Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-08-26T23:22:11Z No. of bitstreams: 1 ValmarDaSilvaSeverianoSobrinho_DISSERT.pdf: 5455840 bytes, checksum: 21030bd15bb16fb2597187481d68f757 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-08-31T19:35:17Z (GMT) No. of bitstreams: 1 ValmarDaSilvaSeverianoSobrinho_DISSERT.pdf: 5455840 bytes, checksum: 21030bd15bb16fb2597187481d68f757 (MD5) / Made available in DSpace on 2016-08-31T19:35:17Z (GMT). No. of bitstreams: 1 ValmarDaSilvaSeverianoSobrinho_DISSERT.pdf: 5455840 bytes, checksum: 21030bd15bb16fb2597187481d68f757 (MD5) Previous issue date: 2016-05-12 / Filmes finos de TiO2 podem ser a resposta para grandes quest?es atuais sobre as melhores maneiras de obter energia, economizar energia e reduzir a polui??o. Tais filmes t?m sido aplicados com sucesso para produ??o de c?lulas solares; como camada em janelas inteligentes, janelas fotocr?micas e eletrocr?micas; al?m de possu?rem propriedades fotocatal?tica interessantes. Este trabalho explora a import?ncia tecnol?gica e cient?fica desse material realizando investiga??es a respeito dos filmes de TiO2, sua forma de deposi??o, t?cnicas de an?lise, detalhando formas atuais de an?lise ?ptica, buscando, de maneira inovadora, comparar tais t?cnicas, validar seu uso, e comparar seus resultados na busca de meios econ?micos da realiza??o de investiga??es a respeito de espessura, estrutura e avalia??o de propriedades fotocatal?ticas do material produzido. Nesse trabalho foram utilizadas, para cria??o de filmes finos, deposi??o f?sica pelo m?todo de magnetron sputterin. Para an?lise ?ptica e c?lculo de espessura e Band Gap dos filmes ser? apresentado o M?todo do Envelope que foi originalmente proposto por Manifacier (Manifacier, Gasiot e Fillard, 1976) sendo que mais tarde Swanepoel (1983) conseguiu melhorar ainda mais a precis?o desse m?todo para encontrar propriedades ?pticas dos filmes finos e sua espessura. Tamb?m ser? apresentado, a aplica??o de equa??es propostas nos trabalhos de Lindgren (Lindgren et al., 2003) e a Lei de Beer-Lambert para c?lculo do Coeficiente de Absor??o dos filmes, outro dado importante para mais tarde determinar o gap dos mesmos, que ser? encontrado pelo M?todo Tauc. Para filmes muito finos, com poucas ou nenhuma franja de interfer?ncia se faz necess?rio o estudo de algum M?todo Computacional para determina??o dos seus par?metros ?pticos e espessura. Para tanto utilizou-se o M?todo PUMA, um M?todo Computacional desenvolvido por pesquisadores da UNICAMP/USP. Os filmes depositados foram analisados por DRX, EDS, al?m de serem submetidos a an?lise ?ptica, MEV transversal buscando validar os m?todos ?pticos em termos das espessuras recuperadas, al?m de encontrado seus Band Gap e seus valores comparados com o esperado pela literatura confrontando tais resultados com a cristalinidade obtida para os filmes. / TiO2 thin films have been successfully used in solar cells, smart windows, photochromic and electrochromic windows and also as photocatalytic coatings. In this work, TiO2 thin films were deposited by magnetron sputtering on a glass substrate and their optical properties, thickness, microstructure and photocatalytic properties were evaluated. Film thicknesses and band gaps were determined by the Swanepoel method using the envelopes in the transmission spectrum and also the PUMA computational method. The films were analyzed by X-ray Diffraction (XRD), Energy Dispersive X-ray Spectroscopy (EDS), Scanning electron microscopy (SEM) and optical analysis. SEM measured thicknesses were compared to those obtained using the optical methods. The PUMA method proved advantageous for thickness determination of thin films, particularly when the interference fringes are not evident in the transmission spectrum. In addition, film thicknesses determined using the PUMA method were in better agreement with SEM measurements than those determined by the Swanepoel Method.

Les composants semi-conducteurs à base de matériaux à grand gap (SiC et GaN) présentent des caractéristiques intéressantes pour la réalisation de convertisseurs d’électronique de puissance toujours plus intégrés. Cependant, le packaging des composants traditionnels en silicium ne semble plus adapté pour ces nouveaux composants et apparaît même comme un facteur limitant. Le développement d’un packaging adapté aux caractéristiques des composants à grand gap est alors nécessaire. Les travaux développés dans cette thèse proposent un nouveau packaging tridimensionnel basé sur un procédé de fabrication de circuit imprimé. L’architecture du module est basé sur le concept « Power Chip On Chip » dont le principe de base permet de réduire les perturbations électromagnétiques. Le procédé de fabrication des circuits imprimés offre une grande flexibilité pour le routage en trois dimensions et permet de s’affranchir de l’interconnexion par fil de bonding entre le package et la puce. La démarche de conception du module s’appuie sur une approche multi-physique afin de qualifier le comportement électromagnétique et thermique du module puis de proposer des voies d’optimisation. Un prototype d’un module implémentant quatre cellules de commutation en parallèle, à base de MOSFET SiC, a été produit avec des moyens de production industriels. Les différents tests réalisés valident l’approche retenue dans ce projet mais soulignent également les aspects technologiques à approfondir pour la réalisation d’un module de puissance industriel. / Wide-band-gap (WBG) semiconductors (SiC and Gan) offer interesting characteristics to realize high density power electronics converters. Conventional packaging used for silicon devices is no more adapted for those now components. Development of dedicated packaging for WBG devices is absolutely required. This PhD thesis presents a new 3D package based on Printed Circuit Board (PCB) industrial process. The module architecture is based on “Power Chip On Chip” concept which allows reducing electromagnetic perturbations. PCB fabrication process offers high design flexibility in three dimensions and allows removing wire bonding to interconnect power die and package. The power module design process is buit on multi-physics design tools in the aim to quantify electromagnetic and thermal behavior of the module. Furthermore, several optimization parameters are highlighted. A power module prototype, with four commutation cells in parallel based on SiC MOSFET, has been produced thanks to industrial facilities. Tests realized on new power module confirm the validity of the concept but furthermore to highlight critical technological parameters to realize an industrial power module.

Poursuivant l'essor des méta-matériaux micro-ondes et photoniques, les cristaux phononiques, organisations périodiques de matériaux acoustiquement différents présentant notamment des bandes d'arrêt, c'est-à-dire de plages de fréquences pour lesquelles aucun mode ne se propage dans la structure, laissent entrevoir des applications acoustiques hors de portée des technologies existantes. Dans cette thèse, nous visons des réalisations aux fréquences RF afin de viser des applications complémentaires des résonateurs ou des filtres acoustiques largement employés dans le domaine des transmissions sans fil. Nous avons tout d'abord développé un procédé de fabrication simple permettant de réaliser des cristaux phononiques à deux dimensions à l'échelle micrométrique sur membrane piézoélectrique, afin de rendre ces systèmes compatibles avec les composants à ondes de Lamb développés au CEA-LETI pour des applications de filtrage de canal dans des architectures de transmission sans fil faible consommation. Ce procédé a été utilisé pour réaliser des cristaux phononiques, ainsi que des résonateurs à ondes de Lamb, ou à ondes de volume et des structures plus complexes comme par exemple des filtres passe-bande. Une étude paramétrique des composants à ondes de Lamb nous a permis d'affiner notre maîtrise de ces dispositifs, ce qui nous a été utile pour la mise au point des lignes à retard permettant de caractériser les propriétés de transmission acoustique des cristaux phononiques. Du point de vue théorique, un modèle de simulation par éléments finis a été mis en place, dans un premier temps pour dimensionner les structures réalisées et prendre en compte les modifications apportées par la réalisation technologique. Nous avons ensuite réalisé des cristaux phononiques que nous avons caractérisés électriquement et optiquement, en collaboration avec l'Institut FEMTO-ST. Les mesures confirment la présence de bandes d'arrêt, aux fréquences attendues, mais d'une largeur a priori bien supérieure à celle prévue par la simulation. Une étude détaillée des diagrammes de bandes attribue ce phénomène à la présence de bandes sourdes dans le cristal ne pouvant être excitées par les transducteurs utilisés. Cet aspect est d'une importance critique dans le dimensionnement de cristaux phononiques en vue d'une utilisation dans des applications pratiques. / In the straight line of photonic and microwave meta-materials, phononic crystals are foreseen to enable novel acoustic applications that existing technologies cannot reach. These phononic crystals are periodic organisation of acoustically different materials exhibiting, for example, qtop bands, which means frequency ranges in which no wave can propagate in the structure. In this thesis we target RF frequencies in order to investigate applications complementary to the conventional resonators or filters widely used in mobile telecommunication systems. We developed a simple process flow to realise micrometric two-dimensional phononic crystals on a piezoelectric membrane. These structures are fabricated along with Lamb wave devices studied in CEA-LETI for channel filtering in low consumption wireless transmission architectures, and with bulk wave resonators or more complex structures like band-pass filters. A parametric study of Lamb wave resonators sharpens our knowledge on these devices, which allow us to design and fabricate delay lines to characterise acoustic transmission properties of phononic crystals. From a theoretical point of view we set up a simulation model using finite element method. This model was used to design the phononic crystal we realised, and to take into account the effects of the modifications brought by the technological realisation. We then fabricated phononic crystals, and electrically and optically characterised them, in collaboration with FEMTO-ST institute. Measurements confirmed the presence of band gaps at the targeted frequency, but over a wider frequency range than predicted by calculation. A detailed study of band diagrams is attributing this phenomenon to the presence of deaf bands, which cannot be excited by interdigitated fingers. This shows that the determination of these deaf bands is of critical importance in designing phononic crystals for practical applications.

abstract: The energy band gap of a semiconductor material critically influences the operating wavelength of an optoelectronic device. Realization of any desired band gap, or even spatially graded band gaps, is important for applications such as lasers, light-emitting diodes (LEDs), solar cells, and detectors. Compared to thin films, nanowires offer greater flexibility for achieving a variety of alloy compositions. Furthermore, the nanowire geometry permits simultaneous incorporation of a wide range of compositions on a single substrate. Such controllable alloy composition variation can be realized either within an individual nanowire or between distinct nanowires across a substrate. This dissertation explores the control of spatial composition variation in ternary alloy nanowires. Nanowires were grown by the vapor-liquid-solid (VLS) mechanism using chemical vapor deposition (CVD). The gas-phase supersaturation was considered in order to optimize the deposition morphology. Composition and structure were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD). Optical properties were investigated through photoluminescence (PL) measurements. The chalcogenides selected as alloy endpoints were lead sulfide (PbS), cadmium sulfide (CdS), and cadmium selenide (CdSe). Three growth modes of PbS were identified, which included contributions from spontaneously generated catalyst. The resulting wires were found capable of lasing with wavelengths over 4000 nm, representing the longest known wavelength from a sub-wavelength wire. For CdxPb1-xS nanowires, it was established that the cooling process significantly affects the alloy composition and structure. Quenching was critical to retain metastable alloys with x up to 0.14, representing a new composition in nanowire form. Alternatively, gradual cooling caused phase segregation, which created heterostructures with light emission in both the visible and mid-infrared regimes. The CdSSe alloy system was fully explored for spatial composition variation. CdSxSe1-x nanowires were grown with composition variation across the substrate. Subsequent contact printing preserved the designed composition gradient and led to the demonstration of a variable wavelength photodetector device. CdSSe axial heterostructure nanowires were also achieved. The growth process involved many variables, including a deliberate and controllable change in substrate temperature. As a result, both red and green light emission was detected from single nanowires. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2012

abstract: This thesis describes the fabrication of several new classes of Ge1-x-ySixSny materials with the required compositions and crystal quality to engineer the band gaps above and below that of elemental Ge (0.8 eV) in the near IR. The work initially focused on Ge1-x-ySixSny (1-5% Sn, 4-20% Si) materials grown on Ge(100) via gas-source epitaxy of Ge4H10, Si4H10 and SnD4. Both intrinsic and doped layers were produced with defect-free microstructure and viable thickness, allowing the fabrication of high-performance photodetectors. These exhibited low ideality factors, state-of-the-art dark current densities and adjustable absorption edges between 0.87 and 1.03 eV, indicating that the band gaps span a significant range above that of Ge. Next Sn-rich Ge1-x-ySixSny alloys (2-4% Si and 4-10% Sn) were fabricated directly on Si and were found to show significant optical emission using photoluminescence measurements, indicating that the alloys have direct band gaps below that of pure Ge in the range of 0.7-0.55 eV. A series of Sn-rich Ge1-x-ySixSny analogues (y>x) with fixed 3-4% Si content and progressively increasing Sn content in the 4-10% range were then grown on Ge buffered Si platforms for the purpose of improving the material's crystal quality. The films in this case exhibited lower defect densities than those grown on Si, allowing a meaningful study of both the direct and indirect gaps. The results show that the separation of the direct and indirect edges can be made smaller than in Ge even for non-negligible 3-4% Si content, confirming that with a suitable choice of Sn compositions the ternary Ge1-x-ySixSny reproduces all features of the electronic structure of binary Ge1-ySny, including the sought-after indirect-to-direct gap cross over. The above synthesis of optical quality Ge1-x-ySixSny on virtual Ge was made possible by the development of high quality Ge-on-Si buffers via chemical vapor deposition of Ge4H10. The resultant films exhibited structural and electrical properties significantly improved relative to state-of-the-art results obtained using conventional approaches. It was found that pure Ge4H10 facilitates the control of residual doping and enables p-i-n devices whose dark currents are not entirely determined by defects and whose zero-bias collection efficiencies are higher than those obtained from samples fabricated using alternative Ge-on-Si approaches. / Dissertation/Thesis / Ph.D. Physics 2013

This thesis is devoted to potential applications of metamaterials in antenna structures as well as metamaterials behaviour, characterisation, structure design, simulation and extraction of parameters. The focus of this work is on the practical application of metamaterial structures for antenna performance enhancement. This thesis comprises three key parts; In the first part, theory of metamaterials is investigated including fields, polarisation, effective and average parameters, parameters extraction and transmission line (TL) model. In part two, zero index metamaterials (ZIM) theory is studied. The use of ZIM to form a highly directive medium is illustrated. A comparative study between different ZIM structures is conducted with a special attention to their operational bandwidth. ANSYS HFSS is used to model ZIM structures where simulation results show a bandwidth between 7.4% and 14.0%. Then two novel ZIM structures with a bandwidth of up to 33% are proposed. The first proposed ZIM is used to form a highly directive shell. Four directive shells are designed and placed around the dipole antenna where a gain increase of up to 6.8 dBi is obtained along the desired direction. Further, proposed ZIM cells are integrated with a quasi-Yagi antenna in order to increase its gain. Simulation results demonstrate gain enhancement for frequencies over which the proposed structure expresses ZIM properties. In part three, a new technique is stablished to design a metamaterial lens. The new technique is based on wave interference phenomena where engineered wave interference results in a desired spatial energy distribution. It is shown theoretically that having 180° phase difference between interfering waves results in a focused emission. Both hypothetical and metamaterial realisation models of a 180° phase shifter for a patch antenna are designed and simulated where a gain enhancement of 8 dBi and 5.77 dBi are achieved, respectively. Further, the concept of intended phase shift between interfering waves is used to design a novel bi-reflectional ground plane which can focus the reflected emission and consequently, increase the antenna directivity. In the theoretical model, the Perfect-E and Perfect-H planes are combined to form a bi-reflectional plane, whereas the practical model is designed using the copper cladding for the Perfect-E plane and the mushroom structure for the perfect-H plane. Both square and hexagonal geometries are used to form the mushroom structure. Simulation results confirm a gain enhancement of 5.4 dBi for the design using the square mushroom structure and a gain enhancement of 3.3 dBi for the design using the hexagonal mushroom structure.

Magister Scientiae - MSc / An electrolytic cell was designed and constructed for the preparation of TiO2 nanotubes. Conditions of anodic oxidation were established to reproducibly prepare TiO2 nanotubes of average length 35-50 μm vertically orientated relative to the plain of a pure titanium metal sheet. A non-aqueous solution of ethylene glycol containing small percentage of ammonium fluoride was used as the electrolyte with an applied voltage of 60 V. The morphology and dimensions of the nanotube arrays were studied by scanning (SEM) and transmission (TEM) electron microscopy. The effect of calcination under different conditions of temperature and atmosphere (nitrogen, argon and air) were assessed by both X-ray diffraction (XRD) and cyclic voltammetry (CV). Cyclic voltammetry studies were made possible by construction of a specially designed titanium electrode upon which the nanotubes were prepared. CV studies established a positive correlation between crystallinity and conductivity of the nanotubes. Doping of the nanotubes with nitrogen and carbon was established by elemental analysis, X-ray photoelectron spectroscopy (XPS) and Rutherford back scattering (RBS). The effect of nonmetal doping on the band gap of the TiO2 nanotubes was investigated by diffuse reflectance spectroscopy (DRS). / South Africa

The application of nanowires (NWs) in solar cells (SCs) is of great interest due to their new promising aspects established in nanoelectronics. Semiconductors associated with plasmonic metal nanoparticles (NPs) such as Silver (Ag), Gold (Au) and Copper (Cu), show enhanced performance in solid state light absorbing SCs owing to plasmonic characteristic of noble metal NPs. Plasmonic NPs presented a significant role in development of visible light harvesting for many applications such as photocatalytic materials, photodynamic in Surface Enhanced Raman Spectroscopy (SERS) and photovoltaics (PVs). Integration of plasmonic NPs in semiconductor materials have opened the routes to expand new PV systems with high efficiency light absorption. In this project, we introduce the synthesis ZnO and TiO2 NWs used as N-type semiconducting substrates and various methods for isolating plasmonic metal NPs, which are later deposited on the semiconducting substrates. Vertically aligned ZnO and TiO2 NWs arrays were grown on the fluorine-doped tin oxide (FTO) conductive glass substrates via hydrothermal method at low temperature and the plasmonic NPs were synthesized by wet chemistry procedures and finally decorated on the NW films by using electrophoretic deposition.  The impact of metal NPs loaded on the ZnO and TiO2 NWs substrates was studied by means of UV-vis spectroscopy and Photoluminescence (PL) spectroscopy. The absorbance spectra of individual NPs were recorded. Remarkably, the reflectance spectra of produced samples presented an enhancement in light absorption of the substrates after uptake of NPs on the ZnO and TiO2 NWs. The optical properties of the as grown ZnO NWs films decorated with Ag NPs (I) in direct contact with substrate and (II) in presence of an Al2O3 insulating spacer layer have been investigated. Both systems exhibited an enhancement in the UV band-edge emission from the ZnO when excited at 325 nm. In contrast, the broad bend defect emission of the samples did not have a significant change compare to bare ZnO substrates. The observed results suggested that the ZnO and TiO2 NWs decorated with plasmonic nanoparticles can boost the optical properties of MOs NWs substrates and hence effectively enhance the separation of photoexcited electron-hole pairs and photo-conversion applications.

Metal chalcogenides (sulfides, selenides and tellurides) are materials of current interest due to their peculiar properties such as optoelectronic, magnetooptic, thermoelectric and piezoelectric displays. These semiconducting materials have potential applications in solar cell devices, infrared detectors and ambient thermoelectric generators. Previously, these materials have been deposited by multiple-source precursor route with several problems associated with this technique. This work describes the synthesis of metal complexes (Zn, Cd, Fe, Ni, Pd, Pt) using the imidodichalcogenodiphosphinate ligand (Woollins ligand). Their thermal decomposition together with structural and spectroscopy analysis was carried out. The complexes were used as single source precursors for the deposition of cadmium selenide, cadmium phosphide, cadmium sulfide, zinc selenide, iron selenide and the tellurides of nickel, palladium, platinum and iron as thin films and powders. These were deposited by AACVD and pyrolysis. The deposited thin films and powders were characterised by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), energy dispersive analysis of X-rays (EDAX), X-ray photoelectron spectroscopy (XPS) and superconducting quantum interference device (SQUID). The cadmium complexes [Cd{iPr2P(Se)NP(Se)iPr2}2] and [Cd{iPr2P(S)NP(Se)iPr2}2] deposited the mixture of hexagonal CdSe and monoclinic Cd2P3 films at the flow rate of 160 sccm at 475 and 500 °C. At the flow rate of 240 sccm, only hexagonal CdSe was deposited from [Cd{iPr2P(Se)NP(Se)iPr2}2] at all temperatures. Hexagonal CdS and the mixture of orthorhombic Cd6P7/cubic Cd7P10 were deposited from [Cd{iPr2P(S)NP(S)iPr2}2]. The zinc complexes [Zn{iPr2P(Se)NP(Se)iPr2}2] and [Zn{iPr2P(S)NP(Se)iPr2}2] both deposited cubic ZnSe at all temperatures with the flow rates of 160 and 240 sccm. The iron complexes [Fe{(SePPh2)2N}2] and [Fe{(SePPh2NPPh2S)2N}2] deposited orthorhombic FeSe2 mixed with monoclinic Fe3Se4 by pyrolysis at 500 and 550 °C. An unresolved pattern was observed from the complex [Fe{(SePPh2NPPh2S)2N}2] at 550 °C. XPS analysis of the deposited FeSe2 showed the surface oxidation of the material, while the magnetic measurements on the sample using SQUID confirmed its ferromagnetic properties. The telluride complexes of nickel, palladium, platinum and iron deposited the metal telluride respectively as: hexagonal NiTe, hexagonal PdTe, hexagonal PtTe2 (mixed with rhombohedral PtTe) and hexagonal FeTe2. Conductivity studies on NiTe and PdTe revealed them to be insulators, while the magnetic measurements on FeTe2 indicated its antiferromagnetic behaviour.

In this work, I studied the hybrid system based on self-assembled guanosine crystal (SAGC) conjugated to wide-bandgap semiconductor gallium nitride (GaN). Guanosine is one of the four bases of DNA and has the lowest oxidation energy, which favors carrier transport. It also has large dipole moment. Guanosine molecules self-assemble to ribbon-like structure in confined space. GaN surface can have positive or negative polarity depending on whether the surface is Ga- or N-terminated. I studied SAGC in confined space between two electrodes. The current-voltage characteristics can be explained very well with the theory of metal-semiconductor-metal (MSM) structure. I-V curves also show strong rectification effect, which can be explained by the intrinsic polarization along the axis of ribbon-like structure of SAGC. GaN substrate property influences the properties of SAGC. So SAGC has semiconductor properties within the confined space up to 458nm. When the gap distance gets up to 484nm, the structure with guanosine shows resistance characteristics. The photocurrent measurements show that the bandgap of SAGC is about 3.3-3.4eV and affected by substrate properties. The MSM structure based on SAGC can be used as photodetector in UV region. Then I show that the periodic structure based on GaN and SAGC can have photonic bandgaps. The bandgap size and the band edges can be tuned by tuning lattice parameters. Light propagation and emission can be tuned by photonic crystals. So the hybrid photonic crystal can be potentially used to detect guanosine molecules. If guanosine molecules are used as functional linker to other biomolecules which usually absorb or emit light in blue to UV region, the hybrid photonic crystal can also be used to tune the coupling of light source to guanosine molecules, then to other biomolecules.