Thema dieser Arbeit ist die Synthese von hexagonalen (Al,Ga,In)N-Heterostrukturen mittels plasma-unterstützter Molekularstrahlepitaxie. Die Proben werden entlang der polaren [0001]-Richtung und der unpolaren [1100]-Richtung auf SiC(0001)- bzw. g-LiAlO2(100)-Substraten gewachsen. Der Einfluß der Wachstumsbedingungen auf die strukturellen, morphologischen, optischen, vibronischen und elektrischen Eigenschaften der Proben wird untersucht. Im Vergleich zu den übrigen III-V-Halbleitern zeichnen sich die hexagonalen Nitride besonders durch die Größe ihrer Fehlpassungen und elektrischen Polarisationsfelder aus. Eine Einführung in diese beiden wichtigen Eigenschaften wird gegeben, insbesondere für [0001]- und [1100]-orientierte Schichten. Um Verspannungen und elektrische Polarisationsfelder in korrekter Art und Weise zu berücksichtigen, wird ein effizientes Modell zur dynamischen Simulation von Röntgenbeugungsprofilen formuliert und auf hexagonale sowie kubische Kristalle angewandt. Die Synthese von GaN-Pufferschichten auf SiC(0001)- und g-LiAlO2(100)-Substraten wird diskutiert. Das GaN-Wachstum auf SiC(0001) erfolgt entlang der üblichen polaren [0001]-Richtung. Ein neuartiger Freiheitsgrad der GaN-Epitaxie wird durch das Wachstum von GaN entlang der unpolaren [1100]-Richtung auf g-LiAlO2(100) erreicht. Eine in-situ Strategie zur reproduzierbaren Abscheidung von GaN-Pufferschichten wird erarbeitet, die auf der Kontrolle der Wachstumsparameter durch Beugung von hochenergetischen Elektronen beruht. Die Schichten sind einphasig innerhalb der Nachweisgrenze von Röntgenbeugung und zeichnen sich durch glatte Oberflächen aus, die für das weitere Wachstum von Heterostrukturen gut geeignet sind. Es wird gezeigt, daß die strukturellen Eigenschaften der Pufferschichten sehr stark von der Substratpräparation abhängen. Ausgezeichnete strukturelle Eigenschaften werden auf sauberen und glatten SiC(0001)-Substraten erzielt, wogegen GaN(1100)-Filme unter der schlechteren Oberflächenqualität der g-LiAlO2(100)-Substrate leiden. GaN/(Al,Ga)N-Multiquantenwells (MQWs) mit identischer Schichtfolge werden auf den beiden Sorten von GaN-Pufferschichten gewachsen. Wegen der verschiedenen Orientierungen der polaren c-Achse relativ zur Wachstumsrichtung treten in der Rekombination von Ladungsträgern erhebliche Unterschiede auf. Es wird gezeigt, daß in [1100]-orientieren Wells Flachbandbedingungen herrschen. Im Gegensatz dazu existieren starke elektrostatische Felder in [0001]-orientierten Wells. Daher ist die Übergangsenergie von [0001]-orientierten Wells rotverschoben relativ zur Übergangsenergie der [1100]-orientierten Wells. Weiterhin besitzen die [0001]-orientierten Wells sehr viel längere Zerfallszeiten in der Photolumineszenz (PL). Beide Ergebnisse sind in quantitativer Übereinstimmung mit theoretischen Vorhersagen, die auf selbstkonsistenten Berechnungen von Bandprofilen und Wellenfunktionen mittels der Poisson- und Schrödingergleichungen in der Effektivmassen-Näherung basieren. Die Emission der [0001]-orientierten Wells ist isotrop, während die Emission der [1100]-orientierten Wells stark (>90%) senkrecht zur [0001]-Richtung polarisiert ist. Diese Ergebnisse sind in sehr guter Übereinstimmung mit den unterschiedlichen Valenzbandstrukturen der Wells. Das Wachstum von (In,Ga)N/GaN-MQWs wird untersucht. Massive Oberflächensegregation von In wird mit Beugung hochenergetischer Elektronen, Sekundärionenmassenspektrometrie, Röntgenbeugung und PL nachgewiesen. Rechteckige In-Profile belegen einen Segregationsmechanismus nullter Ordnung und nicht (wie bei anderen Materialsystemen beobachtet) einen erster Ordnung. Diese In-Segregation während des metallstabilen Wachstums resultiert in MQWs mit geringem Überlapp der Elektronen- und Lochwellenfunktionen, weil die Wells sehr viel dicker als beabsichtigt sind. Eine Verminderung der In-Segregation ist möglich durch N-stabiles Wachstum, führt jedoch zu rauhen Grenzflächen. Eine Strategie zum Wachstum von MQWs mit glatten Grenzflächen und hohen Quanteneffizienzen wird vorgestellt. Die strahlende Rekombination von (In,Ga)N/GaN-MQWs wird diskutiert. Es wird gezeigt, daß sowohl Zusammensetzungsfluktuationen als auch elektrostatische Felder für ein eingehendes Verständnis der Rekombination berücksichtigt werden müssen. Die Temperaturabhängigkeit der strahlenden Lebensdauer wird gemessen, um die Dimensionalität des Systems aufzuklären. Für ein quantitatives Verständnis wird ein Ratengleichungsmodell zur Analyse der Daten benutzt. Bei niedrigen Temperaturen wird die Rekombination von lokalisierten Zustände geprägt, wohingegen ausgedehnte Zustände bei höheren Tenmperaturen dominieren. Diese Analyse zeigt, daß die Lokalisierungstiefe in diesen Strukturen unterhalb von 25 meV liegt. / In this work, we investigate the synthesis of wurtzite (Al,Ga,In)N heterostructures by plasma-assisted molecular beam epitaxy. The layers are grown along the polar [0001] and the non-polar [1100] direction on SiC(0001) and g-LiAlO2(100) substrates, respectively. We examine the impact of deposition conditions on the structural, morphological, optical, vibrational and electrical properties of the films. An introduction is given to the most important properties of wurtzite nitride semiconductors: strain and electrical polarization fields of a magnitude not found in other III-V semiconductors. Particular emphasis is paid on [0001] and [1100] oriented layers. In order to correctly account for these phenomena in the samples under investigation, an efficient model for the dynamical simulation of x-ray diffraction (XRD) profiles is formulated and presented for wurtzite and zincblende crystals. The deposition of GaN buffer layers on two substrates, SiC(0001) and g-LiAlO2(100), is discussed. The conventional polar [0001] direction is obtained on SiC(0001) substrates. A new degree of freedom for GaN epitaxy is demonstrated by the growth of GaN along a non-polar direction, namely, [1100] on g-LiAlO2(100). An in-situ strategy for the reproducible growth of these GaN buffers is developed based on reflection high-energy electron diffraction (RHEED). The films are single-phase within the detection limit of high-resolution XRD and exhibit smooth surface morphologies well suited for subsequent growth of heterostructures. The structural properties of these samples are shown to be very sensitive to substrate preparation before growth. Smooth and clean SiC(0001) substrates result in excellent structural properties of GaN(0001) layers whereas GaN(1100) films still suffer from the inferior morphological and chemical quality of g-LiAlO2(100) substrates. Identically designed GaN/(Al,Ga)N multiple quantum wells (MQWs) are deposited on these two types of buffer layers. Significant differences in recombination due to the different orientations of the polar c-axis with respect to the growth direction are detected in photoluminescence (PL). It is demonstrated that flat-band conditions are established in [1100] oriented wells whereas strong electrostatic fields have to be taken into account for the [0001] oriented wells. Consequently, the transition energy of the [0001] oriented wells is red-shifted with respect to the [1100] oriented wells. Furthermore, [0001] oriented wells exhibit significantly prolonged PL decay times. These results are in quantitative agreement with theoretical predictions based on self-consistent effective-mass Schrödinger-Poisson calculations of the band profiles and wave functions. Finally, while the emission from [0001] oriented wells is isotropic, the emission from [1100] oriented wells is strongly polarized (>90%) normal to the [0001] axis in sound agreement with the different valence band structures of the wells. The growth of (In,Ga)N/GaN MQWs is studied. Massive In surface segregation (evidenced by RHEED, XRD, secondary-ion mass-spectrometry and PL) is shown to result in top-hat profiles and is therefore a zeroth order process instead of a first order process as observed for other materials systems. In segregation during metal-stable growth results in quantum wells with poor electron-hole wavefunction overlap since the actual well width is much larger than the intended one. Reduction of In segregation by N-stable conditions is possible but inevitably delivers rough interfaces. A strategy for obtaining (In,Ga)N/GaN MQWs with smooth interfaces and high quantum efficiency is devised. The radiative recombination from (In,Ga)N/GaN MQWs is examined. It is demonstrated that both compositional fluctuations and electrostatic fields have to be taken into account for a thorough understanding of the emission from these structures. The temperature dependence of the radiative decay time is measured to probe the dimensionality of the system. For a quantitative understanding, a rate-equation model is utilized for analyzing the data. For low temperatures, recombination is governed by localized states whereas for high temperatures extended states dominate. This analysis shows that the localization depth in these structures is below 25 meV.

Neste trabalho foram realizadas algumas deposições de filmes de Nitreto de Titânio sobre substrato de aço inoxidável. Foi utilizado o processo conhecido como triodo magnetron sputtering. Os parâmetros de deposição foram mantidos entre as deposições, exceto pela voltagem de bias no substrato, que foi variada de uma deposição para outra. Medições in-situ das tensões residuais no filme depositado foram realizadas. As medições foram feitas através do método da curvatura do substrato, utilizando-se um sensor capacitivo posicionado dentro da câmara de deposição. Embora o dispositivo não tenha sido capaz de quantificar os valores de tensão, foi possível identificar a natureza das mesmas, indicando se elas são de caráter trativo ou compressivo. Comprovou-se a possibilidade do uso de sistemas capacitivos para medições em sputtering. Observou-se que os filmes depositados apresentaram tensões de caráter trativo durante as deposições. / In this work, a series of depositions of titanium nitride thin films was conducted in a triode unbalanced magnetron sputtering chamber. Similar parameters were selected during each deposition, except for the substrate bias voltage, which was different for every deposition. An in-situ measurement of film residual stresses was carried out as the depositions proceeded. This measurement was based on substrate curvature, which was assessed by a home-built capacitive sensor positioned inside the sputtering chamber. Although the measurement device was not able to quantify the stress values, it was possible to identify if they were tensile or compressive. It was proved the possibility of using capacitive measurement devices in sputtering processes. It was possible to observe that the films underwent tensile stresses during the deposition.

Neste trabalho são apresentados resultados da caracterização estrutural e morfológica de filmes de oxinitreto de silício (SiOxNy) depositados pela técnica de deposição química a vapor assistida por plasma (PECVD) a baixa temperatura (320°C). O objetivo deste trabalho é relacionar a composição química de ligas amorfas de SiOxNy com suas propriedades ópticas, estruturais, morfológicas e mecânicas visando sua aplicação em dispositivos elétricos, optoeletrônica e microestruturas. A proposta é dar continuidade a trabalhos prévios desenvolvidos no grupo, que demonstraram a viabilidade de controlar a composição química e, como conseqüência, controlar as propriedades como o índice de refração, constante dielétrica e fotoluminescência de filmes de SiOxNy. As condições de deposição foram ajustadas de forma a obter dois tipos de material: filmes de SiOxNy de composição química controlável entre a do SiO2 e a do de Si3N4 e filmes de SiOxNy com composição rica em Si. O material foi caracterizado pelas técnicas de elipsometria, índice de refração por prisma acoplado, RBS (Rutherford Backscattering Spectroscopy), FTIR (Fourier Transform Infrared Spectroscopy), XANES (X-Ray Absorption Near Edge Spectroscopy) na borda K do Si, O e N, medida de stress residual e microscopia eletrônica de varredura (Scanning Electron Microscopy) e de transmissão (Transmission Electron Microscopy). Os resultados mostraram que os filmes com composição química intermediária entre a do SiO2 e a do Si3N4 apresentam arranjo estrutural estável com a temperatura, mantendo as ligações e a estrutura amorfa mesmo após tratamentos térmicos a 1000°C. Também fora demonstrada a possibilidade de obter um material com baixo stress residual e índice de refração ajustável entre 1,46 e 2, resultados ótimos para aplicações em MOEMS (micro-opto-electro- mechanical systems). Já nas amostras ricas em Si foi observada a formação de diferentes fases, sendo uma delas formada por aglomerados de Si e a outra por material constituído por uma mistura de ligações Si-O e Si-N. Este material apresenta a formação de nanocristais de Si, dependendo do conteúdo de Si e das condições do tratamento térmico, permitindo assim, sua aplicação em dispositivos emissores de luz. / In this work results on the morphological and structural characterization of silicon oxynitride (SiOxNy) films deposited by plasma enhanced chemical vapor deposition technique (PECVD) at low temperature (320°C) are presented. The main goal is to correlate the chemical composition of amorphous SiOxNy alloys to their optical, structural, morphological and mechanical properties intending applications on electrical, optoelectronic and micromechanical devices. The proposal is to continue previous research developed in this group, which demonstrated the possibility of tuning the chemical composition and, consequently, the SiOxNy films properties such as refractive index, dielectric constant and photoluminescence by the precise control of the deposition parameters. The deposition conditions were adjusted in order to obtain to material types, SiOxNy films with tunable chemical composition between SiO2 and Si3N4 and silicon-rich SiOxNy. The characterization was performed by elipsometry, refractive index by coupled prism, RBS (Rutherford Backscattering Spectroscopy), FTIR (Fourier Transform Infrared Spectroscopy), XANES (X-Ray Absorption Near Edge Spectroscopy) on K edge of Si, O and N, residual stress measurement and Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The films with chemical composition between SiO2 and Si3N4 presented stable structural arrangement with temperature, maintaining the chemical bonds and the amorphous structure after high temperature annealing. Also the results demonstrated the possibility of producing a low residual stress material and an adjustable refractive index since in the 1.46 to 2 range, excellent result for MOEMS devices (micro-opto-electro- mechanical systems applications. For silicon rich-samples the formation of different phases was observed, one formed by Si clusters and other one by a mixture of Si-O and Si-N bonds. Depending on the Si content and on the annealing conditions this material can present nanocristals, results which allowed us to understand and to optimize this material for light emitting devices applications.

This thesis explores the application of two-dimensional (2D) materials such as graphene and single layer hexagonal boron nitride (h-BN) which are produced by liquid phase exfoliation for use in printed electronics and energy composite applications. In Chapter 2 I give a broad overview of the electrical, mechanical and optical properties of 2D materials among other nanomaterials that were used in the thesis such as carbon nanotubes and conductive polymers. Additionally I review the techniques and theory behind the exfoliation and dispersion of functional layered materials. In Chapter 3 I present the coating and printing techniques which were used in this thesis along with the experimental techniques and methods which I use to characterise my inks, films and devices. Chapter 4 is the first experimental chapter of the thesis and demonstrates the printing of 2D material heterostructures to create fully printed dieletrically gated field effect transistors with 2D materials on textile and polymer substrates. In this chapter I also demonstrate reprogrammable volatile memory, p and n type inverters, complementary inverters, and logic gates which pave the way to fully printed integrated circuits, operational at room temperature and pressure with 2D materials processed in liquid. In Chapter 5, I review spray coating (a highly industrial scalable printing technique), in terms of the optimisation of its parameters to achieve thin films of nanomaterials on three-dimensional (3D) surfaces. I then demonstrate that it is possible to create large area (∼750 cm2) transparent conducting films around curved surfaces with spray coating enabling a semi-transparent (around 360°) spherical touch sensor for interactive devices. Chapter 6 explores printed photonics for applications in terahertz (THz) frequencies. Here I demonstrate the feasibility of liquid phase exfoliated graphene to create THz saturable absorbers (SAs) which could enable many applications in THz frequencies such as tomography or time-resolved spectroscopy that require mode-locked (i.e. enabling a train of short pulses to be derived from continuous-wave operation) THz pulses. I also demonstrate that these SAs can be inkjet printed on demand providing unprecedented compactness in a quantum cascade laser system. Finally in Chapter 7, I look at the application of graphene in microbial fuel cells (MFC). I demonstrate that enhanced MFC output arises from the interplay of the improved surface area, enhanced conductivity, and catalytic surface groups of a graphene based electrode. As a final step graphene based anodes and cathodes which were entirely platinum free were combined to create an environmentally sustainable energy source.

Os aços inoxidáveis duplex (AIDs) são materiais com um excelente desempenho tanto mecânico como à corrosão. Inúmeras pesquisas tem sido desenvolvidas para aprimorar a soldabilidade destas ligas. Algumas transformações de fase, que são passíveis de ocorrer durante o processo de soldagem, podem prejudicar seriamente o desempenho das juntas. Foram simuladas microestruturas da região da zona afetada pelo calor submetida a temperaturas elevadas (ZACTE), utilizando um modelo proposto de fluxo de calor. Abordaram-se aspectos fundamentais da precipitação de austenita secundária, de nitreto de cromo e as suas interações na ZACTE de soldas multipasse. Finalmente, foram realizados testes de tenacidade e de resistência à corrosão para avaliar o efeito das transformações de fase estudadas no desempenho das juntas soldadas. Os tratamento térmicos e simulações da ZACTE foram realizadas num equipamento GleebleÒ. As microestruturas foram analisadas mediante microscopia ótica e eletrônica de varredura e de transmissão. Junto com a microscopia eletrônica foram realizadas microanálises químicas das fases estudadas. Baseando-se nos resultados obtidos, verificou-se que nem todos os AIDs são susceptíveis de ferritizar. Este fato tem uma grande influência no comportamento metalúrgico e na soldabilidade destes aços. Quanto aos aspectos fundamentais da metalurgia destes aços, observou-se uma estreita interação entre a precipitação da austenita secundária e os nitretos de cromo, chegando-se a propor um mecanismo de nucleação da austenita secundária intragranular a partir dos nitretos. Por último, foi constatado que o efeito deletério da austenita secundária intragranular na resistência à corrosão pode ser evitado mediante a adequada elaboração do procedimento de soldagem. / Duplex stainless steels (DSS) have excellent mechanical and corrosion properties. Many researches have been developed regarding the weldability of these alloys. There are some phase transformations that take place during the welding process, which may impair the welded joint behavior. High temperature heat-affected zone (HTHAZ) microstructures were simulated using a proposed heat flow model. Fundamental aspects of the secondary austenite and chromium nitride precipitation, and its interactions in the HTHAZ of multipass welds, were studied. In addition, toughness and corrosion tests were done to evaluate the influence of the studied phase transformations on the weld behavior. A GleebleÒ system was used to do the heat treatments and HTHAZ simulations. The microstructures were analyzed by means of optic and electron microscopy. Along with the electron microscopy it was done chemical microanalysis of the studied phases. Based on results, it was verified that not all DSSs can be ferritized. This fact has a strong influence on metallurgical behavior and weldability of these alloys. Regarding to the metallurgical fundamental aspects of these steels, it was observed a remarkable interaction between secondary austenite and chromium nitride precipitation. Thus, it was proposed a mechanism of intragranular secondary austenite precipitation from chromium nitrides. It was also verified, how the deleterious effect of intragranular secondary austenite in the corrosion resistance can be avoided by means of appropriate welding procedures.

Les nitrures d’éléments III, à savoir GaN, InN, AlN et leurs alliages, forment une famille de matériaux semi-conducteurs dont les propriétés sont particulièrement intéressantes pour la réalisation de diodes électroluminescentes (LEDs). Leur intérêt réside en particulier dans leur bande interdite qui est directe et qui couvre une large bande spectrale de l’infrarouge (0,65eV pour InN) à l’ultraviolet (6,2eV pour AlN). En raison de l’absence de substrats accordés en maille avec ces matériaux, les couches minces hétéroépitaxiées de nitrure sont généralement touchées par des problèmes de qualité cristalline. Grâce au phénomène de relaxation des contraintes en surface, les nanofils offrent une solution prometteuse pour résoudre ce problème. Ils combinent de nombreux autres avantages : en comparaison des couches minces, l’efficacité quantique interne des LEDs peut être améliorée (surface effective plus importante permettant de diminuer l’effet Auger à courant injecté identique, absence de champ de polarisation en utilisant les facettes non polaires des nanofils) et l’extraction des photons est facilitée par l’effet guide d’onde des nanofils. Cependant, une des difficultés est de parvenir à contrôler la synthèse de ces nano-objets pour garantir une homogénéité des propriétés structurales d’un fil à l’autre et au sein d’un même fil. Dans ce contexte, mon travail de thèse a consisté à étudier d’un point de vue expérimental et théorique l’impact des inhomogénéités structurales sur les propriétés optoélectroniques de dispositifs à nanofils de type LED. J’ai pu mettre en évidence et modéliser un effet de concentration du courant dans les régions riches en indium lorsque les courants injectés sont modérés. Pour de forts courants, le courant se concentre à proximité du contact sur la coquille dopée p. Théoriquement, j’ai montré que la dérive des porteurs de charge dans les puits quantiques et leur diffusion unipolaire et ambipolaire en présence d’un gradient de compositions des puits étaient négligeables. Par ailleurs, je me suis également intéressé à l’interprétation des caractéristiques courant-tension. A l’aide d’un modèle simple, j’ai également identifié la présence de courant de fuite par effet tunnel dans des structures présentant une densité importante de défaut. Dans une seconde partie de ma thèse, je me suis également intéressé à la caractérisation de nanofils à structure coeur-coquille par la technique de courant induit par faisceau d’électrons (Electron Beam Induced Current). La dépendance des cartographies EBIC en fonction de la tension appliquée et de l’énergie du faisceau incident a été modélisée. Ce travail m’a notamment amené à proposer une nouvelle méthode de caractérisation permettant de cartographier les résistivités du coeur et de la coquille des nanofils. / III-nitrides i.e. GaN, InN, AlN and their alloys are semiconductors of choice to fabricate optoelectronic devices such as Light Emitting Diodes (LEDs). One of their most interesting features relies in their direct band gap that covers a very wide spectral range, from infrared (0.65 eV for InN) to UV (6.2 eV for AlN). However, the lack of lattice-matched substrate has been responsible for strong crystalline quality issues in heteroepitaxial thin films. Thanks to stress relaxation at their surface, nanowires provide a smart solution to this problem. Besides, they have a few more assets. In comparison to thin films, nanowires can improve the internal quantum efficiency of LEDs because of their higher effective surface that leads to lowered current densities and thus mitigated Auger effect. The internal quantum efficiency also benefits from the possibility to grow the active region on non polar facets, thus getting rid of the detrimental high internal polarization-induced electric field in quantum wells. Furthermore, the photon extraction efficiency is enhanced by the guiding effect of nanowires. However, despite all this promising advantages, one of the main challenges remains the control of structural homogeneity from wire to wire but also inside single wires.In this context, my work has consisted into studying from an experimental and theoretical point of view the consequences of these structural inhomogeneities on the optoelectronic properties of nanowire based LED devices. I have shown that the current tends to gather into indium-rich regions for moderate bias. At higher bias, the dominant current path though the junction is generally located under the p-contact on the nanowire shell. I have theoretically demonstrated that the unipolar and ambipolar diffusion of carriers as well as their drift induced by a composition gradient inside the quantum wells is not significant in the devices I have studied. Moreover, I took also an interest in the detailed analyze of I-V curves. Thanks to a simple model, I have identified the presence of leakage current related to defect- and phonon-assisted tunneling effect. In the second part of my work, I have focused onto the characterization of core-shell wires using the Electron Beam Induced Current technique. The bias-dependant and acceleration voltage-dependant EBIC maps has been explained with a theoretical model based on equivalent circuits. This study leads me to suggest a new experimental method that can be used to map the nanowire core and shell resistivity.

This thesis, submitted to the University of Manchester, covers a range of topics related to current research in two-dimensional materials under the title: 'Investigations into the interfacial interaction of graphene with hexagonal boron nitride.'In the last decade, two-dimensional materials have become a rich source of original research and potential applications. The main advantage lies in the ability to produce novel composite structures, so-called 'layered heterostructures', which are only a few atomic layers thick. One can utilise the unique properties of several species of crystal separately, or how they interact to realise a diverse range of uses. Two such crystals are graphene and hexagonal boron nitride. Hexagonal boron nitride has, so far, been used primarily as a substrate for graphene, allowing researchers to get the most out of graphene's impressive individual properties. However, in this thesis, the non-trivial van der Waals interaction between graphene and hexagonal boron nitride is examined. The interface potential reveals itself as a relatively large-scale, orientation-dependant superlattice, which is described in chapters 1 and 2.I In Chapter 4, the effect of this superlattice is examined by measurement of its effect upon the electrons in graphene, where its modulation leads to the creation of second and third generation Dirac points, revealing Hofstadter's Butterfly. As well as an excellent example of the physics possible with graphene, it also presents a new tool with which to create novel devices possessing tailored electronic properties. II In chapter 5, the consequential effect of the superlattice potential on the structure of graphene is studied. Results are discussed within the framework of the Frenkel-Kontorova model for a chain of atoms on a static background potential. Results are consistent with relaxation of the graphene structure leading to the formation of a commensurate ground state. This has exciting consequences for the production of heterostructures by demonstrating that alignment angle can have large effects upon the physical properties of the crystals. III In chapter 6, the van der Waals potential is shown to be responsible for the self-alignment of the two crystals. This effect is important for the fabrication of perfectly aligned devices and may lead to new applications based on nanoscale motion.

Made available in DSpace on 2016-12-23T14:08:11Z (GMT). No. of bitstreams: 1 Roberto Balarini Junior - Parte 1.pdf: 4732272 bytes, checksum: 0c0798e2e5b19f7834c4ce1d56156d8f (MD5) Previous issue date: 2013-11-27 / Este trabalho é uma investigação tribológica envolvendo o par cerâmico composto por esferas de nitreto de silício (Si3N4) deslizando contra discos de óxido de alumínio (Al2O3) em água. No total, dez ensaios foram conduzidos com a intenção de reproduzir o fenômeno de Ultra Baixo Coeficiente de Atrito (UBCA) em laboratório, o qual é caracterizado pela obtenção de valores de coeficiente de atrito (&#956;) da ordem dos milésimos (&#956; < 0,01) no regime estacionário. Uma vez alcançado os valores de UBCA, o objetivo principal deste trabalho foi o de investigar o período de running-in, através de uma série de análises em relação ao comportamento do coeficiente de atrito durante o regime transitório, incluindo correlações com algumas variáveis, como rugosidade superficial, erros de batimento axial, íons formados durante o deslizamento e desgaste das cerâmicas. Para isto, as curvas de coeficiente de atrito por tempo foram expandidas para intervalos de tempos pré-determinados e o comportamento de &#956; em cada um destes intervalos foi investigado e comparado entre os ensaios realizados, sendo que o caráter oscilatório do coeficiente de atrito foi inserido nas análises do período transitório. Em geral, foi comprovado que maiores valores de rugosidade superficial resultaram em maiores períodos de running-in e que existe uma tendência de aumento de desgaste com o aumento do tempo de transição. Para todos os ensaios, a taxa de desgaste das esferas de Si3N4 foi superior à dos discos de Al2O3. Em adição, através de comparações entre a medida da soma das rugosidades das superfícies desgastadas com a espessura mínima do filme lubrificante, este trabalho confirma a hipótese de que é necessário um regime de lubrificação misto (hidrodinâmico e limítrofe) para a obtenção do regime de UBCA, sendo que, para a eficácia do modo de lubrificação esperado, estima-se que é necessário concentrações de íons de silício (Si) superiores a 1,3 mg/l, aproximadamente. Esta quantidade de íons Si é supostamente a mínima necessária para a formação de uma camada de sílica adequada para conferir a parcela de lubrificação limítrofe necessária para a obtenção do regime de UBCA / This work is a tribological investigation involving the ceramic pair composed by balls of silicon nitride (Si3N4) sliding against disks of aluminum oxide (Al2O3) under water. A total of ten tests were conducted in order to reproduce the phenomenon of Ultra Low Friction Coefficient (ULFC) in laboratory, which is characterized by obtaining values of friction coefficient (&#956;) below of 0,01 in the steady state. Once reached these values, the main objective of this study was to investigate the running-in period by a series of analyses in relation to the behavior of the friction coefficient during the running-in period, including correlations with some variables such as surface roughness, axial parallelism errors, ions formed during the sliding and wear of samples. For this reason, the curves of friction coefficient versus time were expanded for some predetermined intervals and the behavior of &#956; for each one of these intervals was investigated and compared between themselves, and the oscillatory behavior of the friction coefficient was inserted into the analysis of the running-in period. In general, it was concluded that higher values of surface roughness resulted in longer periods of running-in and that there is a trend of increasing wear with increasing time of transition. For all tests, the wear rate of the silicon nitride balls was higher than alumina disks. In addition, by comparing the measure of the sum of the roughness of the worn surfaces with minimum thickness of the lubricant film, the present work confirms the hypothesis that it is necessary a mixed lubrication (hydrodynamic combined with boundary) to obtain the regime of ULFC and for effective lubrication expected mode it is estimated that is required an ions concentration of silicon (Si) higher than 1.3 mg/l approximately. This amount of ions Si is supposed to be the minimum necessary for the formation of a silica layer enable to confer the boundary lubrication participation for obtaining the ULFC

Ces travaux de thèse portent sur les phénomènes d’amplification du signal de diffusion Raman par effet de surface et par effet de pointe. Des réseaux de motifs métalliques de taille nanométrique arrangés spatialement ont été fabriqués par la méthode de transfert Langmuir-Blodgett et par lithographie à faisceau d’électrons. De telles structures de géométries contrôlées déposées à la surface de lamelles de microscope ont été développées afin d’amplifier le signal Raman de molécules adsorbées par effet SERS (Surface Enhanced Raman Spectroscopy). Ces nanostructures triangulaires en or de taille proche de la longueur d’onde ont des bandes de résonance plasmon dans le domaine spectral visible. En utilisant une source de laser appropriée dans ce domaine spectral, les facteurs d’amplification Raman d’une couche mono-moléculaire d’un dérivé azobenzène sont de plusieurs ordres de grandeur, et ce pour les deux techniques de nano-lithographie employées. Afin de compléter ces premiers résultats, des réseaux de fils d’or avec de grands facteurs de forme ont été fabriqués. Ces derniers montrent des résonances plasmons multipolaires et des facteurs d’amplification de l’ordre de 105. Les techniques de microscopie en champ proche ont également été développées afin de localiser précisément l’exaltation Raman et d’accroitre la résolution spatiale de mesures Raman. Des pointes métalliques en or de taille nanométrique ont ainsi permis d’amplifier localement le signal de diffusion de molécules placées à leur proximité par effet TERS (Tip Enhanced Raman Spectroscopy). Les développements logiciels et mécaniques entre un microscope confocal Raman et un microscope à force atomique ont été implémentés afin de contrôler simultanément les deux instruments. Ce montage expérimental a été appliqué à l’étude de nanofils semi-conducteurs de nitrure de gallium permettant de suivre leur signal vibrationnel avec une résolution spatiale inférieure à 200 nm. / This thesis work focuses on Raman scattering enhancements by metallic nanostructures. In the first part of this work, arrays of metallic patterns with nanometer dimensions were fabricated by the Langmuir-Blodgett deposition technique and electron-beam lithography. Such structures made of gold were fabricated onto microscope slides with the goal to enhance the Raman signal through SERS effect (Surface Enhanced Raman Spectroscopy). These patterns formed by an assembly of triangular nanostructures with sizes of hundreds of nanometers, exhibit plasmon resonance bands in the visible spectral region. By using an appropriate excitation laser source with respect to the plasmon frequency, Raman enhancement factors of a monolayer were found to be of several order of magnitude for both Langmuir-Blodgett and electron-beam lithography platforms. To further complement these results, gold wires arrays with large aspect ratio made by electron-beam lithography showed multipolar plasmon resonances with enhancement factors up to 105. In the second part of this thesis, near-field Raman microscopy has been developed with the aim to localize precisely the Raman enhancement and improve spatial resolution of Raman measurements. Atomic force microscopy gold tips have been used to locally enhance scattering signal of molecules in close proximity to the tip opening new opportunities. This approach known as TERS (Tip Enhanced Raman Spectroscopy) is of significant interest to probe nanomaterials, nanostructures or monolayers. Software and mechanical developments have been made between a confocal Raman microscope and an atomic force microscope to control simultaneously both instruments. This experimental setup was used to characterize gallium nitride semi-conductors nanowires with spatial resolution better than 200 nm.

Filmes finos de CNx foram depositados em temperatura ambiente, 350, 400, 500oC, por deposição a vapor de carbono sobre os substratos de Si(100) ou Si(111) com irradiação simultânea por íons derivado de gás N2 ou de mistura gasosa Ar-N2. A energia de íons variou de 150 a 600 eV e a razão de chegada, R(I/A), definida pela razão do fluxo de íons de nitrogênio incidentes relativa ao fluxo de átomos de carbono transportados ao substrato, foi de 1,0-2,5. A pressão de gás na câmara de vácuo foi mantida a 1,6 ×10-2 Pa durante o processo de deposição. A taxa de deposição dos filmes foi governada pelo sputtering químico. O rendimento de sputtering químico por íons de nitrogênio foi praticamente independente da energia de íons utilizada, enquanto que o rendimento de sputtering químico por íons de Ar e nitrogênio foi dependente da energia de íons devido ao efeito multiplicativo dos íons. Os espectros Raman medidos mostraram dois picos em torno de 1350 e 1560 cm-1, chamados do pico D e do G, respectivamente, e foram analisados em termos de: posição e largura do pico G, e razão das intensidades ID/IG. Os comportamentos destes parâmetros obtidos em função de R(I/A) foram explicados razoavelmente através do modelo de três estágios, sugerido por Ferrari et al., levando em consideração uma transição da fase característica de grafite a de fulereno, na qual a incorporação suficiente de nitrogênio em camadas grafíticas promove a formaao de anéis pentagonais que pode induzir o enrugamento em camadas, facilitando ligaoes entre as camadas através de átomos de carbono hibridizados de sp3. Um indício da ocorrência desta transição pode ser visto nos difratogramas de raios X dos filmes correspondentes. Neste contexto, os espectros Raman e de XPS dos filmes de CNx depositados previamente com o método RF magnetron sputtering reativo foram analisados e explicados consistentemente, levando-se em consideração a concentração de nitrogênio nos filmes. / Thin CNx films were deposited at room temperature, 350, 400, 500oC, by carbon vapor deposition on Si(100) or Si(111) substrates with simultaneous irradiation by íons derived from N2 gas or from a gas mixture of Ar-N2. The ion energy varied from 150 to 600 eV and the arrival rate ratio, R(I/A), defined as the ratio of the flux of incident nitrogen ions relative to flux of carbon atoms transported to the substrate, was in the range of 1.0-2.5. The gas pressure in the vacuum chamber was maintained at 1.6 × 10-2 Pa during the deposition. The deposition rate of the films was governed by chemical sputtering. The chemical sputtering field by nitrogen ions was practically independent of the ion energy used, while the chemical sputtering field by Ar and nitrogen ions was dependent on it due to the multiplicative effect of the ions. Raman spectra measured showed two peaks around 1350 and 1560 cm-1, called D and G peaks, respectively, and were analyzed in terms of: the G peak position and width, and the peak intensity ratio ID/IG. The behaviors of these parameters as a function of R(I/A) were explained reasonably through the three-stage model, suggested by Ferrari et al., taking into account a transition from a graphitelike phase to a fullerenlike phase, in which a sufficient incorporation of nitrogen into graphitic planes promotes a formation of pentagonal rings which can induce buckling of graphitic planes, facilitating cross-linking between the planes through sp3-hybridized carbon atoms. Evidence for this transition could be seen in X-ray diffratograms of the corresponding films. In this context, Raman and XPS spectra of CNx films previously deposited with the reactive RF magnetron sputtering method were analyzed and explained consistently, considering the nitrogen concentration in the films.