine functionalized derivatives of graphene via a HATU catalyzed amide reaction of primary-amine-containing moieties with graphene oxide (GO) – an oxyfunctional graphene derivative. In contrast to non-specificity of graphene, this functionalization of GO has enabled highly specific interactions with analytes. Devices fabricated from the protein (concanavalin – A) and DNA functionalized graphene derivatives were demonstrated to enable label-free, specific detection of bacteria and DNA molecules, respectively, with single quanta sensitivity. Room temperature electrical characterization of the sensors showed a generation of ~ 1400 charge carriers for single bacterium attachment and an increase of 5.6 X 10[superscript]12 charge carriers / cm[superscript]2 for attachment of a single complementary strand of DNA. This work has shown for the first time the viability of graphene for bio-electronics and sensing at single quanta level. Taking the bio-interfacing of graphene to the next level, we demonstrate the instantaneous swaddling of a single live bacterium (Bacillus subtilis) with several hundred sq. micron (~ 600 µm[superscript]2) areal protein-functionalized graphene sheets. The atomic impermeability and high yield strength of graphene resulted in hermetic compartmentalization of bacteria. This enabled preservation of the dimensional and topological characteristics of the bacterium against the degrading effects of harsh environments such as the ultrahigh vacuum (~ 10[superscript]-5 Torr) and high intensity electron beam (~ 150 A/cm[superscript]2) in a transmission electron microscope (TEM) column. While an unwrapped bacterium shrank by ~ 76 % and displayed significant charge buildup in the TEM column; a wrapped bacterium remained uncontracted and undamaged owing to the graphenic wraps. This work has shown for the first time an impermeable graphenic encasement of bacteria and its application in high vacuum TEM imaging without using any lengthy traditional biological TEM sample preparation techniques. In an inch-scale, we fabricated robust free-standing paper composed of TWEEN/Graphene composite which exhibited excellent chemical stability and mechanical strength. This paper displayed excellent biocompatibility towards three mammalian cell lines while inhibiting the non-specific binding of bacteria (Bacillus cereus). We predict this composite and its derivatives to have excellent applications in biomedical engineering for transplant devices, invasive instrument coatings and implants. We also demonstrate a novel, ultra-fast and high yield process for reducing GO to reduced graphene oxide (RGO) using a facile hydride-based chemistry. The RGO sheets thus-produced exhibited high carrier mobilities (~ 100-600 cm[superscript]2/V•s) and reinstatement of the ambipolar characteristic of graphene. Raman spectra and UV-Vis spectroscopy on the RGO sheets displayed a high degree of restoration of the crystalline sp2 lattice with relatively low defects. We fabricated graphene nanoribbons (GNRs) – 1D structural derivatives of graphene – using a nano-scale cutting process from highly oriented pyrolytic graphite (HOPG) blocks, with widths pre-determinable between 5 nm to 600 nm. The as-produced GNRs had very high aspect ratio in the longitudinal direction (~ 0.01); exhibited predominantly mono-layered structure (< 10 % bilayer); and smooth edges (Raman I[subscript]D/G ~ 0.25 -0.28). Low temperature electrical transport measurements on back-gated thin film GNR devices were performed and a carrier mobility of ~ 20 ± 4 cm[superscript]2/V•s with sheet resistances of 2.2-5.1 MΩ / □ was extracted. Despite the ~ 50 nm thicknesses of the films, a clear bandgap scaling was observed with transport via variable range hopping (VRH) in 2 and 3 dimensions. This work demonstrates the first fully functional narrow pristine GNR thin-film field effect transistors (FETs). In addition we fabricated graphene quantum dots (GQDs) – 0D derivatives of graphene with dimensions < 100 nm – using a slight variation of our nano-scale cutting strategy, where the cleavage process is carried out in two dimensions. A high degree of control on the dimensions (Std. Dev. of ~ 5 nm for 50 X 50 nm square GQDs) and shape (pre-determinable between square, rectangle, triangle and trapezoid) of the as-synthesized GQDs is demonstrated. The optical properties of the GQDs such as the UV-Vis absorbance and photoluminescence were studied and their facile tunability was demonstrated depending on their dimensions. This work demonstrates for the first time the high throughput fabrication of GQDs with tunable dimensions and shape.

Master of Science / Department of Grain Science and Industry / Xiuzhi Susan Sun / Soybean oil-based resin for transparent flexible coating applications were formulated by dihydroxyl soybean oil (DSO) with commercial epoxy monomers (i.e., epoxidized soybean oil (ESO) and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (ECHM)). The resin was formed to thermoset polymers using cationic ring-opening photopolymerization. The ether crosslinking and post-polymerization of the polymeric network were observed using Fourier transform infrared spectroscopy. Thermal properties of the bio-based coating materials and their copolymerization behaviors were examined using a differential scanning calorimetry and a thermogravimetric analyzer. Crosslink density and molecular weight between crosslink were obtained from dynamic mechanical analysis. ECHM/DSO (1: 1.43 weight ratio) films showed the highest elongation at break (49.2 %) with a tensile strength of 13.7 MPa. After 2 months storage, the elongation at break and tensile strength of films were 32 % and 15.1 MPa, respectively. ESO/DSO films (w/w ratios of 1:0.1, 1:0.15, and 1:0.2) exhibited stable flexibility around 11-13 % of elongations at break without significant reductions of tensile strengths (2.5 to 4.4 MPa) during 2-months shelf life. Optical transparencies of the films were comparable to commercial glass and polymers, and water uptake properties (0.72 and 2.83%) were significantly low.

Master of Science / Department of Civil Engineering / Robert J. Peterman / With limited research being conducted solely on lightweight concrete prestressed bond and current development-length equations based on tests performed on normal-weight members, more investigation on lightweight concrete prestress bond is necessary. Additionally, the effects of water-reducing agents on normal-weight and lightweight concrete need further exploration. The aim of this study was to examine these areas using two locally available lightweight aggregates from Kansas and one from North Carolina to determine if lightweight prestressed concrete bridge girders are a useful alternative for the Kansas Department of Transportation. The lightweight concrete mixes developed were capable of attaining 5000 psi compressive strength in 16 hours and 7000 psi in 28 days. During the large block pull-out test, the average maximum force at pull-out and first observable slip was higher for the block cast with a three inch slump then the companion specimen poured at a nine-inch slump. During flexural testing, the two beams not reaching nominal moment capacity, KC-9 and STA-9, failed in compression without strand end slip. The moment capacity was considerably greater for three-inch slump members than the companion specimen placed with nine-inch slump concrete.

Master of Science / Department of Mechanical and Nuclear Engineering / Douglas S. McGregor / Purification of cadmium, zinc and tellurium was attempted to improve the quality of cadmium-zinc-telluride (CdZnTe) crystal growth. Specifically, vacuum distillation, zone refining and H[subscript]2 gas flow assisted zone refining were all investigated as methods to purify the constituent elements of CdZnTe. A unique multi-chamber ampoule was used to enable a purification sequence starting with double vacuum distillation followed by zone refining all without sample handling after the initial step. Modifications due to unique material properties of Cd and Zn were developed. Glow discharge mass spectroscopy (GDMS) analysis was used to measure impurity concentrations of 74 elements. Cd purification using vacuum distillation proved to be an effective method to reduce the impurity level of 5N starting material to a purity between the range of 6N5 and 7N5, as measured using GDMS and laser ablation mass spectroscopy. Combined Zn double vacuum distillation and zone refining in an enclosed Ar atmosphere using 5N starting material yielded material with a purity between the range of 5N8 to 6N8. Tellurium purification using combined double vacuum distillation followed by zone refining under continuous H[subscript]2 flow of 4N specified raw material resulted in high purity tellurium between the range of 6N3 and 7N4.

Doctor of Philosophy / Department of Chemistry / Viktor Chikan / This dissertation reports the colloidal synthesis of iron silicide, hafnium oxide core-gold shell and water soluble iron-gold alloy for the first time. As the first part of the experimentation, plasmonic and superparamagnetic nanoparticles of gold and iron are synthesized in the form of core-shell and alloy. The purpose of making these nanoparticles is that the core-shell and alloy nanoparticles exhibit enhanced properties and new functionality due to close proximity of two functionally different components. The synthesis of core-shell and alloy nanoparticles is of special interest for possible application towards magnetic hyperthermia, catalysis and drug delivery. The iron-gold core-shell nanoparticles prepared in the reverse micelles reflux in high boiling point solvent (diphenyl ether) in presence of oleic acid and oleyl amine results in the formation of monodisperse core-shell nanoparticles. The second part of the experimentation includes the preparation of water soluble iron-gold alloy nanoparticles. The alloy nanoparticles are prepared for the first time at relatively low temperature (110 oC). The use of hydrophilic ligand 3-mercapto-1-propane sulphonic acid ensures the aqueous solubility of the alloy nanoparticles. Next, hafnium oxide core-gold shell nanoparticles are prepared for the first time using high temperature reduction method. These nanoparticles are potentially important as a high κ material in semiconductor industry. Fourth, a new type of material called iron silicide is prepared in solution phase. The material has been prepared before but not in a colloidal solution. The Fe3Si obtained is superparamagnetic. Another phase β-FeSi2 is a low band gap (0.85 eV) semiconductor and is sustainable and environmentally friendly. At last, the iron monosilicide (FeSi) and β-FeSi2 are also prepared by heating iron-gold core-shell and alloy nanoparticles on silicon (111) substrate. The nucleation of gaseous silicon precursor on the melted nanoparticles results the formation of nanodomains of FeSi and β-FeSi2. A practical application of these nanoparticles is an important next step of this research. Further improvement in the synthesis of β-FeSi2 nanoparticles by colloidal synthetic approach and its application in solar cell is a future goal.

Doctor of Philosophy / Department of Chemistry / Kenneth J. Klabunde / Solar energy driven catalytic systems have gained popularity in environmental remediation recently. Various photocatalytic systems have been reported in this regard and most of the photocatalysts are based on well-known semiconducting material, Titanium Dioxide, while some are based on other materials such as Silicon Dioxide and various Zeolites. However, in titania based photocatalysts, titania is actively involved in the catalytic mechanism by absorbing light and generating exitons. Because of this vast popularity of titania in the field of photocatalysis it is believed that photocatalysis mainly occurs via non-localized mechanisms and semiconductors are extremely important. Even though it is still rare, photocatalysis could be localized and possible without use of a semiconductor as well. Thus, to support localized photocatalytic systems, and to compare the activity to titania based systems, degradation of organic air pollutants by nanostructured silica, titania and mixed silica titania systems were studied. New materials were prepared using two different approaches, precipitation technique (xerogel) and aerogel preparation technique. The prepared xerogel samples were doped with both metal (silver) and non-metals (carbon and sulfur) and aerogel samples were loaded with Chromium, Cobalt and Vanadium separately, in order to achieve visible light photocatalytic activity. Characterization studies of the materials were carried out using Nova BET analysis, DR UV-vis spectrometry, powder X-ray diffraction, X-ray photoelectron Spectroscopy, FT-IR spectroscopy, Transmission Electron Microscopy, etc. Kinetics of the catalytic activities was studied using a Shimadzu GCMS-QP 5000 instrument using a closed glass reactor. All the experiments were carried out in gaseous phase using acetaldehyde as the model pollutant. Kinetic results suggest that chromium doped silica systems are good UV and visible light active photocatalysts. This is a good example for a localized photocatalytic activity. In contrast, our xerogel system shows comparatively high visible light photocatalytic activity for the titania based system, showing the importance of non-localized nature of photocatalysis. The Cobalt doped silica system shows interesting dark catalytic activity towards acetaldehyde and several other pollutants. Thus, in summary, based on the different activities we observed during our studies these materials could be successfully used to improve the quality of both indoor and outdoor air.

Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Gurpreet Singh / Molecular precursor derived ceramics (also known as polymer-derived ceramics or PDCs) are high temperature glasses that have been studied for applications involving operation at elevated temperatures. Prepared from controlled thermal degradation of liquid-phase organosilicon precursors, these ceramics offer remarkable engineering properties such as resistance to crystallization up to 1400 °C, semiconductor behavior at high temperatures and intense photoluminescence. These properties are a direct result of their covalent bonded amorphous network and free (-sp2) carbon along with mixed Si/B/C/N/O bonds, which otherwise can not be obtained through conventional ceramic processing techniques. This thesis demonstrates synthesis of a unique core/shell type nanowire structure involving either siliconboroncarbonitride (SiBCN) or siliconoxycarbide (SiOC) as the shell with carbon nanotube (CNT) acting as the core. This was made possible by liquid phase functionalization of CNT surfaces with respective polymeric precursor (e.g., home-made boron-modified polyureamethylvinylsilazane for SiBCN/CNT and commercially obtained polysiloxane for SiOC/CNT), followed by controlled pyrolysis in inert conditions. This unique architecture has several benefits such as high temperature oxidation resistance (provided by the ceramic shell), improved electrical conductivity and mechanical toughness (attributed to the CNT core) that allowed us to explore its use in energy conversion and storage devices. The first application involved use of SiBCN/CNT composite as a high temperature radiation absorbant material for laser thermal calorimeter. SiBCN/CNT spray coatings on copper substrate were exposed to high energy laser beams (continuous wave at 10.6 μm, 2.5 kW CO2 laser, 10 seconds) and resulting change in its microstructure was studied ex-situ. With the aid of multiple techniques we ascertained the thermal damage resistance to be 15 kW/cm2 with optical absorbance exceeding 97 %. This represents one order of magnitude improvement over bare CNTs (1.4 kW/cm2) coatings and two orders of magnitude over the conventional carbon paint (0.1 kW/cm2) currently in use. The second application involved use of SiBCN/CNT and SiOC/CNT composite coatings as energy storage (anode) material in a Li-ion rechargeable battery. Anode coatings (~1mg/cm2) prepared using SiBCN/CNT synthesized at 1100 °C exhibited high reversible (useable) capacity of 412 mAh/g even after 30 cycles. Further improvement in reversible capacity was obtained for SiOC/CNT coatings with 686 mAh/g at 40 cycles and approximately 99.6 % cyclic efficiency. Further, post cycling imaging of dissembled cells indicated good mechanical stability of these anodes and formation of a stable passivating layer necessary for long term cycling of the cell. This improved performance was collectively attributed to the amorphous ceramic shell that offered Li storage sites and the CNT core that provided the required mechanical strength against volume changes associated with repeated Li-cycling. This novel approach for synthesis of PDC nanocomposites and its application based testing offers a starting point to carry out further research with a variety of PDC chemistries at both fundamental and applied levels.

Master of Science / Department of Mechanical & Nuclear Engineering / Gurpreet Singh / Carbon nanotubes (CNT) and polymer-derived ceramics (PDC) have gained considerable research attention due to their unique structure and physical properties. Carbon nanotubes are known for their exceptional mechanical (Young’s modulus= 1 TPa) and thermal properties (thermal conductivity = 4000 W/m.K). However, CNTs tend to lose their unique -sp2 carbon structure and cylindrical geometry at temperatures close 400°C in air. PDC, which are obtained by the controlled degradation of certain organosilicon polymers however exhibit high temperature stability (upto approx. 1400 °C). To this end, a hybrid composite material consisting of PDC functionalized CNT is of interest as it can combine the unique physical properties of the two materials for applications requiring operation under harsh conditions. Here, we report synthesis and chemical characterization of an Al-modified polysilazane polymer, which was later utilized to functionalize the outer surfaces of four commercially available CNTs. This polymer-CNT composite upon heating in nitrogen environment resulted in Si(Al)CN-CNT ceramic composite. The composite was characterized using a variety of spectroscopic methods such Raman, FTIR and electron microscopy. The thermal stability of the ceramic composite was studied by use of Thermogravimetric analysis (TGA) that showed an improvement in the thermal stability compared to bare nanotubes. Further, we also demonstrate that a stable dispersion of the composite in organic solvents such as toluene can be spray coated on a variety of substrates such as copper disks and foils. Such coatings have application in high energy laser power meters. This research opens new avenues for future applications of this novel material as coatings on surfaces that require both good thermal properties and protection against degradation in high temperature environments. We also suggest the future use of this material as an electrode material in high electrochemical capacity rechargeable batteries.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / The integration of high-κ dielectrics with silicon and III-V semiconductors is important due to the need for high speed and high power electronic devices. The purpose of this research was to find the best conditions for fabricating high-κ dielectrics (oxides) on GaN or Si. In particular high-κ oxides can sustain the high breakdown electric field of GaN and utilize the excellent properties of GaN. This research developed an understanding of how process conditions impact the properties of high-κ dielectric on Si and GaN. Thermal and plasma-assisted atomic layer deposition (ALD) was employed to deposit TiO₂ on Si and Al₂O₃ on polar (c-plane) GaN at optimized temperatures of 200°C and 280°C respectively. The semiconductor surface treatment before ALD and the deposition temperature have a strong impact on the dielectric’s electrical properties, surface morphology, stoichiometry, and impurity concentration. Of several etches considered, cleaning the GaN with a piranha etch produced Al₂O₃/GaN MOS capacitors with the best electrical characteristics. The benefits of growing a native oxide of GaN by dry thermal oxidation before depositing the high-κ dielectric was also investigated; oxidizing at 850°C for 30 minutes resulted in the best dielectric-semiconductor interface quality. Interest in nonpolar (m-plane) GaN (due to its lack of strong polarization field) motivated an investigation into the temperature behavior of Al₂O₃/m-plane GaN MOS capacitors. Nonpolar GaN MOS capacitors exhibited a stable flatband voltage across the measured temperature range and demonstrated temperature-stable operation.