The main automotive catalytic media, precious metal-doped ceria-zirconia oxides, fundamental system character is unknown. Understanding the catalytic system properties should allow for the production of an optimal model catalyst. This goal of this study is to gain understanding of ceria-zirconia-palladium systems and to determine a reproducible method for preparing catalysts with minimal surface-carbon. This study investigates ceria-zirconia-palladium catalyst preparation via aqueous chemistry methods and a sputter deposition technique for doping ceria-zirconia oxide mixtures. Prepared catalysts are characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). XPS allows the surface species, after catalyst doping and annealing, to be evaluated. Prepared catalyst EM analysis allows for surface morphology and particle characteristic evaluation. Prepared catalysts are exposed to UHV conditions, palladium sputtered-coated, and annealed at various temperatures. Temperature dependency is observed in both percentage of carbon, metal, and oxygen species present. This study led to a reproducible, low-carbon content, doping method for use in future pollutant reaction studies.

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The adhesion and durability of model epoxy/silane/SiO2/Si bonded systems were investigated under various conditions, including the type of surface preparation, pH of the environmental media, temperature, cyclic thermal stress, and external applied stress. The fundamental debond mechanism was studied for bonded systems exposed to selected environments. The bond failure mode was characterized by examining the failed bond surfaces using X-ray photoelectron spectroscopy. The effectiveness of combining the oxygen plasma treatment and silane coupling agent (SCA) derivatization in adhesion promotion for an epoxy bonded to a silicon surface was evaluated in this research. SCAs with different amine functionalities were studied. The oxygen plasma treatment time was varied systematically to achieve a different extent of oxidation on the Si wafer. The surface chemistry/composition of various silane derivatized Si surfaces was investigated. The studies revealed that SCA interaction with the Si surface was enhanced by the oxygen plasma pre-treatment of the Si substrates. XPS surface analysis results showed that the SCA/SiO2 ratio did not correlate strongly with the increase in oxygen plasma pretreatment time. However, for Si surfaces treated for longer oxygen plasma pretreatment times, more silanol groups may be available to interact with the hydrolyzed silanol groups on silane, resulting in a stronger SCA-Si attachment. Three different tests were employed to determine adhesion and durability of the model epoxy/SCA/SiO2/Si bonded specimens. The immersion test qualitatively evaluates the bond durability for various systems exposed to different chemical and thermal conditions. Second, a novel probe test was used to quantitatively determine adhesion under critical debonding conditions for bonded specimens with different SCA preparations. A general trend of bond durability varied in the manner SCA-2 > SCA-3 > SCA-1 > no silane. Bond durability also increased for samples: model epoxy/SCA modified/O2 plasma treated/Si as the oxygen plasma pre-treatment time increased. Third, bond durability was studied using the wedge DCB (double cantilever beam) test under subcritical debonding conditions with environment-assisted crack growth as a function of applied strain energy release rate. Higher crack velocity and the absence of a Gthreshold value were noted in tests at 70 oC. The Gthreshold value increased as the strength of the interface increased and as the chemical aggressiveness of the environment decreased. For tests involving 25 oC -70 oC thermal cycling, only limited crack growth was found. / Ph. D.

Un-doped, Tb3+ as well as Yb3+ doped ZnO nanocrystals with different concentrations of RE3+ (Tb3+, Yb3+) ions were successfully synthesized via sol-gel method to produce rare earth activated zinc oxide nanophosphors. The phosphor powders were produced by drying the precursor gels at 200˚C in ambient air. Based on the X-ray diffraction results, it was found that the pure and RE3+ doped ZnO nanophosphors were highly polycrystalline in nature regardless of the incorporation of Tb3+ or Yb3+ ions. Moreover, the diffraction patterns were all indexed to the ZnO Hexagonal wurtzite structure and belong to P63mc symmetry group. The Raman spectroscopy confirmed the wurtzitic structure of the prepared samples. Elemental mapping conducted on the as prepared samples using Scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer (EDX) revealed homogeneous distribution of Zn, O, and RE3+ ions. The high resolution transmission electron microscope (HR-TEM) analyses indicated that the un-doped and RE3+ doped samples were composed of hexagonal homogeneously dispersed particles of high crystallinity with an average size ranging from 4 to 7 nm in diameter, which was in agreement with X-ray diffraction (XRD) analyses. ZnO:Tb3+ PL study showed that among different Tb3+ concentrations, 0.5 mol% Tb3+ doped ZnO nanoparticles showed clear emission from the dopant originating from the 4f-4f intra-ionic transitions of Tb3+ while the broad defects emission was dominating in the 0.15 and 1 mol% Tb3+doped ZnO. Optical band-gap was extrapolated from the Ultraviolet Visible spectroscopy (UV-Vis) absorption spectra using TAUC‟s method and the widening of the optical band-gap for the doped samples as compared to the un-doped sample was observed. The PL study of ZnO:Yb3+ samples was studied using a 325 nm He-Cd laser line. It was observed that the ZnO exciton peak was enhanced as Yb3+ions were incorporated in ZnO matrix. Furthermore, UV-VIS absorption spectroscopic study revealed the widening of the band-gap in Tb3+ doped ZnO and a narrowing in the case of Yb3+ doped ZnO system. X-ray photoelectron spectroscopy demonstrated that the dopant was present in the doped samples and the result was found to be consistent with PL data from which an energy transfer was evidenced. Energy transfer mechanism was evidenced between RE3+ and ZnO nanocrystals and was discussed in detail. / Physics / M.Sc. (Physics)

Clusters/nanoparticles are aggregates of a “small” number of building blocks, atoms or molecules, ranging from two up to millions of atoms. Two main groups of clusters have been studied using photoelectron spectroscopy based on synchrotron radiation. They are dry/wet alkali-halide clusters, including pure water clusters, and metal-based nanoparticles. For the dry alkali halide clusters, analysis of the data and theoretical modeling has allowed us insights into the local electronic properties at nanoscale: a change of polarizability of ions in the alkali-halide clusters due to the varying environment has been suggested. The study of the wet salt clusters shows that the alkali-halides are already solvated at the nanoscale reached by water clusters doped with salt vapor. The photoelectron angular distribution of water cluster shows lower anisotropy parameters as compared to the separate monomers. A model based on intracluster scattering has been built to partly explain the reduction. In the last part of the thesis, metal-based multi-component nanoparticles have been produced by self-assembly processes using reactive magnetron sputtering. Depending on the specific metal element, oxidation processes have been applied before or after the aggregation. Clearly radial distributions such as core-shell and “sandwich-like” structures have unambiguously determined by photoelectron spectroscopy.

The work of this thesis comprises extensive Noncontact Atomic Force Microscopy (NC-AFM) characterization of clean metal-oxide (YSZ(100)/(111) and MgO(100)) and graphitic (HOPG) supports as templates for the novel, photochemically induced nucleation of cobalt oxide nanostructures, particularly Cobalt (III) Oxide. The nanostructure-support surfaces were also studied by X-ray Photoelectron Spectroscopy (XPS) to verify the nature of the supported cobalt oxide and to corroborate the surface topographic and phase NC-AFM data. Heteroepitaxial growth of Co2O3 nanostructures proves to exhibit a variety of different growth modes based on the structure of the support surface. On this basis, single-crystal support surfaces ranging from nonpolar to polar and atomically flat to highly defective and reactive were chosen, again, yielding numerous substrate-nanostructure interactions that could be probed by high-performance surface science techniques.

Aim of this student research project was to develop an Aluminium Oxide (Al2O3 ) ALD process from trimethylaluminum (TMA) and Ozone in comparison of two shower head designs. Then studying the detailed characteristics of Al2O3 ALD process using various measurement techniques such as Spectroscopic Ellipsometry (SE), x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM). The real-time ALD growth was studied by in-situ SE. In-situ SE is very promising technique that allows the time-continuous as well as time-discrete measurement of the actual growth over an ALD process time. The following ALD process parameters were varied and their inter-dependencies were studied in detail: exposure times of precursor and co-reactant as well as Argon purge times, the deposition temperature, total process pressure, flow dynamics of two different shower head designs. The effect of varying these ALD process parameters was studied by looking upon ALD cycle attributes. Various ALD cycle attributes are: TMA molecule adsorption (Mads ), Ligand removal (Lrem ), growth kinetics (KO3 ) and growth per cycle (GPC).

The interactions which occur between both polar and non-polar fluid phases and surfaces of various carbon materials: Activated Carbon (AC), non-porous Carbon Black (CB) and Multiwall Carbon Nanotubes (MWCNTs)with different surface chemistry have been studied. These are currently of great interest as they govern the interfacial behaviour of carbons in a wide range of applications; separation adn composite technologies being two prime examples. Consequently, techniques for chemical modification of carbon surfaces ar also of interest. Surface oxygen functional groups have been introduced, or modified, using the following oxidation techniques: liquid-phase oxidation (both AC and CB), Fenton and Birch reduction treatment (MWCNTs) and in a more controlled manner using gas-phase ozone treatment (CB). The chemistry of all the resulting carbon surfaces were characterised using X-ray Photoelectron Spectroscopy (XPS), which gives a quick and direct quantitative measure of the external surface composition. This technique, which has not yet been extensively employed in detailed adsorption studies, is a promising alternative to Temperature Programmed Desorption (TPD) and Boehm titration method in the determination of oxygen and other surface groups. Physical effects of the various surface modifications have been studied using a variety of techniques appropriate for the material in question. Scanning Electron Microscopy (SEM) images show some deteriorating effects of the liquid-phase oxidations on the structure of both activated carbon and carbon black materials. Conversely, surface areas from nitrogen adsorption at 77oK, coupled witj immersion calorimetry data for toluene, show thet the physical structure of the carbon blacks is not modified by ozone treatment. This has allowed a detailed study of the effects of surface oxygen level (i.e. polarity) on vapour adsorption. Regarding the MWCNT materials, detailed High-Resolution Electron Microscopy (HRTEM) photographs show that the multi-wall structure of the nanotubes in not significantly disrupted during the introduction of active functional groups by the Fenton or Birch treatment and therefore keeping intact their mechanical properties which augurs well for their use as reinforcement in composite structures whilst also improving their dispersion properties in polar fluids. A systematic shift to higher adsorption values, due to the increasing specific interactions between the alcohol -OH groups and the surface oxygen groups, is observed in all the isotherms of alcohols from the CB series as the total surface oxygen concentration ([O]T) increases. Moreover, this effect was observed to be most significant for methanol confirming that the mechanism of adsorption is dominated by hydrogen bonding and therefore dependant on the surface concentration of oxygen sites; whereas it becomes less marked in the case of ethanol and isopropanol respectively due to the increasing non-specific, dispersion, interactions of the alkyl chain with the non-polar carbon surface. Overall correlations were observed between the surface oxygen concentration [O]T, the resulting enthalpy of immersion -^Hi values and the characteristic energy E of the Dubinin-Radushkevich-Kaganer (DRK) equation obtained for toluene and these alcohols and the influence of the carbon surface chemistry on the character of the adsorption isotherms is also discussed. This behaviour is also observed and much more pronounced in the case of water adsorption on other oxidised carbon materials (AC, CB and MWCNT) due to the higher polarity of water molecules. The water adsorption data were analysed using in particular the Dubinin-Serpinsky (DS) equation and also some of its recent variations such as Barton and D'Arcy & Watt equations. The DS2 and various Barton equations were found to fit best the AC and CB materials modified by liquid-phase oxidations and also for the CB 03 series with increasing level of oxidation while both D'Arcy & Watt equations gave the best fittings for the MWCNTs materials. It was also shown that the resulting parameters ao (for the DS equation) describing the surface concentration of primary polar adsorption sites and as the limiting water adsorption value were both linked to the surface oxygen level [O]T. Regarding interfacial bonding, the oxidised CB and MWCNT materials are expected to show an improved physicochemical wetting of their surfaces by various resin compunds

[pt] Os tópicos mais importantes a ser tratados nesta tese de doutorado são os vários problemas envolvidos na síntese de nanotubos contendo nitrogênio. Isto é principalmente motivado pelas possíveis aplicações que podem ser dadas a este tipo de estruturas. A motivação central está relacionada ao fato da possibilidade de fazer dopagens tipo -p e -n em nanotubos de carbono, incorporando átomos como boro ou nitrogênio. Isto está muito longe de ser uma trivialidade devido a que devemos levar em conta que se os nanotubos de carbono forem pensados como bases estruturais para nanocompósitos e dispositivos nanoeletronicos, é necessário controlar cuidadosamente a reatividade das paredes, sua dureza mecânica e o gap eletrônico por meio de um controle da quantidade de átomos inseridos nas paredes ou entre elas. Portanto, do ponto de vista de diferentes aplicações, é importante ter a possibilidade de dopar controladamente os nanotubos. Neste trabalho apresentam-se o quadro descritivo da dependência dos parâmetros de síntese, assim como uma investigação detalhada da formação de outras estruturas co-produto do processo de formação de nanotubos. Como uma idéia pioneira proposta neste trabalho, é enfatizado o uso de fontes puras de C/N em processos de síntese baseados em deposição química na fase de vapor. Desta maneira foi possivel determinar os efeitos da atmosfera de reação e o pretratamento do catalizador como agentes favoráveis ou desfavoráveis para a síntese efetiva de nanotubos de carbono. / [en] The main topic of this thesis is the study of various issues related to the synthesis of nitrogen containing nanotubes. This is mainly inspired in the possible applications such structures can have. The practical background lies in the fact that defined n- and p-doping of carbon nanotubes can be achieved by substituting carbon atoms from the tube walls by heteroatoms such as boron or nitrogen (N). This is far from been a triviality because we must keep in mind that if carbon nanotubes are to be used as future building blocks in nanocomposites and nanoelectronic devices, it is imperative to fine tune their wall reactivity, mechanical strength and electronic band gap by controlling the amount of foreign atoms inserted into the tube lattices. Therefore, from an applications standpoint, it is important to be able to carefully control the insertion of different dopants into nanotubes. In this work, a complete picture of the dependence on the combined synthesis parameters is established and a fundamental insight into the formation of N doped nanotubes and other structures (co- products) is provided. As a pioneering idea of this whole work, the use of pure C/N feedstocks in chemical vapor deposition methods is emphasized. With this, it was possible to determine the effects of the reaction atmosphere and the catalyst pretreatment as either favoring or disfavoring agents towards the synthesis of N-doped nanotubes.

Abstract This thesis is dedicated to realizations and physical understanding of electronic and photocatalytic properties after decorating transition metals to the semiconducting molybdenum disulfide. Synthesized via facile wet chemical methods, the MoS₂-Au, MoS₂-Au-Ni and MoS₂-Ag-Ni composites were formed as binary or ternary compounds. The Au nanoparticles are stably joined to the MoS₂ matrix without deteriorating layered structures of the host. After introducing the Au nanoglue as a common buffer, a metallic contact is reached between Ni and MoS₂, and attributed to new electron migration channel via MoS₂ edge contact. Adapting the Ag as the buffer element can attach the Ni to the basal plane of the MoS₂ beside edge contact. The Ni-Ag-MoS₂ composite effectively splits water under visible light irradiation and produce hydrogen. The excellent photocatalytic activity is attributed to effective charge migration through dangling bonds at the MoS2-Ag-Ni alloy interface and the activation of MoS₂ basal planes. / Original papers The original publications are not included in the electronic version of the dissertation. W. Cao, V. Pankratov, M. Huttula, X. Shi, S. Saukko, Z. Huang, M. Zhang. Gold nanoparticles on MoS2 layered crystal flakes. Materials Chemistry and Physics, 158, 89−95 (2015). DOI: 10.1016/j.matchemphys.2015.03.041 X. Shi, S. Posysaev, M. Huttula, V. Pankratov, J. Hoszowska, J.-Cl. Dousse, F. Zeeshan, Y. Niu, A. Zakharov, T. Li, O. Miroshnichenko, M. Zhang, X. Wang, Z. Huang, S. Saukko, D. L. González, S. van Dijken, M. Alatalo, W. Cao. Metallic contact between MoS₂ and Ni via Au nanoglue. Small, 14, 1704526 (2018). DOI: 10.1002/smll.201704526 http://jultika.oulu.fi/Record/nbnfi-fe2018060525279 X. Shi, M. Huttula, V. Pankratov, J. Hoszowska, J.-Cl. Dousse, F. Zeeshan, Y. Niu, A. Zakharov, Z. Huang, G. Wang, S. Posysaev, O. Miroshnichenko, M. Alatalo, W. Cao. Quantification of bonded Ni atoms for Ni-MoS₂ metallic contact through X-ray photoemission electron microscopy. Microscopy and Microanalysis, 24, 458−459 (2018). DOI: 10.1017/S1431927618014526 http://jultika.oulu.fi/Record/nbnfi-fe2018082834233 X. Shi, M. Zhang, W. Cao, X. Wang, M. Huttula. Efficient photocatalytic hydrogen evolution via activated multilayer MoS₂. Manuscript. X. Shi, Z. Huang, M. Huttula, T. Li, S. Li, X. Wang, Y. Luo, M. Zhang, W. Cao. Introducing magnetism into 2D nonmagnetic inorganic layered crystals: a brief review from first-principles aspects. Crystals, 8, 24 (2018). DOI: 10.3390/cryst8010024 http://jultika.oulu.fi/Record/nbnfi-fe201802153441