Silicon has been the mainstay of the microelectroncs industry for over four decades. There is no material which can match the balance it affords between cost-benefit, mass consumability, process versatility, and nano-scale electron device performance. It is, therefore, the logical (and perhaps inevitable) platform for the development of integrated opto-electronics - a technology that is being aggressively developed to meet the next generation of bandwidth demands that are already beginning to strain interconnect architectures all the way down to the intra-chip level. While silicon-based materials already provide a variety of passive optical functionalities, the success of a genuine silicon-based optoelectronics will depend upon the ability of engineers to overcome those limitations in the optical properties of bulk silicon that occur at critical junctions in device requirements (eg. modulator and laser). Such solutions must not render the device processing incompatible with CMOS, for then the "silicon advantage" is lost. Achieving reliable and efficient electroluminescence in silicon remains the most intractable of these problems to date. Reliability problems in recently developed light emitting devices operating near a wavelength of 1.54 f..Lm, based on the thermally induced formation of silicon nano-clusters in erbium-doped silicon rich silicon oxide thin films, has reinforced the need for a further understanding of the luminescence mechanisms in this material. Indeed, the efficient and stable sensitized photoluminescence from Er3+ ions (near the telecom wavelength), embedded in an oxide matrix, based on a quasi-resonant energy transfer from nanostructured silicon, has the potential to make possible compact waveguide amplifiers and thin film electroluminescence. This thesis represents a study into the luminescence mechanisms in erbium-doped silicon oxide (SiOx, x~2) thin films grown by electron cyclotron resonance plasma enhanced chemical vapour deposition. Importantly, the film growth relies on in-situ erbium doping through the cracking of a volatile organalanthanide Er(tmhd)3 source. Rutherford backscattering spectroscopy has been used to map the film composition space generated from an ECR-PECVD parameter subspace consisting of precursor gas flow rates and the erbium precursor temperature. The response of the film photoluminescence spectra in both visible and infrared bands consistenly reveals three classes of luminescence centres, whose relative ability to emit light is shown in this study to exhibit a considerable degree of variability through the control of the film composition, subsequent thermal anneal temperature, duration, and process ambient. These three classes consist of optically active Er3 + ions, silicon nano-clusters phase separated during thermal annealing, and oxide-based defects (which may additionally include organic chromophores). The latter two of these species show the ability to sensitize the Er3 + luminescence. In fact, sensitization by intrinsically luminescent defects is a rarely studied phenomenon, which seems to be an important phenomenon in the present films owing to a potentially unique Er incorporation complex. To further investigate the ability of the oxide defects in this regard, an optimally luminescent film has been subject to a damaging ion irradiation to induce a photoluminescence quenching. The subsequent recovery of this luminescence with stepwise isochronous annealing has been correlated with Doppler broadening positron annihilation spectroscopy measurements made with a slow positron beam. Irradiation to a sufficiently high fluence has demonstrated a unique ability to de-couple luminescent sensitizers and Er3+ ions, producing enhanced blue and violet emissions. / Thesis / Master of Science (MS)

Ce travail de thèse concerne l’étude de différents revêtements type « Diamond-Like Carbon » élaborés par un procédé CVD assisté par un plasma basse fréquence (40 kHz). Deux revêtements de référence sont d’abord étudiés : des couches de carbone amorphe hydrogéné (a-C:H) et des couches de carbure de silicium amorphe hydrogéné (a-SiC:H). L’évolution de leurs propriétés mécaniques (dureté, module d’Young) et tribologiques (frottement, usure) est décrite en fonction des paramètres du procédé et corrélée à leur microstructure. Les résultats obtenus pour ces deux couches de référence sont ensuite exploités pour proposer deux systèmes complémentaires : des revêtements a-C:H dopées et des systèmes multicouche a-C:H/a-SiC:H. Ces deux solutions présentent des contraintes résiduelles réduites par rapport à un revêtement a-C:H monocouche ce qui permet d’envisager une augmentation importante des épaisseurs de dépôt tout en conservant des propriétés mécaniques et tribologiques intéressantes. Enfin, en vue d’une application industrielle de ces revêtements sur des pièces de moteur par exemple, l’optimisation de leur adhérence par insertion de sous-couches adaptées ainsi que de leurs performances tribologiques en conditions lubrifiées par l’intermédiaire de texturation de surface est alors envisagée / Hydrogenated amorphous carbon films (a-C:H) and hydrogenated silicon carbide films (a-SiC:H) are deposited by low frequency (40 kHz) plasma enhanced chemical vapour deposition (LF PECVD). Structural, mechanical and tribological properties of those single layers have been first studied in relation with process parameters. Then those results have been used to study two other systems. The first one corresponds to silicon doped a-C:H thin films and the second one to multilayered coatings consisting in a stack of a-C:H and a-SiC:H layers. Those coatings offer potential advantages such as lower residual stress level comparing to that of a-C:H stress level which gives the opportunity to deposit thicker films, and also attractive mechanical and tribological properties. Moreover, in case of applications like car engine parts for example, adhesion and tribological properties under lubrication have to be improved. Solutions as incorporating underlayer or texturing surface are thus also investigated in this study

Neste trabalho, filmes amorfos de oxinitreto de silício (alfa-SiO IND.XN IND.Y:H) foram crescidos pelo processo de Plasma Enhanced Chemical Vapor Deposition (PECVD) a temperatura da 320ºC. No processo de deposição foi utilizada a mistura dos gases óxido nitroso (N IND.2O) e silano (SiH IND.4), variando-se a razão entre os seus fluxos (Re= N2O/SiH4) num intervalo de 0,25 Re 5,00. Foram obtidos filmes com diferentes composições químicas, sendo ricos em O (65 at.%) para Re 2,00 e ricos em Si (44 at. %) para Re 1,50. A técnica de Rutherford backscattering spectroscopy (RBS) foi utilizada para determinar a composição química dos filmes. Os dados de RBS mostram um decréscimo da quantidade de O, enquanto que as quantidades de Si e N aumentam com o decréscimo de Re. A morfologia dos filmes foi estudada por Small Angell X-ray scattering (SAXS), Transmissio Electron Microscopy (TEM) e medida de densidade pelo método de flutuação. Os dados de SAXS revelam a presença de centros espalhadores com raio médio que varia de 10 Ã a 100 Ã. Os resultados de TEM mostram a presença de aglomerados esféricos dispersos numa matriz de mesmas espécies atômicas. A concentração de poros nos filmes é inferior a 10% e diminui com o aumento do conteúdo de oxigênio. Tanto a estrutura de ordem local quanto as ligações químicas foram investigadas pelas técnicas de X-ray Absorption Near Edge Structure (XANES), Extented X-ray Absorption Fine Structure (EXAFS) e Fourier Transform Infrared Spectroscopy (FTIR). foi desenvolvido um potencial modelo de interação para simular a estrutura atômica do oxinitreto de silício amorfo e compará-la com os dados experimentais. As simulações computacionais foram realizadas utilizando o método de Monte Carlo (MC)-Metropolis. A análise estrutural das amostras ricas em O, tanto do ponto de vista experimental quanto teórico (obtidos por MC), mostram que a estrutura básica da rede é um tetraedro, onde o átomo central é o Si conectado por O e N. Os resultados experimentais das amostras ricas em si, apontam para a formação de agregados de Si, embebidos dentro de uma matriz de Si-O-N. Tratamentos térmicos a vácuo em temperaturas entre 550 e 1000 ºC promovem a efusão de hidrogênio e segregação de diferentes fases. / In this work, thin films of amorphous silicon oxynitride(alfa-SiOxNy:H) were deposited by Plasma Enhanced Chemical Vapor Deposition (PECVD) at 320 ºC. In the deposition process a mixture of nitrous oxide (N2O) and silane (SiH4) was used, varying their flow ratio (Re= N2O/SiH4) in an interval of 0,25 Re 5,00. Films with different chemical composition were obtained, being O-rich (65 at.%) for Re 2,00 and Si-rich (44 at.%) for Re 1,50. The Rutherford backscattering spectroscopy (RBS) was used to determine the atomic content of the films. The RBS data showed a decrease of the oxygen content while the Si and N contents increase with the decrease of Re. The films morphology was studied by Small Angle X-ray scattering (SAXS), Transmission Electron Microscopy (TEM) and density measurements by the flotation method. The SAXS data revealed the presence of scattering centers with mean radius from 10 Ã to 100 Ã. The TEM data showed the presence of spherical clusters dispersed in a matrix of the same atomic species. The concentration of pores in the material is less than 10% and decreases with the increase of oxygen content. The local atomic structure and chemical bonds were investigated by X-ray Absorption Near Edge Structure (XANES), Extended X-ray Absorption Fine Structure (EXAFS) and Fourier Transform Infrared spectroscopy (FTIR). A model of interatomic potential was developed to simulate the atomic structure of the amorphous silicon oxynitride in order to be compared with the experimental data. The computer simulations were performed by the Monte Carlo (MC) Metropolis method. The structural analysis of the O-rich samples, obtained by both experimental and theoretical simulations (obtained by MC), showed that the basic structure of the network is tetrahedral, being Si the central atom connected by O and N. The experimental results of the Si-rich samples indicate the formation of Si aggregates, embedded in a Si-O-N matrix. Annealing in vacuum, at temperatures between 550 e 1000 ºC, promoted hydrogen effusion and segregation of different phases.

Este trabalho apresenta um método de fabricação de micropontas de silício que já contém os contatos elétricos integrados à sua estrutura. O processo de fabricação das microestruturas é o foco desta pesquisa e nossa motivação futura é desenvolver dispositivos para emissão eletrônica por efeito de campo (Field Emission Devices - FED. O método em questão baseia-se: (i) no underetch anisotrópico, que ocorre em substratos de silício (100) quando orientados de maneira conveniente, em solução de KOH; (ii) na utilização de filme de oxinitreto de silício (SiOxNy), que visa o mascaramento no processo de corrosão durante a formação das micropontas e também, o suporte mecânico para as trilhas metálicas que formam o eletrodo de polarização. Tal material, obtido por Deposição Química a Vapor assistida por Plasma (Plasma Enhanced Chemical Vapour Deposition - PECVD), apresenta baixo stress interno e tem a função de isolar eletricamente os eletrodos do substrato de Si. Esse filme de SiOxNy viabilizou a obtenção de trilhas autosustentadas, planas e lisas, com dimensões de até 6 milímetros. Através de técnicas convencionais de fotolitografia construímos contatos elétricos de cromo auto-alinhados sobre as micropontas. Metodologicamente definimos e caracterizamos, por meio de microscopia óptica, diferentes etapas da formação das micropontas, determinamos suas respectivas taxas de corrosão e consequentemente o tempo total de sua formação, em função das dimensões iniciais da máscara. As estruturas foram fabricadas na forma de matrizes com 50, 98, 112 e 113 micropontas. O espaçamento entre elas varia de 130 a 450 ?m. O diâmetro do ápice e a altura são de aproximadamente 1 e 54 ?m respectivamente. A principal vantagem deste método de fabricação é a eliminação da necessidade de utilização de microposicionadores externos e de acionamento manual, para a integração de contatos elétricos à estrutura. Finalmente, o êxito deste método deveu-se essencialmente às propriedades exclusivas do filme de SiOxNy. / This work presents a fabrication method of silicon microtips with integrated electrical contacts into the structure. Our motivation is the future development of field emission devices - FED, however our focus in this research is the microstructure fabrication process. This method is based on: (i) anisotropic under-etch method that occurs in the silicon substrate (100), when it is oriented in convenient crystallographic direction, using KOH solution; (ii) the employment of silicon oxinitride films (SiOxNy) which aims to mask the corrosion process during the formation of the microtips, and also to give mechanically support for the metallic tracks of their electrodes. Such material, which is obtained by Plasma Enhanced Chemical Vapour Deposition - PECVD, exhibits internal low stress and was used to obtain electric insulation between the electrodes and the Si substrate. These SiOxNy films made possible the achievement of flat and smooth selfsustained tracks, whose dimensions can reach 6 millimeters. Through conventional photolitographic techniques, we built chromium self-aligned electrical contacts on those microtips. Methodologically, we define and characterize different stages of microtips formation, by means of optical microscopy, and we determine their respective etch rates. And consequently the entire formation time in function of the initial mask dimensions. Those structures had been manufactured in the shape of matrices with 50, 98, 112 and 113 microtips which distance between each other can vary from 130 to 450 ?m. Its diameter in the microtip apex and its height are about 1 and 54 ?m respectively. The main advantage of this fabrication method is the lack of the requirement of manual external micropositioners for the integration of electrical contacts to structure itself. Finally, this method succeeds due essentially to the SiOxNy exclusive film properties.

Este trabalho apresenta um método de fabricação de micropontas de silício que já contém os contatos elétricos integrados à sua estrutura. O processo de fabricação das microestruturas é o foco desta pesquisa e nossa motivação futura é desenvolver dispositivos para emissão eletrônica por efeito de campo (Field Emission Devices - FED. O método em questão baseia-se: (i) no underetch anisotrópico, que ocorre em substratos de silício (100) quando orientados de maneira conveniente, em solução de KOH; (ii) na utilização de filme de oxinitreto de silício (SiOxNy), que visa o mascaramento no processo de corrosão durante a formação das micropontas e também, o suporte mecânico para as trilhas metálicas que formam o eletrodo de polarização. Tal material, obtido por Deposição Química a Vapor assistida por Plasma (Plasma Enhanced Chemical Vapour Deposition - PECVD), apresenta baixo stress interno e tem a função de isolar eletricamente os eletrodos do substrato de Si. Esse filme de SiOxNy viabilizou a obtenção de trilhas autosustentadas, planas e lisas, com dimensões de até 6 milímetros. Através de técnicas convencionais de fotolitografia construímos contatos elétricos de cromo auto-alinhados sobre as micropontas. Metodologicamente definimos e caracterizamos, por meio de microscopia óptica, diferentes etapas da formação das micropontas, determinamos suas respectivas taxas de corrosão e consequentemente o tempo total de sua formação, em função das dimensões iniciais da máscara. As estruturas foram fabricadas na forma de matrizes com 50, 98, 112 e 113 micropontas. O espaçamento entre elas varia de 130 a 450 ?m. O diâmetro do ápice e a altura são de aproximadamente 1 e 54 ?m respectivamente. A principal vantagem deste método de fabricação é a eliminação da necessidade de utilização de microposicionadores externos e de acionamento manual, para a integração de contatos elétricos à estrutura. Finalmente, o êxito deste método deveu-se essencialmente às propriedades exclusivas do filme de SiOxNy. / This work presents a fabrication method of silicon microtips with integrated electrical contacts into the structure. Our motivation is the future development of field emission devices - FED, however our focus in this research is the microstructure fabrication process. This method is based on: (i) anisotropic under-etch method that occurs in the silicon substrate (100), when it is oriented in convenient crystallographic direction, using KOH solution; (ii) the employment of silicon oxinitride films (SiOxNy) which aims to mask the corrosion process during the formation of the microtips, and also to give mechanically support for the metallic tracks of their electrodes. Such material, which is obtained by Plasma Enhanced Chemical Vapour Deposition - PECVD, exhibits internal low stress and was used to obtain electric insulation between the electrodes and the Si substrate. These SiOxNy films made possible the achievement of flat and smooth selfsustained tracks, whose dimensions can reach 6 millimeters. Through conventional photolitographic techniques, we built chromium self-aligned electrical contacts on those microtips. Methodologically, we define and characterize different stages of microtips formation, by means of optical microscopy, and we determine their respective etch rates. And consequently the entire formation time in function of the initial mask dimensions. Those structures had been manufactured in the shape of matrices with 50, 98, 112 and 113 microtips which distance between each other can vary from 130 to 450 ?m. Its diameter in the microtip apex and its height are about 1 and 54 ?m respectively. The main advantage of this fabrication method is the lack of the requirement of manual external micropositioners for the integration of electrical contacts to structure itself. Finally, this method succeeds due essentially to the SiOxNy exclusive film properties.

In the crystalline Si solar cell industry, there is a push to reduce module cost through a combination of thinner substrates and increased cell efficiency. Achieving solar cells with sub-100 µm substrates cost-effectively is a formidable task because such thin substrates impose stringent handling requirements and thermal budget due to their flexibility, ease of breakage, and low yield. Moreover, as the substrate thickness decreases the surface passivation quality dictates the performance of the cells. Crystalline Si heterojunction (HJ) solar cells based on hydrogenated amorphous silicon (a-Si:H) have attracted significant interest in recent years due to their excellent surface passivation properties, potential for high efficiency, low thermal budget and low cost. HJ cells with ultra-passivated surfaces showing > 700 mV open-circuit voltages (Voc) and > 20% conversion efficiency have been demonstrated. In these cells, it has been identified that high-quality a-Si:H films deposited by a low-damage plasma process is key to achieving such high cell performance. However, the options for low-damage plasma deposition process are limited. The main objectives of this work are to develop a low-plasma damage a-Si:H thin film deposition process based on remote plasma chemical vapor deposition (RPCVD) and to demonstrate high efficiency HJ solar cells on bulk substrates as well as on ultra-thin silicon and germanium substrates obtained by a novel, low-cost semiconductor-on-metal (SOM) technology. This manuscript presents a detailed description of the RPCVD system and the process leading to the realization of high quality a-Si:H thin films and high efficiency HJ solar cells. First, p-type a-Si:H thin films are developed and optimized, then HJ solar cells are subsequently fabricated on bulk and ultra-thin Si and Ge SOM substrates without intrinsic a-Si:H passivation. Single HJ cells on ~ 500 µm bulk Si and ~25 µm ultra-thin substrates exhibited conversion efficiencies of η = 16% (Voc = 615 mV, Jsc = 34 mA/cm2, and FF = 77%) and η = 11.2% (Voc = 605 mV, Jsc = 29.6 mA/cm2, and FF = 62.8%), respectively. The performance of the ~25 µm cell was further improved to η = 13.4% (Voc = 645 mV, Jsc = 31.4 mA/cm2, and FF = 66.2%) by implementing the dual HJ architecture without front side i-layer passivation. For single HJ cells based on Ge substrates, the results were η = 1.78 % (Voc = 148 mV, Jsc = 35.1 mA/cm2, and FF = 1.78%) on ~500 µm bulk Ge, compared to η =5.3% (Voc = 203 mV, Jsc = 44.7 mA/cm2, and FF = 5.28%) on ~ 50 µm Ge SOM substrates. Respectively, the results obtained on ultra-thin SOM substrates are among the highest reported in literature for based on comparable architecture and substrate thickness. In order to achieve improved cell performance, dual HJ cells with i-layer passivation of both surfaces were fabricated. First, optimized RPCVD-based i-layer films were developed by varying the deposition temperature and H2 dilution ratio (R). It was found that excellent surface passivation on planar substrates with as-deposited minority carrier lifetimes > 1 ms is achievable by using deposition temperature of 200 ºC and moderate dilution ratio 0.5 ≤ R ≤ 1, even without the more rigorous RCA pre-cleaning process typically used in literature for achieving comparable results. Subsequently, dual HJ solar cells with i-layer films were demonstrated on planar and textured bulk Si substrates showing improved conversion efficiencies of η = 17.3% (Voc = 664 mV, Jsc = 34.34 mA/cm2 and FF = 76%) and η = 19.4% (Voc = 643 mV, Jsc = 38.99 mA/cm2, and FF = 77.5%), respectively. / text

Thin-film silicon tandem solar cells based on a hydrogenated amorphous silicon (a-Si:H) top-cell and a hydrogenated microcrystalline silicon (μc-Si:H) bottom-cell are a promising photovoltaic technology as they use a combination of absorber materials that is ideally suited for the solar spectrum. Additionally, the involved materials are abundant and non-toxic which is important for the manufacturing and application on a large scale. One of the most important factors for the application of photovoltaic technologies is the cost per watt. There are several ways to reduce this figure: increasing the efficiency of the solar cells, reducing the material consumption and increasing the throughput of the manufacturing equipment. The use of very-high frequencies has been proven to be beneficial for the material quality at high deposition rates thus enabling a high throughput and high solar cell efficiencies. In the present work a scalable very-high frequency plasma-enhanced chemical vapor deposition (VHF-PECVD) technique for state-of-the-art solar cells is developed. Linear plasma sources are applied which facilitate the use of very-high frequencies on large areas without compromising on the homogeneity of the deposition process. The linear plasma sources require a dynamic deposition process with the substrate passing by the electrodes in order to achieve a homogeneous deposition on large areas. State-of-the-art static radio-frequency (RF) PECVD processes are used as a reference in order to assess the potential of a dynamic VHF-PECVD technique for the growth of high-quality a-Si:H and μc-Si:H absorber layers at high rates. In chapter 4 the influence of the deposition process of the μc-Si:H i-layer on the solar cell performance is studied for static deposition processes. It is shown that the correlation between the i-layer growth rate, its crystallinity and the solar cell performance is similar for VHF- and RF-PECVD processes despite the different electrode configurations, excitation frequencies and process regimes. It is found that solar cells incorporating i-layers grown statically using VHF-PECVD processes obtain a state-of-the-art efficiency close to 8 % for growth rates up to 1.4 nm/s compared to 0.53 nm/s for RF-PECVD processes. The influence of dynamic deposition processes on the performance of μc-Si:H solar cells is studied. It is found that μc-Si:H solar cells incorporating dynamically grown i-layers obtain an efficiency of 7.3 % at a deposition rate of 0.95 nm/s. There is a small negative influence of the dynamic deposition process on the solar cell efficiency compared to static deposition processes which is related to the changing growth conditions the substrate encounters during a dynamic i-layer deposition process. The changes in gas composition during a dynamic i-layer deposition process using the linear plasma sources are studied systematically using a static RF-PECVD regime and applying a time-dependent gas composition. The results show that the changes in the gas composition affect the solar cell performance if they exceed a critical level. In chapter 5 dynamic VHF-PECVD processes for a-Si:H are developed in order to investigate the influence of the i-layer growth rate, process parameters and deposition technique on the solar performance and light-induced degradation. The results in this work indicate that a-Si:H solar cells incorporating i-layers grown dynamically by VHF-PECVD using linear plasma sources perform as good and better as solar cells with i-layers grown statically by RF-PECVD at the same deposition rate. State-of-the-art stabilized a-Si:H solar cell efficiencies of 7.6 % are obtained at a growth rate of 0.35 nm/s using dynamic VHF-PECVD processes. It is found that the stabilized efficiency of the a-Si:H solar cells strongly decreases with the i-layer deposition rate. A simplified model is presented that is used to obtain an estimate for the deposition rate dependent efficiency of an a-Si:H/μc-Si:H tandem solar cell based on the photovoltaic parameters of the single-junction solar cells. The aim is to investigate the individual influences of the a-Si:H and μc-Si:H absorber layer deposition rates on the performance of the tandem solar cell. The results show that a high deposition rate of the μc-Si:H absorber layer has a much higher potential for reducing the total deposition time of the absorber layers compared to high deposition rates for the a-Si:H absorber layer. Additionally, it is found that high deposition rates for a-Si:H have a strong negative impact on the tandem solar cell performance while the tandem solar cell efficiency remains almost constant for higher μc-Si:H deposition rates. It is concluded that the deposition rate of the μc-Si:H absorber layer is key to reduce the total deposition time without compromising on the tandem solar cell performance. The developed VHF-PECVD technique using linear plasma sources is capable of meeting this criterion while promoting a path to scale the processes to large substrate areas.

Le phénomène d'injection de charges dans des isolants synthétiques et la distorsion du champ électrique qui en découlent représentent un frein au développement des câbles pour le transport d'énergie électrique sous haute tension continue (HVDC). Les solutions au problème sont le plus souvent recherchées en influant sur la formulation des matériaux, en l'occurrence le polyéthylène. La voie explorée dans cette thèse est une alternative consistant à créer une barrière permettant le contrôle de l'injection de charges dans un film de polyéthylène basse densité (LDPE) sous contrainte électrique. La solution proposée et étudiée consiste à modifier la surface du film polymère en y insérant des nanoparticules métalliques, susceptibles de jouer le rôle de pièges profonds et d'écranter le champ électrique, contrôlant ainsi l'injection. Pour cela, des nanoparticules d'argent (NPs d'Ag) sont déposées et recouvertes d'une matrice semi-isolante organosiliciée de type SiOxCy:H. La couche mince nanocomposite est élaborée par procédé plasma. Son épaisseur totale est d'environ 50 nm. Les nanoparticules sont obtenues par pulvérisation cathodique et la matrice environnante est réalisée avec un dépôt chimique en phase vapeur assisté par plasma. Le procédé d'élaboration est mis en œuvre dans le même réacteur en utilisant une décharge asymétrique RF à couplage capacitif entretenue à 13.56 MHz à basse pression du gaz. Une étude de l'influence des conditions opératoires du plasma sur les caractéristiques des NPs d'Ag et sur la matrice environnante a été réalisée. Les caractéristiques définies des NPs d'Ag sont la densité, la taille moyenne et la dispersion des nanoparticules. Les analyses physico-chimiques et structurales de la couche nanocomposite ont permis de valider la maîtrise de la formation des nanoparticules et de ses propriétés. L'évaluation de l'efficacité du dépôt a permis de définir les caractéristiques essentielles pour un contrôle des phénomènes d'injection de charges. Les analyses du comportement de l'ensemble étudié sous contrainte électrique ont été obtenues par des mesures de distribution de charges d'espace par méthode électroacoustique, de courant et de potentiel de surface. Les résultats montrent que la modification de la surface d'un film polymère par une couche mince nanocomposite contenant des NPs d'Ag enterrées à une profondeur contrôlée de la surface de la matrice organosiliciée permet le contrôle parfait de l'injection de charge dans un film de LPDE sous des niveaux de champ électrique usuels pour les applications HVDC. L'impact des caractéristiques de la couche nanocomposite sur l'efficacité du procédé a été évalué. Cette étude prouve le concept et ouvre la voie de la maîtrise des interfaces pour le contrôle de l'injection de charges dans des isolants polymères. / Charge injection phenomenon in electrically insulating polymers and the resultant electric field distortion remain obstacles to the development of cables for electrical energy transport under high voltage direct current (HVDC). Routes to solve the problem are most often looked for by acting on the material formulation, polyethylene in the present case. As alternative route, we explore in this thesis the possibility to develop a barrier layer allowing fine control of the charge injection in low density polyethylene (LDPE) films. The proposed and further studied solution is to tailor the surface of the polymer film by introducing metallic nanoparticles that would act as deep traps and would produce field screening, thus controlling charge injection. To achieve this, silver nanoparticles (AgNPs) are deposited on the LDPE and covered by a thin organosilicon layers of the type SiOxCy:H. The nanocomposite layer with total thickness of about 50 nm is elaborated in a plasma process. The AgNPs are obtained by sputtering of a silver target and the organosilicon matrix is then deposited in a plasma enhanced chemical vapor deposition (PECVD). The deposition process is realized in the same reactor in the plasma of an asymmetric RF capacitively coupled discharge maintained at 13.56 MHz at low gas pressure. The obtained characteristics for the AgNPs are for their mean size, density and dispersion. The physico-chemical and structural analyses of the nanocomposite layer allowed identifying the plasma operating conditions to control the AgNPs properties. From the evaluation of the efficiency of the AgNPs/organosilicon stack against charge injection, a detailed description of the required properties of the nanocomposite layer for the control of the charge injection phenomenon was derived. The behaviour of the studied structure, nanocomposite layer deposited on the surface of LDPE film, under electrical stress was studied by space charge measurement through the Pulsed Electro-Acoustic (PEA) method, current and surface potential decay measurements. The obtained results show that tailoring the surface of polyethylene film by very thin nanocomposite layer containing AgNPs embedded at a controlled distance from the free surface of the organosilicon matrix permits suppression of charges injection in LDPE films. The impact of nanocomposite layer structure on the efficiency of the barrier effect was evaluated. The mitigation effect is observed up to the typical service electric field for HVDC applications. This study presents a proof-of-concept and opens the way for interface tailoring to control the charge injection in electrically insulating polymers.

Neste trabalho, filmes amorfos de oxinitreto de silício (alfa-SiO IND.XN IND.Y:H) foram crescidos pelo processo de Plasma Enhanced Chemical Vapor Deposition (PECVD) a temperatura da 320ºC. No processo de deposição foi utilizada a mistura dos gases óxido nitroso (N IND.2O) e silano (SiH IND.4), variando-se a razão entre os seus fluxos (Re= N2O/SiH4) num intervalo de 0,25 Re 5,00. Foram obtidos filmes com diferentes composições químicas, sendo ricos em O (65 at.%) para Re 2,00 e ricos em Si (44 at. %) para Re 1,50. A técnica de Rutherford backscattering spectroscopy (RBS) foi utilizada para determinar a composição química dos filmes. Os dados de RBS mostram um decréscimo da quantidade de O, enquanto que as quantidades de Si e N aumentam com o decréscimo de Re. A morfologia dos filmes foi estudada por Small Angell X-ray scattering (SAXS), Transmissio Electron Microscopy (TEM) e medida de densidade pelo método de flutuação. Os dados de SAXS revelam a presença de centros espalhadores com raio médio que varia de 10 Ã a 100 Ã. Os resultados de TEM mostram a presença de aglomerados esféricos dispersos numa matriz de mesmas espécies atômicas. A concentração de poros nos filmes é inferior a 10% e diminui com o aumento do conteúdo de oxigênio. Tanto a estrutura de ordem local quanto as ligações químicas foram investigadas pelas técnicas de X-ray Absorption Near Edge Structure (XANES), Extented X-ray Absorption Fine Structure (EXAFS) e Fourier Transform Infrared Spectroscopy (FTIR). foi desenvolvido um potencial modelo de interação para simular a estrutura atômica do oxinitreto de silício amorfo e compará-la com os dados experimentais. As simulações computacionais foram realizadas utilizando o método de Monte Carlo (MC)-Metropolis. A análise estrutural das amostras ricas em O, tanto do ponto de vista experimental quanto teórico (obtidos por MC), mostram que a estrutura básica da rede é um tetraedro, onde o átomo central é o Si conectado por O e N. Os resultados experimentais das amostras ricas em si, apontam para a formação de agregados de Si, embebidos dentro de uma matriz de Si-O-N. Tratamentos térmicos a vácuo em temperaturas entre 550 e 1000 ºC promovem a efusão de hidrogênio e segregação de diferentes fases. / In this work, thin films of amorphous silicon oxynitride(alfa-SiOxNy:H) were deposited by Plasma Enhanced Chemical Vapor Deposition (PECVD) at 320 ºC. In the deposition process a mixture of nitrous oxide (N2O) and silane (SiH4) was used, varying their flow ratio (Re= N2O/SiH4) in an interval of 0,25 Re 5,00. Films with different chemical composition were obtained, being O-rich (65 at.%) for Re 2,00 and Si-rich (44 at.%) for Re 1,50. The Rutherford backscattering spectroscopy (RBS) was used to determine the atomic content of the films. The RBS data showed a decrease of the oxygen content while the Si and N contents increase with the decrease of Re. The films morphology was studied by Small Angle X-ray scattering (SAXS), Transmission Electron Microscopy (TEM) and density measurements by the flotation method. The SAXS data revealed the presence of scattering centers with mean radius from 10 Ã to 100 Ã. The TEM data showed the presence of spherical clusters dispersed in a matrix of the same atomic species. The concentration of pores in the material is less than 10% and decreases with the increase of oxygen content. The local atomic structure and chemical bonds were investigated by X-ray Absorption Near Edge Structure (XANES), Extended X-ray Absorption Fine Structure (EXAFS) and Fourier Transform Infrared spectroscopy (FTIR). A model of interatomic potential was developed to simulate the atomic structure of the amorphous silicon oxynitride in order to be compared with the experimental data. The computer simulations were performed by the Monte Carlo (MC) Metropolis method. The structural analysis of the O-rich samples, obtained by both experimental and theoretical simulations (obtained by MC), showed that the basic structure of the network is tetrahedral, being Si the central atom connected by O and N. The experimental results of the Si-rich samples indicate the formation of Si aggregates, embedded in a Si-O-N matrix. Annealing in vacuum, at temperatures between 550 e 1000 ºC, promoted hydrogen effusion and segregation of different phases.

Orientador: Mario Antonio Bica de Moraes / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-09T10:56:06Z (GMT). No. of bitstreams: 1 Gelamo_RogerioValentim_D.pdf: 1517991 bytes, checksum: fd93a7ffa508ced1257f9474d2674aed (MD5) Previous issue date: 2007 / Resumo: Filmes finos de polisiloxanos, polisilazanos e policarbosilanos, sintetizados por Deposição Química de Vapor Assistida por Plasma (PECVD), foram irradiados com os íons He +, Ne +, Ar +e Kr +, com energia de 170 keV, e fluências de 1x10 14 , 5x10 14 , 1x10 15 , 5x10 15e 1x10 16 íons/cm 2 . A irradiação iônica promoveu modificações significativas na composição elementar, na estrutura química, e consequentemente nas propriedades físicas dos filmes. Com o uso de espectroscopias de retro-espalhamento Rutherford (RBS) e de recuo frontal (FRS), observou-se que as razões atômicas C/Si, O/Si, N/Si e H/Si sofreram modificações. Em especial, a razão H/Si foi drasticamente diminuída, devido à perda de hidrogênio causada pela irradiação. Oxigênio foi quimicamente incorporado aos filmes, devido à recombinação das ligações pendentes, formadas durante a irradiação, com o ar ambiente. Com relação à estrutura química dos filmes, extinção e formação de novos grupos e de ligações químicas foram observadas com o uso de espectroscopias infravermelha no modo reflexão-absorção (IRRAS) e de fotoelétrons excitados por raios-X (XPS). A densidade volumétrica dos filmes aumentou significativamente com a irradiação. As constantes ópticas, medidas através de espectroscopia ultravioleta-visível e elipsometria, foram também afetadas. Com o aumento da fluência dos íons, o coeficiente de absorção e o índice de refração aumentaram e o gap óptico diminuiu. Medidas de nanoindentação mostraram notáveis aumentos nas durezas dos filmes. Nas mais altas fluências utilizadas, a dureza chegou a valores comparáveis e até maiores que a dos aços ferramenta. Os filmes são convertidos de polímero para a fase cerâmica e a intensidade da conversão é dependente da fluência dos íons. Observou-se ainda que, de modo geral, as modificações são fortemente dependentes das massas dos íons, já que as modificações mais significativas são obtidas com o uso de He+ e Ne+ . A explicação referente a esse efeito é dada em função das transferências de energia eletrônica e nuclear / Abstract: Thin films of polysiloxanes, polysilazanes and polycarbosilanes, synthesized by Plasma Enhanced Chemical Vapor Deposition (PECVD), were irradiated with 170 keV He + , Ne + , Ar + and Kr + ions, at 170 keV at fluences of 1x10 14 , 5 x10 14 , 1x10 15 , 5x10 15 and 1 x10 16 ions/cm -2 . The irradiation promoted significant modifications in the atomic composition, chemical structure, and consequently in the physical properties of the films. Changes in the atomic composition were examined using Rutherford back-scattering spectroscopy (RBS) and forward recoil spectroscopy (FRS). The former was used to determine the C/Si, N/Si and O/Si atomic ratios, while the H/Si ratio was measured by the latter. As a general behavior, these ratios changed with ion irradiation and the decrease in the H/Si ratio was particularly high, as hydrogen was drastically removed by ion bombardment. Oxygen was chemically incorporated into the films due to the reactions involving dangling bonds formed during irradiation, and ambient air. Regarding the chemical structure of the films, extinction and formation of new bonding groups and chemical bonds were observed as a function of the ion fluence using infrared reflection-absorption spectroscopy (IRRAS) and X-ray photoelectron spectroscopy (XPS). The volume density of the films increased significantly with irradiaton. The optical constants, determined using ultraviolet-visible spectroscopy and ellipsometry, were also affected by ion irradiation. With increasing ion fluence, the absorption coefficient and refractive index increased, and the optical gap decreased. From nanoindentation measurements. remarkable increases in surface hardness were determined. For the higher fluences, the surface hardness of the films is in the range, or even higher, of that of martensitic tool steels. Thus, ion irradiation changed the relatively soft polymer film into a high density, hard, ceramic material. It was observed that the most significant modifications occur for He+ and Ne+ ions. An explanation to this finding is offered in terms of the electronic and nuclear energy transfer functions / Doutorado / Física da Matéria Condensada / Doutor em Ciências