This dissertation focuses on bridging the pressure and complexity gap between heterogeneous catalysis and surface science by introducing new instrumental tools that can operate under catalytically relevant conditions (i.e. atmospheric pressures and temperatures higher than room temperature). Thus, some of the few detailed examples of the polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) as an in situ vibrational spectroscopic tool for the elevated-pressure investigation of gas/solid interfaces on planar single crystal model catalyst systems were presented in this work. Furthermore, for the first time in the literature, PM-IRAS technique was applied to study complex multi-component model catalyst structures exhibiting three dimensional morphologies such as metal nanoparticles deposited on a metal-oxide thin film. In order to achieve a molecular understanding of the properties of CO+NO catalytic reaction at elevated temperatures and pressures on Pd based catalysts, adsorption trends of each of the reactant molecules were studied separately on Pd (111). The adsorption properties of CO/Pd (111) and NO/Pd (111) systems both under UHV conditions and at elevated pressures were discussed in a comparative manner to highlight the pressure dependent behavioral differences between these two probe molecules by emphasizing the risks of extrapolating UHV trends to elevated pressure regimes. CO+NO reaction mechanism and kinetics was also studied on Pd (111) by in situ PM-IRAS. Factors affecting the conversion and the selectivity of the Pd (111) model catalyst towards CO+NO reaction at elevated pressures were discussed. Formation of isocyanate containing species?? was also observed and the catalytic implications of this observation was elaborated. Finally, design and characterization of a complex model catalyst composed of supported Pd nano-particles was investigated using CO adsorption at elevated pressures. Catalytic activity of the defect sites on the supported Pd nano-particles towards CO dissociation was demonstrated and compared with Pd (111) to elucidate the significance of the surface morphology of the active sites in a catalytic reaction.

This diploma thesis presents experimental evidence of a theoretical concept which predicts the self-organization of delta-layers of silicon nanoclusters in the buried oxide of a MOS-like structure. This approach of "bottom-up" structuring might be of eminent importance in view of future semiconductor memory devices. Unconventionally, a 15nm thin SiO2 layer, which is enclosed by a 50nm poly-Si capping layer and the Si substrate, is irradiated with Si+ ions. Ion impact drives the system to a state far from thermodynamic equilibrium, i.e. the local composition of the target is modified to a degree unattainable in common processes. A region of SiOx (x<2) - where x is a function of depth - is formed which is not stable. During annealing, the system relaxes towards equilibrium, i.e. phase separation (via spinodal decomposition and nucleation) sets in. Within a certain time window of annealing, the structure of the system matches with a structure similar to the multidot non-volatile memory device, the principal character of which is a 2D layer of Si nanoclusters of ~3nm in diameter which is embedded in a 3D SiO2 matrix at a distance of ~3nm from the Si substrate. The physical mechanisms of ion mixing of the two Si-SiOx interfaces and subsequent phase separation, which result in the desired sample structure, are elucidated from the viewpoint of computer simulation. In addition, experimental evidence is presented based on various methods, including TEM, RBS, and SIMS. Of particular importance is a novel method of Si nanocluster decoration which applies Ge as contrast enhancing element in TEM studies of tiny Si nanoclusters.

The optical properties of matter are determined by the coupling of the incident electromagnetic radiation to oscillators within the material. The oscillators can be electrons, ions or molecules. Close to a resonance the dielectric function exhibits strong dispersion and may be negative. A negative dielectric function gives rise to a complex wave vector which is associated with no allowed states for photons, i.e. high extinction and bulk reflectance, as well as the possibility to support surface waves. It is possible to manufacture a dielectric material that generates a complex wave vector. Such materials are called photonic crystals and they may exhibit a frequency range without allowed states for photons, i.e. an energy gap. A photonic crystal has a periodically varying dielectric function and the lattice constant is of the same order of magnitude as the wavelengths of the gap. In this thesis, two optical phenomena causing a complex wave vector are combined. Polar materials, which have lattice resonance in the thermal infrared causing strong dispersion, are studied in combination with a periodic structure. The periodicity introduced is achieved using another material, but also by structuring of the polar material. One, two and three dimensional structures are considered. The polar materials used are silicon dioxide and silicon carbide. It is shown, both by calculations and experiments that the two optical phenomena can co-exist and interact, both constructively and destructively. A possible application for the combination of the two phenomena is discussed: Selective emittance in the thermal infrared. It is also shown that a polar material can be periodically structured by a focused ion beam in such way that it excites surface waves.

Pollution created by textile dyeing operations attracts significant attention because an effluent containing a complex mixture of coloured and potentially toxic compounds can be released with the discharged water. Developing dyes and dyeing conditions to reduce the amount of residual dye contained in any effluent has been one of many approaches to minimise this environmental impact. However, the presence of coloured discharge cannot be totally eliminated using only this strategy. Thus, development of efficient post-dyeing wastewater treatment methods capable of removing coloured products from the water is of paramount importance. TiO2-mediated photocatalytic degradation of organic dye molecules via oxidation is the focus of the study reported in this thesis. TiO₂ significantly increases the rate of photodegradation of a wide range of organic dyes under mild operating conditions, and is able to mineralise a wide spectrum of organic contaminants. TiO₂ is also one of the very few substances appropriate for the industrial applications. One of primary aims of this thesis is to test the hypothesis that augmenting standard TiO₂ photocatalysts with Au nanoparticles could increase performance of a catalyst, while immobilizing TiO₂ on SiO₂ support may improve the cost of the process efficiency, i.e. more photocatalytic degradation per particle of TiO₂. Combining TiO₂ doped with gold nanoparticles on SiO₂ support has the potential to provide the highest photocatalytic ability at the lowest cost. The first half of the thesis is concerned with establishing and optimizing experimental conditions for monitoring photodegradation via UV-Visible spectroscopy. Effects of various conditions such as temperature, sequence of addition of reagents, exposure to light vs. experiments in dark, sampling methods, and the use of quenching agent were examined. The main conclusions from this study are that light-induced photodegradation using titanium dioxide nanoparticles catalysts is comparatively more efficient than purely chemical catalytic (e.g. non-light mediated) degradation, even if the latter is performed at elevated temperature. Further, the rate of dye degradation is affected considerably by the parameters of the system. The degradation rate depends strongly on the pH of the solution, due to charges on both the catalyst surface and in the dye. In general, at pH ≤ 6.8, which is the zero charge point for TiO₂, reactions proceeded faster than those at higher pH. Six dyes from four different classes of dyes used in industry were used in this study, and all showed different photodegradation behaviour. The second half of thesis tests the photocatalytic abilities of various TiO₂-based catalysts: pure TiO₂ (commercial and custom-made in our laboratory), TiO₂-supported gold nanoparticles (Au/TiO₂), SiO₂-supported TiO₂ (TiO₂/SiO₂), and SiO₂-supported Au/TiO₂. The best photocatalytic performance was observed for the custom-made TiO₂ code-named as e-TiO₂, which was synthesized using the sol-gel method in dry ethanol. TiO₂-supported Au55 nanoparticles showed a similar level of catalytic ability but are significantly more expensive. It was observed that dye adsorption played a significant role in the case of SiO₂-immobilized photocatalysts.

The synthesis of highly ordered carbonaceous materials, including carbon nanofibers, has been the subject of a disparate and burgeoning literature over the past decade. Growth of carbon nanotubes via an atypical catalytic route, the decomposition of halogenated reactants as chlorobenzene (CB) over 10% (w/w) Ni/SiO2 is investigated. The C (carbon) yield and structural order are a function of reaction time and temperature. Greater degree of structural order and C yield is observed from CB relative to benzene, suggesting Cl/catalyst interaction(s) and metal site restructuring. Evaluation of the effect of H2 on C growth from CB reveals that C yield is sensitive to % (v/v) H2 with selectivity maxima at 40% (v/v) H2. Further, C yield is significantly influenced by the nature of the heteroatom substituent on the benzene ring; presence of strong electron withdrawing groups favors C yield and weak electron withdrawing or donating groups favors competing side reactions. The effect of the strong electron withdrawing group, Cl, varies with the chemical structure of the carbon source. Presence of Cl promotes C yield in the case of aromatic and straight chained (aliphatic) compounds whereas it promotes formation of benzene in the case of cyclic (aliphatic) compounds. Results are interpreted in term of substituent/ catalyst interaction and the mechanism of solid C formation. Further, effect of % (v/v) H2 on C growth characteristics varies significantly with the precursor. The C growth characteristics are strongly dependent on the nature of the support used, as demonstrated for the following supports: SiO2, Ta2O5, Al2O3, NaY, activated carbon and graphite at 10% (w/w) Ni loading. Ni/SiO2 results in maximum C yield. Variation in Ni loading significantly influences the C yield; higher loading favors greater C yield. C grown on Ni/NaY was found to be relatively more structured to C obtained on the other supports. EDX analysis of the carbon product was used to assess the possibility of Cl intercalation and it reveals presence of 0.4 at% Cl on carbon grown on Ni/Al2O3.

In this study, barium strontium titanate (BST) thin films with different compositions (Ba0.9Sr0.1TiO3, Ba0.8Sr0.2TiO3, Ba0.7Sr0.3TiO3, Ba0.5Sr0.5TiO3) were produced by chemical solution deposition technique. BST solutions were prepared by dissolving barium acetate, strontium acetate and titanium isopropoxide in acetic acid and adding ethylene glycol as a chelating agent and stabilizer to this solution, at molar ratio of acetic acid/ethylene glycol, 3:1. The solution was then coated on Si and Pt//Ti/SiO2/Si substrates at 4000 rpm for 30 seconds. Crack-free films were obtained up to 600 nm thickness after 3 coating &amp / #8211 / pyrolysis cycles by using 0.4M solutions. Crystal structure of the films was determined by x-ray diffraction while morphological properties of the surface and the film-substrate interface was examined by scanning electron microscope (SEM). Dielectric constant, dielectric loss and ferroelectric parameters of the films were measured. Sintering temperature, film composition and the thickness of the films were changed in order to observe the effect of these parameters on the measured electrical properties. The dielectric constant of the films was decreased slightly in 1kHz-1 MHz range. It was seen that dielectric constant and loss of the films was comparable to chemical solution deposition derived films on literature. Maximum dielectric constant was obtained for the Ba0.7Sr0.3TiO3 composition at a sintering temperature of 800&amp / #730 / C for duration of 3 hours. Dielectric constant increased whereas dielectric loss decreased with increasing film thickness. BST films have composition dependent Curie temperature. For Ba content greater than 70 %, the material is in ferroelectric state. However, fine grain size of the films associated with chemical solution deposition and Sr doping causes the suppression of ferroelectric behaviour in BST films. Therefore, only for Ba0.9Sr0.1TiO3 composition, slim hysteresis loops with very low remanent polarization values were obtained.

In this study, we used ion implantation technique to synthesize semiconductor (Ge, Si) nanocrystals in SiO2 matrix. Ge and Si nanocrystals have been successfully formed by Ge and Si implantation and post annealing. Implanted samples were examined by characterization techniques such as TEM, XPS, EDS, SAD, SIMS, PL, Raman and FTIR spectroscopy and the presence of Ge and Si nanocrystals in the SiO2 matrix has been evidenced by these measurements. It was shown that implantation dose, implantation energy, annealing temperature, annealing time and annealing ambient are important parameters for the formation and evolution of semiconductor nanocrystals embedded in SiO2 matrix. The size and size distribution of Ge and Si nanocrystals were estimated successfully by fitting Raman and PL spectra obtained from Ge and Si implanted samples, respectively. It was demonstrated that Si implanted and post annealed samples exhibit two broad PL peaks at &amp / #8764 / 625 and 850 nm, even at room temperature. Origin of these peaks was investigated by temperature, excitation power and excitation wavelength dependence of PL spectrum and etch-measure experiments and it was shown that the peak observed at &amp / #8764 / 625 nm is related with defects (clusters or chain of Si located near the surface) while the other is related to the Si nanocrystals. As an expected effect of quantum size phenomenon, the peak observed at &amp / #8764 / 850 nm was found to depend on the nanocrystal size. Finally, the formation and evolution of Ge and Si nanocrystals were monitored by FTIR spectroscopy and it was shown that the deformation in SiO2 matrix caused by ion implantation tends to recover itself much quicker in the case of the Ge implantation. This is a result of effective segregation of Ge atoms at relatively low temperatures.

Our aim was to establish a methodology for laser assisted oxidation of semiconductor and metal surfaces. One advantage of laser oxidation is the fact that radiation is heavily absorbed in a thin surface layer of the sample and the other is its ability for local oxidation. In addition to this, laser beam can be directed into some areas that other processes cannot reach. For these reasons, Nd:YAG pulsed laser working at 1064 nm wavelength is used for the oxidation purposes of Si and Ta films. First, SiO2 layer was obtained for various O2 pressures and laser powers. The thickness, refractive index, structural, dielectric, electrical and optical characteristics of the SiO2 layers have been determined. We have established that there exists an interval of laser power in which the oxidation occurs without surface melting. The oxidation process is controlled by the laser power rather than by the substrate temperature (673 &ndash / 748 K). It was found that better film quality is obtained at higher substrate temperatures and laser power greater than 3.36 J/cm2. Second, rf-sputtered Ta films were oxidized by laser, because Ta2O5 appears to be a good promising candidate to replace SiO2 because of its high dielectric constant, high breakdown voltage and relevant small leakage current values. It was found that the substrate temperature is an important parameter to obtain denser layers with reduced amount of suboxides and the most suitable substrate temperature range is around 350 C to 400 C. &amp / #946 / -orthorhombic crystal structure was obtained when the substrate temperature is 350 &ndash / 400 C for thinner films (up to 20 &ndash / 25 nm) and 300 &ndash / 350 C for thicker films (40 nm). The refractive index values of laser grown thin tantalum oxide films were between ~1.9 and 2.2 being close to those of bulk Ta2O5 (2.0 &ndash / 2.2). Oxide thicknesses in uniform Gaussian&ndash / like shapes were measured as around the twice of those initial Ta films. Effective dielectric constant values reached ~26 when the substrate temperature was increased from 250 C to around 400 C. It was shown that the leakage current density level decreases with increasing substrate temperature. However, the refractive index values of the films were smaller than those of thermally grown films. Porous structure formed during laser oxidation might be the reason for lower refractive indices and can be improved by post&ndash / oxidation annealing.

ABSTRACT PREPARATION OF PLZT THIN FILMS BY CHEMICAL SOLUTION DEPOSITION AND THEIR CHARACTERIZATION Kaplan, Burkan M.S., Department of Metallurgical and Materials Engineering Supervisor: Prof. Dr. Macit &Ouml / zenbaS November 2005, 125 pages In this study, La3+ was substituted into lead zirconate titanate (PZT) system by Pb1-xLax(ZryTi1-y)1-x/4O3 nominal stochiometry and it was processed via chemical solution deposition on (111)-Pt/Ti/SiO2/Si-(100) substrate.PLZT solutions were prepared by mixing two solutions, one of which was obtained by dissolving lead acetate and lanthanum acetate hydrate in 2 methoxyethanol at high temperature. This solution was then mixed with the second solution containing zirconium propoxide and titanium isopropoxide. 40ml/0.4M solution was prepared and spin coated on Pt/Ti/SiO2/Si substrates at 3000 rpm for 30 seconds. After 4 coating cycles, film thickness was reached to 600 nm. A systematic study was carried out in different regions of PLZT phase diagram tetragonal, rhombohedral and on the morphotropic phase boundry (MPB) to obtain optimized results of ferroelectric, dielectric and optical properties of the material. During the period of the work, effect of parameters on these properties such as heat treatment conditions, chemical composition of the film, microstructure and thickness of the film was investigated. The films were characterized structurally and electrically. For structural properties, X-ray diffraction technique (XRD), energy dispersive spectrometry (EDS) and Scanning Electron Microscope (SEM) were used to observe phases and surface characterization. For electrical measurements, ferroelectric tester was used to obtain dielectric constant, loss tangent and hysteresis curves. Optical transmittance of the films was also investigated by UV-VIS Spectrophotometer and optical film constants were calculated by modified envelope method. It was observed that the optimum heat treatment conditions were achieved at 7500C for 3 hours. The highest ferroelectric and dielectric properties such as remanent polarization and dielectric constant were obtained using that temperature. The dielectric constant of the films was measured in the frequency range of 1kHz-1MHz and remained almost constant in this region. The change of dielectric constant and ferroelectric hysteresis loops were obtained as a function of Zr/Ti ratio and La content. The grain size as a function of sintering temperature and La content was investigated. It was seen that as the sintering temperature was increased, the grain size of the films increased. The same tendency was also observed when the La content was increased. Fatigue behavior of PLZT thin films was also investigated by Radiant Ferroelectric Tester at 50 kHz and &plusmn / 15V. Change of remanent polarization (Pr) as a function of cumulative switching cycles (N) was drawn with the log scale of x-axis. Furthermore, leakage current characteristics of the films were also obtained by the ferroelectric tester at &amp / #61617 / 15V. It has been observed that as the La content of the film was increased, leakage current of the PLZT films decreased. Keywords: PLZT, (111)-Pt/Ti/SiO2/Si-(100) substrate, Chemical Solution Deposition.

Multi-walled carbon nanotubes (MWCNTs) and integrated MWCNTs/ SiO2 nanoparticles (NPs) were loaded as additives into nanocomposite polyvinylidene fluoride (PVDF) membranes fabricated via phase inversion methods, and the effects of these additives on the structure and vacuum membrane distillation (VMD) performance of the membranes have been studied. With an appropriate amount of MWCNTs (2 wt.% to PVDF) blended into the membrane, VMD performance of membrane was improved significantly due to higher membrane porosity, contact angle and surface roughness without extreme compromise of liquid entry pressure of water (LEPw), which could reach up to 72 psi. Further integration of MWCNTs with a small amount of SiO2 nanoparticles (NPs) showed a synergic effect resulting in further improvement of VMD flux due primarily to the increase in surface pore size. When the amount of SiO2 NPs additive was large, the effects of NPs dominates the VMD performance. However, the asymmetric structure of PVDF membrane disappears, which exercises an unfavourable effect on VMD performance. All fabricated membranes exhibited a great desalination potential with extremely high salt rejection (>99.98%). The incorporation of MWCNTs did not improve the tensile properties of the membrane.