On s'est intéressé dans ce travail à l'élaboration, la caractérisation et la modélisation des propriétés optiques d'une nouvelle génération de cristaux photoniques hybrides à une dimension à base d'un composé organique l'hexaméthyldisiloxane dilué dans l'oxygène ou l'azote, et pur en alternance avec le silicium. Après un bref rappel sur l'historique des cristaux photoniques, et leur originalité qui réside en l'existence de bandes interdites photoniques (BIP) qui sont à la base de leurs applications potentielles dans la communication optique et l'optoélectronique. Nous avons ensuite présenté les matériaux de base utilisés pour l'élaboration de nos cristaux photoniques et qui sont: l'hexaméthyldisiloxane (HMDSO) et le silicium, qu'on a déposé en couches minces par les techniques de PECVD et de pulvérisation cathodique magnétron RF. La composition de ces couches a été analysée par spectroscopie infrarouge à transformé de Fourrier et leurs indices de réfraction déterminés par spectroscopie de transmission et de réflexion. Les deux premiers cristaux photoniques hybrides sont issus de même matériaux organiques le HMDSO qu'on a dilué respectivement avec l'oxygène et l'azote. Pour le premier cristal nous avons fait varier le flux d'oxygène jusqu'à obtenir des nouvelles phases formées de HMDSO et SiO2. Pour le deuxième cristal nous avons dilué le HMDSO avec l'azote en faisant varier la puissance RF de dépôt jusqu'à obtenir deux phases formées de SiCxNyOzH et -Si3N4. Les deux cristaux photoniques sont ainsi de matériau présentant un bon contraste d'indice propice à l'émergence de la bande interdite photonique. Le troisième cristal photonique hybride est quant à lui constitué des couche de HMDSO pur alternées avec des couches de silicium. Nous avons interprété les résultats expérimentaux à l'aide d'un modèle théorique basé sur la méthode de matrice de transfert. Enfin nous avons étudié dans les trois cristaux photoniques l'effet d'incorporation des défauts et nous avons montré l'existence de mode localisé à l'intérieur de la bande interdite photonique / In this work, we focused on the elaboration, characterization and modelization of the optical properties of a new generation of one-dimensional hybrid photonic crystals based from an organic compound hexamethyldisiloxane diluted in oxygen or nitrogen, and pure alternating with silicon. After a brief review of the history of photonic crystals, their originality lies in the existence of photonic band gaps (BIPs) which are the basis of their potential applications in optical communication and optoelectronics. Then we presented the basic materials used for the production of our photonic crystals, which are: hexamethyldisiloxane (HMDSO) and silicon, which have been deposited in thin layers by PECVD and RF magnetron sputtering techniques. The composition of these layers was analyzed by Fourrier transform infrared spectroscopy and their refractive indixes determined by transmission and reflection spectroscopy. The two hybrid photonic crystals were obtained from the same organic materials HMDSO which were diluted with oxygen and nitrogen, respectively. For the first crystal we have varied the flow of oxygen and we obtain a new phases formed of HMDSO and SiO2. For the second crystal we have diluted the HMDSO with nitrogen by varying the RF deposition power until two phases are formed of SiCxNyOzH and -Si3N4. These two photonic crystals are thus materials presenting a good contrast of index leads to the emergence of the photonic band gap. The third hybrid photonic crystal consists of layers of pure HMDSO alternating with layers of silicon. We have interpreted the experimental results using a theoretical model based on the transfer matrix method. Finally, we studied in the three photonic crystals the effect of incorporation of the defects and we have shown the existence of located mode within the photonic band gap

No description available.

This work deals generally with surface diagnostic and optical properties of thin layers which are created by plasma polymerization of hexamethyldisiloxane monomer. The influence of oxygen adittion on thin layers properties was studied, too. This polymer layers are commercially made to protect reflective layers in the headlights. Thin layers were made in deposition chamber AluMet 1800V at Zlin Precision Company. Teoretical part of this work deals with methods which are used for deposition of thin layers, mainly physical (PVD) and chemical (PECVD, CVD) depositions. The conditions which influenced plasma polymerization itself are discussed as well as, monomers which are used for plasma polymerization and stability of thin polymer layers. Also there are mentioned the most frequent plasma processes diagnostic methods applicable during the deposition (optical emission spectroscopy) and methods for thin layers diagnostic (wettability, UV-VIS and infrared spectroscopy). Spectrometer Jobin Yvon Triax 320 was used for emission spectra acquisition during the plasma deposition. There were analyzed only two spectra created at same conditions as power at 3 kW and monomer flow rate at 100 sccm; the first one was in pure monomer, the second was obtained with oxygen addition of 150 sccm into the monomer flow. There was not found any essential differences between these spectra in the range 300 nm to 800 nm. Besides the thin layers analyzes after their formation, the samples were exposed to common aging conditions with respect to their use. One third of the prepared samples was exposed by ultraviolet radiation for 48 hours (exposure power of 0.68 W.m-2 at 340 nm) and the other part of samples was inserted for four days into NaCl solution of 50 g.l-1. The surface properties of layers were studied by their contact angle with three liquids (water, diiodmethane, and glycerol) that allowed their surface energy calculation. Results of this measuring are as following: Oxygen addition decreased contact angle of water after exposure of UV radiation. If the highest flow rate of monomer was used and oxygen was added, NaCl degradation did not have any significant influence on contact angle to water. Optical properties of prepared thin films were characterized by UV-VIS spectroscopy. Optical properties were measured only for samples after deposition and samples that were exposed by ultraviolet radiation. Results showed that oxygen addition into the reacting mixture increased the light absorption in UV-VIS (300-800 nm). The absorption was significantly increased after exposure of ultraviolet radiation. With respect to the application of these thin layers is necessary to say that this influence is undesirable. On the other hand, absorption of thin layers deposited at 2 kW, without oxygen addition and flow rate of monomer at 125 sccm a 150 sccm was decreased. Results of this work can be useful for investigation and study of deposited thin layers. The most useful can be with another work which deals with plasma diagnostics during the deposition even more closely. Then it will be possible to adjust and predict properties of deposited layers.

Submitted by RICARDO SHINDI HOSOKAWA null (rickhoso@bol.com.br) on 2017-01-03T23:30:20Z No. of bitstreams: 1 Delineação de padrões na superfície da poliamida por processo de plasma.pdf: 4742915 bytes, checksum: 268d0bc1d9923e2f37c24eceb7007ce5 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2017-01-05T18:24:40Z (GMT) No. of bitstreams: 1 hosokawa_rs_me_bauru.pdf: 4742915 bytes, checksum: 268d0bc1d9923e2f37c24eceb7007ce5 (MD5) / Made available in DSpace on 2017-01-05T18:24:40Z (GMT). No. of bitstreams: 1 hosokawa_rs_me_bauru.pdf: 4742915 bytes, checksum: 268d0bc1d9923e2f37c24eceb7007ce5 (MD5) Previous issue date: 2016-11-17 / Neste trabalho foi investigada a possibilidade de se criar padrões regularmente distribuídos sobre a superfície da poliamida (PA), utilizando o processo de deposição de filmes em plasmas de baixa pressão. Para tal, um único procedimento foi empregado utilizando-se uma malha metálica comercial (60 μm) como máscara para delinear pilares na superfície da poliamida. Os plasmas de deposição foram gerados a partir de atmosferas contendo 70% de hexametildisiloxano (HMDSO) e 30% de oxigênio a uma pressão total de 23 Pa, já incluído o valor de 3 Pa referente à pressão de fundo. O plasma foi ativado pela aplicação do sinal de radiofrequência (13,56 MHz, 150 W) no suporte de amostras enquanto o eletrodo superior permaneceu aterrado. O tempo de deposição, t, foi alterado de 15 a 90 min. Na etapa inicial do trabalho o filme foi uniformemente depositado sobre o polímero sem a utilização de máscara. Uma segunda etapa de experimentos foi realizada, utilizando-se condições idênticas às anteriores, mas com o auxílio da trama metálica sobre as amostras para guiar a deposição do filme somente nos poros da máscara. Filmes organosilicones, compostos por estruturas granulares e com espessuras dependentes de t, foram uniformemente depositados sobre a PA quando a máscara não foi utilizada. A deposição do filme independentemente da condição de t, aumenta a rugosidade superficial e transforma a amostra inicialmente hidrofílica em hidrofóbica. Muito embora t afete de forma suave a composição química, estrutura molecular e a molhabilidade do filme, seu efeito na espessura da camada é substancial. Padrões na forma de pilares foram regularmente definidos na superfície da PA com a deposição do filme organosilicone e a utilização da máscara. A altura dos pilares cresce com t alcançando até 1 µm. Para os maiores valores de t empregados, as máscaras não atuaram efetivamente como sombra na região dos fios. Observou-se que a molhabilidade da superfície ficou estável com o tempo de envelhecimento e não foi afetada pelos padrões. / In this work it was investigated the possibility of creating patterns regularly distributed on the surface of the polyamide (PA), using the process of film deposition in low pressure plasmas. For such, a single procedure was employed using a commercial metallic mesh (60 μm) as a mask to delineate pillars on the polyamide surface. The depositing plasmas were generated from atmospheres containing 70% of hexamethyldisiloxane (HMDSO) and 30% of oxygen at a total pressure of 23 Pa, already included the amount of 3 Pa related to the background pressure. The plasma was activated applying a radiofrequency signal (13.56 MHz, 150 W) to the sample holder while grounding the topmost electrode. Deposition time, t, was changed from 15 to 90 min. In the initial stage of the work the film was evenly deposited on the polymer without the usage of mask. A second step of experiments was performed, using the same conditions as earlier, but with the aid of the metallic frame on the samples to guide the film deposition only in the pores of the mask. Organosilicones films consisting of granular structures and thickness dependent of t were evenly deposited on the PA when the mask was not used. The film deposition, independently of condition of t, increases the surface roughness and transforms the sample initially hydrophilic to hydrophobic. Although t affects smoothly the chemical composition, molecular structure and wettability of the film, its effect on the layer thickness is substantial. Patterns in the form of pillars were regularly defined on the surface of PA with the organosilicon film deposition and the usage of the mask. The height of the pillars grows with t reaching up to 1 micrometers. For higher values of t, the masks did not act effectively as shadow in the wire region. It was observed that the surface wettability was stable with the aging time and it was not affected by the patterns.

Made available in DSpace on 2016-06-02T19:19:56Z (GMT). No. of bitstreams: 1 MENA_Rodrigo_2013.pdf: 2867164 bytes, checksum: bfe45eefdca81e4813750dfe0d6cfc15 (MD5) Previous issue date: 2013-07-31 / Financiadora de Estudos e Projetos / It is known that polypropylene is degraded in the presence of UV radiation, making difficult its use in applications where occurs this kind of radiation. This situation arises a need to improve the properties of polypropylene under photodegradation. Some work was done in order to improve the surface properties of the polypropylene film with deposition of organosilicon, but the photoprotection caused by these films is still poorly studied. The purpose of this study was to deposit a film prepared from organosilicon plasmas of HMDSO (Hexamethyldisiloxane) on the surface of polypropylene films and verify the protection provided against photodegradation. Depending on the plasma deposition conditions, we detected a variation in the protection exerted by the deposited film. Among the tests, the chemical vapor deposition on low pressure plasma by radio frequency of 13.56 MHz using a mixture of gases with pressure O2/HMDSO added 6 Pa and a power of 80 W for a period of 1 h showed the best protection results, measured by comparing the evolution of the area in the region with the carbonyl peak at 1722 cm-1. FEG-SEM analysis showed that the film generated have adhesion to the substrate. Profilometry analyzes demonstrated that increasing the deposition time increases the film thickness and decreases its surface roughness. / É sabido que o polipropileno sofre degradação na presença de radiação UV, dificultando a sua utilização em aplicações onde ocorre incidência deste tipo de radiação. Surge assim a necessidade de se melhorar as propriedades do polipropileno em relação à fotodegradação. Alguns trabalhos foram desenvolvidos no sentido de melhorar as propriedades superficiais do polipropileno com a deposição de filmes de organosilicone, mas a fotoproteção originada por estes filmes ainda é pouco estudada. O propósito do presente trabalho foi o de depositar um filme organosilicone preparado a partir de plasmas de HMDSO (Hexametildisiloxano) sobre a superfície de filmes de polipropileno e verificar a proteção fornecida contra a fotodegradação. Dependendo das condições de deposição a plasma empregadas, detectou-se uma variação na proteção exercida pelo filme depositado. Dentre os testes realizados, a deposição de vapor químico por plasma de baixa pressão de radiofrequência de 13,56 MHz usando uma mistura de gases de O2/HMDSO com pressão de somada de 6 Pa e com uma potência de 80 W pelo período de 1 h foi a que apresentou melhores resultados de proteção, medida pela comparação da evolução da área da carbonila na região com pico em 1722 cm-1 As análises SEMFEG demonstraram que o filme formado tem adesão ao substrato. As análises de perfilometria demonstraram que o aumento do tempo de deposição aumenta a espessura do filme e diminui sua rugosidade.

The thesis deals with the surface modification of cotton fabric by low-pressure micro-wave plasma discharge. The main materials used for this experiment are cotton fabrics and hexamethyldisiloxane. The experiment itself is focused on the modification of cotton fabric to improve hydrophobic atributes. An argon process gas was used in the surface modification. The individual treated samples were operated with changes in process gas flow and the time during which the above-mentioned modifications was performed. Two methods were used to analyze the results of the experiment. The first one was aimed at determining changes in hydrophobic atributes in the form of wetta-bility in an unmodified sample compared to other modificated samples using the drop-let method. An electron microscope was used for the subsequent study of possible changes in surface topography. From the point of view of the examined results, the difference in hydrophobic properties was observed when using the droplet method to-gether with the change in the topography of the surface obtained on the electron mi-croscope in the cotton samples examined. The actual evaluation of individual methods points to the desirable changes in modified cotton compared to unmodified cotton. Further information regarding the results of the experiment, depending on the changes in individual parameters in the cotton treatment process using low pressure microwave plasma discharge, are presented in thesis.

The theoretical part of the thesis is focused on surface treatments, their evaluation from the point of view visual properties, plasma-enhanced chemical vapor deposition and analysis of thin layers prepared by plasma polymerization. The experimental part of the thesis deals with surface treatment of stainless steel AISI 304. Thin layers of pp-HMDSO (plasma-polymer) and of DLC are deposited on the steel´s surface for the purpose of preparing transparent layer, which protect steel´s surface against of making finger prints visible. As an objective method is chosen an immersion test in artificial sweat solution according to standard ČSN EN ISO 105-E04. Evaluation of the test is measured by a gloss-meter and by a colorimeter. Prepared layers are identificated by FTIR method.

The theme of this work is the preparation and characterization of multilayer barrier coatings to polymer and metal substrates based on SiOx and organic molecules. It deals with the determination of their properties in terms of oxygen permeability and corrosion protection. The starting materials for the preparation of these layers are hexamethyldisiloxane, octafluorocyclobutane and 4,12-dichloro[2.2]paracyclophane. These layers have been prepared with regard to their use as barrier coatings for use in archeology, with the focus on corrosion protection of coated items and other specific requirements museums. For these samples was realized characteristic of both in terms of their physical properties – the ability to resist permeation of oxygen and in terms of their chemical composition. The fourier transformation infrared spectroscopy (FTIR), scanning elektron microscopy (SEM), oxygen transmission rate (OTR), contac angle measurement and corrosion testing were used for the above-mentioned characterisations.

[pt] Neste trabalho estudamos filmes depositados por três organosilícios em forma líquida pelo método de deposição química na fase vapor assistido por plasma (PECVD) sobre chapas de aço inoxidável 316L e lâminas de silício cristalino <100>. Os líquidos empregados foram o Hexametidissilazano (HMDSN), Hexametidissiloxano (HMDSO) e Hexametildissilano (HMDS). Determinamos as propriedades estruturais, mecânicas e tribológicas dos filmes crescidos, e a viabilidade do seu uso como revestimento protetor. Foram depositados dois conjuntos de amostras para cada líquido, o primeiro a 200C e o segundo 300oC. Em cada um dos conjuntos, a tensão de autopolarização no crescimento foi variada indo de -150V até -450V. Tentou-se caracterizar filmes crescidos a temperatura ambiente, porém não obtivemos êxito, pois delaminavam. Os filmes foram caracterizados por técnicas de perfilometria, onde determinamos que os filmes crescidos com temperaturas de 200C tiveram a maior taxa de deposição. Estes filmes para todos os líquidos possuem uma tensão interna entre 1 e 2 GPa. Os filmes foram analisados também por espectroscopia de fotoelétrons induzidos por raios-x (XPS), espectroscopia de absorção no infravermelho e espectroscopia de emissão ótica (GDOES) onde identificamos as concentrações atômicas e as ligações químicas presentes nos filmes. Com a espectroscopia Raman observamos que os filmes têm presença de carbonos com hibridização sp2. Os filmes sintetizados têm um forte caráter polimérico, e para os crescidos com tensões de autopolarização maiores que -250V, observamos a presença das bandas D e G características de filmes de carbono amorfo. As análises feitas por nanoindentação determinou que os filmes tinham dureza entre 18 e 21 GPa. A microscopia de força atômica evidenciou que os filmes têm uma rugosidade rms em torno de 0,3nm. Medida de tribologia mostraram que os filmes têm um coeficiente de atrito de 0,25. Após as medidas de tribologia, foram feitas imagens de perfilometria para determinar o desgaste. Os filmes se mostraram resistentes, com a menor taxa de 7nm/min quando submetido a uma força de 0,3 Newtons e como contra corpo uma esfera de aço inoxidável (AISI302), e após as medidas os filmes não delaminaram. Com relação ao envelhecimento do filme, alguns foram sintetizados a mais de 4 anos, e continuam bem aderidos tanto sobre o substrato de aço, como o de silício. Verificamos também a viabilidade do uso do hexametildissílazano (HMDSN) como camada adesiva para a deposição de filmes de carbono amorfo hidrogenado sobre chapas de aço inoxidável com sucesso. Fizemos também a deposição de um filme depositado a partir do hexametildissiloxano (HMDSO) sobre um parafuso de aço inoxidável para verificar a viabilidade para deposições sobre materiais com geometrias diferentes, com sucesso, o filme bem aderido em sua superfície. / [en] In this work, we study films deposited by three organosilanes in liquid phase by the plasma deposition method (PECVD) on 316L stainless steel plates and crystalline silicon slides <100>. The liquids employed were Hexamethyldisilazane (HMDSN), Hexamethyldisiloxane (HMDSO) and Hexamethyldisilane (HMDS). We determined the structural, mechanical and tribological properties of grown films, and the feasibility of their use as a protective coating. Two sets of samples were deposited for each liquid, the first at 200C and the second at 300C. In each set, the bias at the growth was varied ranging from -150V to -450V. Attempts were made to characterize films grown at room temperature, but we did not succeed because they delaminated. The films were characterized by profilometry techniques, where we determined that the films grown with temperatures of 200oC had the highest deposition rate. The films were also analyzed by x-ray photoelectron spectroscopy (XPS), infrared absorption spectroscopy (FTIR) and glow discharge optical emission spectroscopy (GDOES), where we identified the atomic concentrations and the chemical bonds present in the films. With the Raman spectroscopy we observed that the films have presence of carbons with hybridization sp2. The films synthesized have a strong polymeric character, and for those grown with bias higher than -250V, we observed the presence of D- and G- bands that are characteristics of amorphous carbon films. Analysis by nanoindentation determined that the films had a hardness between 18 and 21 GPa. Atomic force microscopy showed that the films have a roughness RMS around 0.3nm. Measurement of tribology showed that the films have a coefficient of friction of 0.25. After the tribology measurements, profilometry images were made to determine the wear. The films were resistant, with the lowest rate of 7 nm/min when subjected to a force of 0.3 Newtons and as against a body of stainless steel (AISI302), and after the measurements the films did not delaminate. Regarding the aging of the film, some were synthesized for more than 4 years, and remain well adhered both on the steel substrate and silicon. We also verified the feasibility of using hexamethyldisilazane (HMDSN) as an adhesive layer for the deposition of hydrogenated amorphous carbon films on stainless steel substrate successfully. We also deposited a film from the hexamethyldisiloxane (HMDSO) on a stainless steel screw to verify the feasibility for deposition on materials with different geometries, successfully, the film was well adhered on its surface.

This thesis deals with surface analysis and characterization of optical features of thin films created by hexamethyldisiloxane (HMDSO) plasma polymerization on silicon wafers. The RF plasma industrial deposition equipment was used for the thin layers formation. These thin films serve as protective coatings on the reflective layer in the car light or solar panels. Theoretic part gives basic information about plasma, its occurrence, features, diagnostics and applications. Thin layers, their production and characterization are discussed here, too. Theoretic description of monomer material (including the group of other organosilicones) is also presented here. The FTIR spectroscopy and elipsometry are mentioned as the main methods for thin films characterisation. Because material during its practical use degrades due to external conditions, the influence of them on the thin layer properties is studied using the accelerated aging of created films. Industrial deposition chamber AluMet 1800V made by Leybold Optics, Ltd. installed in Zlin Precision company was used for the thin films production. Thin films were created under different conditions that were selelected near to the real conditions used in technology. Various applied powers (2-5 kW) were used for the deposition under different monomer flows. Further, the influence of oxygen addition on the created film properties was investigated. The deposition process was monitored by optical emission spectroscopy. The spectrometer Jobin Yvon Triax 320 with CCD detector was used. The selected part from every samples set was exposed by UV radiation (48 hours at radiation density of 0.68 W/m2 at 340 nm) to simulate the probable conditions during the layers real use. The surface properties were investigated by measurement of reflected light spectral intensity in the visible range at different angles. The angle between incident and reflected beam was varied in the interval of 40 - 150° with 10° step. The influence of sample preparation conditions as well as their aging effect was studied at the selected angles. Spectral reflectance doesn´t depend significantly on applied discharge power and oxygen addition. The significant shift of reflectance into the red part of spectrum was observed at UV exposed samples more or less independently on the applied discharge power of monomer flow rate. Addition of oxygen during the deposition suppresses this effec significantly. Characterization of thin layer structure was done by FTIR spectroscopy. No significant changes were observed in the structure at different discharge powers of monomer flow rates except total absorption intensities that are proportional to the layr thickness. The oxygen addition, of course, changes the structure significantly. These results are only preliminary because the layers were very thin (deposition conditions were near to the common process standard) and thus the signal/noise ratio was relatively low.