Neste trabalho foram estudadas as características elétricas e ópticas de filmes de carbono tipo diamante (DLC Diamond-Like Carbon) depositados em um sistema de sputtering RF magnetron reativo em substratos de silício e vidro. Foram depositadas amostras em condições de processo distintas em cada tipo de substrato, sendo duas condições de pressão (5 mTorr e 10 mTorr) e para cada uma, quatro condições de potência de RF (100 W, 150 W, 200 W e 250 W). Os filmes depositados foram submetidos às seguintes técnicas de caracterização: perfilometria, para obtenção da espessura dos filmes e com isso a taxa de deposição; elipsometria, para obtenção do índice de refração; obtenção de curvas I-V, para obtenção da resistividade elétrica e cálculo do ganho de foto corrente, e da curva C-V de alta frequência, para cálculo da constante dielétrica dos filmes; transmitância óptica, para o cálculo do gap óptico através do método de Tauc; fotoluminescência, para determinar a emissão característica deste gap e espectroscopia de infravermelho por transformada de Fourier (FTIR), para se observar os tipos de ligações presentes no filme e calcular a relação entre hibridizações sp3 e sp2 entre átomos de carbono e hidrogênio no filme. As variações de algumas características dos filmes de DLC com os parâmetros de processo são apresentadas e comparadas. De acordo com as características dos filmes obtidos neste trabalho, com a variação dos parâmetros de processo, é possível sua aplicação como dielétrico de campo, por apresentarem baixa constante dielétrica, sendo o valor mais baixo obtido igual a 3,4; como material dielétrico de porta considerando os filmes com alta constante dielétrica, chegando a 6,7; como material para cobertura, devido à alta uniformidade (até 95%); e, o que foi mais explorado neste trabalho, para aplicações como sensores foto sensíveis, sendo que o maior ganho de foto corrente obtido foi 67 vezes. A possibilidade de produção de filmes de DLC com diferentes propriedades através da variação das condições de processo mostra sua versatilidade para uso em diferentes aplicações. / In this work it was studied electrical and optical characteristics of diamond-like carbon (DLC) films deposited in a reactive RF magnetron sputtering system on silicon and glass substrates. Samples were deposited at different process conditions in each type of substrate at two pressure conditions (5 mTorr and 10 mTorr) and four conditions of RF power (100 W, 150 W, 200 W and 250 W). The DLC films were characterized by the following techniques: high step meter analysis, to obtain the thickness of the films and thus the deposition rate; Ellipsometry to obtain the refractive index; electrical characterization by the I-V curve, to obtain the resistivity and calculate the photo current gain, and high-frequency C-V curve, to calculate the dielectric constant of the films; optical transmittance, to calculate the optical gap by the Tauc method; photoluminescence analysis, to determine the characteristic emission of this gap; Fourier transform infrared spectroscopy (FTIR), to observe the different carbon-hydrogen bonds and calculate its sp3/sp2 hybridizations ratio. The way some characteristics of DLC films vary with the process parameters are presented and compared in this work. According to the characteristics of the DLC films obtained in this work, with the variation of the process parameters it is possible their application as low k dielectric insulators, because of its low dielectric constant, being the lowest obtained value 3.4; as dielectric gate material, reaching 6.7 in the films deposited in this work, as coating material due to its high uniformity (95%), and which was further explored in this work, for applications like photo-sensitive sensors, since it was obtained samples with photo current gain up to 65. The possibility of producing DLC films with different properties by varying process parameters shows its versatility for using in different applications.

Neste trabalho foram estudadas as características elétricas e ópticas de filmes de carbono tipo diamante (DLC Diamond-Like Carbon) depositados em um sistema de sputtering RF magnetron reativo em substratos de silício e vidro. Foram depositadas amostras em condições de processo distintas em cada tipo de substrato, sendo duas condições de pressão (5 mTorr e 10 mTorr) e para cada uma, quatro condições de potência de RF (100 W, 150 W, 200 W e 250 W). Os filmes depositados foram submetidos às seguintes técnicas de caracterização: perfilometria, para obtenção da espessura dos filmes e com isso a taxa de deposição; elipsometria, para obtenção do índice de refração; obtenção de curvas I-V, para obtenção da resistividade elétrica e cálculo do ganho de foto corrente, e da curva C-V de alta frequência, para cálculo da constante dielétrica dos filmes; transmitância óptica, para o cálculo do gap óptico através do método de Tauc; fotoluminescência, para determinar a emissão característica deste gap e espectroscopia de infravermelho por transformada de Fourier (FTIR), para se observar os tipos de ligações presentes no filme e calcular a relação entre hibridizações sp3 e sp2 entre átomos de carbono e hidrogênio no filme. As variações de algumas características dos filmes de DLC com os parâmetros de processo são apresentadas e comparadas. De acordo com as características dos filmes obtidos neste trabalho, com a variação dos parâmetros de processo, é possível sua aplicação como dielétrico de campo, por apresentarem baixa constante dielétrica, sendo o valor mais baixo obtido igual a 3,4; como material dielétrico de porta considerando os filmes com alta constante dielétrica, chegando a 6,7; como material para cobertura, devido à alta uniformidade (até 95%); e, o que foi mais explorado neste trabalho, para aplicações como sensores foto sensíveis, sendo que o maior ganho de foto corrente obtido foi 67 vezes. A possibilidade de produção de filmes de DLC com diferentes propriedades através da variação das condições de processo mostra sua versatilidade para uso em diferentes aplicações. / In this work it was studied electrical and optical characteristics of diamond-like carbon (DLC) films deposited in a reactive RF magnetron sputtering system on silicon and glass substrates. Samples were deposited at different process conditions in each type of substrate at two pressure conditions (5 mTorr and 10 mTorr) and four conditions of RF power (100 W, 150 W, 200 W and 250 W). The DLC films were characterized by the following techniques: high step meter analysis, to obtain the thickness of the films and thus the deposition rate; Ellipsometry to obtain the refractive index; electrical characterization by the I-V curve, to obtain the resistivity and calculate the photo current gain, and high-frequency C-V curve, to calculate the dielectric constant of the films; optical transmittance, to calculate the optical gap by the Tauc method; photoluminescence analysis, to determine the characteristic emission of this gap; Fourier transform infrared spectroscopy (FTIR), to observe the different carbon-hydrogen bonds and calculate its sp3/sp2 hybridizations ratio. The way some characteristics of DLC films vary with the process parameters are presented and compared in this work. According to the characteristics of the DLC films obtained in this work, with the variation of the process parameters it is possible their application as low k dielectric insulators, because of its low dielectric constant, being the lowest obtained value 3.4; as dielectric gate material, reaching 6.7 in the films deposited in this work, as coating material due to its high uniformity (95%), and which was further explored in this work, for applications like photo-sensitive sensors, since it was obtained samples with photo current gain up to 65. The possibility of producing DLC films with different properties by varying process parameters shows its versatility for using in different applications.

Les films minces de Diamond-Like Carbon sont couramment employés dans les moteurs automobiles. Leur très faible coefficient de frottement et leur haute dureté permettent en effet d’optimiser les performances et la durée de vie des véhicules. Cependant, la plupart des lubrifiants utilisés dans les moteurs sont élaborés pour fonctionner avec des surfaces métalliques. Il est donc envisageable d’améliorer le comportement tribologique de films de DLC en leur conférant un caractère métallique par l’introduction d’éléments dopants en quantité limitée et contrôlée (15 % au maximum) dans la matrice de carbone amorphe. Un réacteur de dépôt industriel muni d’une technologie de dépôt hybride a été utilisé. Celle-ci combine la PECVD pour l’élaboration du DLC hydrogéné à la pulvérisation cathodique magnétron pour le dopage. Quatre éléments ont été introduits à différentes concentrations dans le DLC : aluminium, cuivre, molybdène et niobium. Les propriétés physico-chimiques des dépôts ont été caractérisées par XPS (composition et liaisons chimiques) et spectroscopie Raman (structure). La dureté, le frottement et l’usure à sec et en conditions lubrifiées, ainsi que l’énergie de surface des films ont également été caractérisés. Deux études in situ de tenue des DLC en température ont été conduites par spectroscopie Raman. Par comparaison avec un film de DLC pur, le dopage entraîne une modification de la structure du DLC, et par conséquent une réduction de la dureté des couches. Cependant, excepté dans le cas du cuivre, ceci s’accompagne d’une diminution significative du coefficient de frottement et de l’usure à sec des couches. En revanche, en dépit de ce résultat prometteur, l’impact sur les propriétés tribologiques en milieu lubrifié est plus modéré et fortement lié à la composition du lubrifiant employé. Enfin le transfert industriel du dopage a été étudié et validé dans le cas du dopage à l’aluminium. / Diamond-Like Carbon thin films are commonly used in automotive engines. Thanks to their very low friction coefficient and high hardness, it is indeed possible to optimize the performances and the lifetime of vehicles. However, most of the lubricants that are used in engines are designed to be in contact with metallic surfaces. So it might be possible to improve the global tribological behaviour of DLC films by giving them a metallic character. This can be achieved with the introduction of doping elements in limited and controlled amount (maximum 15 at. %) in the amorphous carbon matrix. An industrial scale reactor has been used with a hybrid coating technology combining PECVD for the deposition of hydrogenated DLC and magnetron sputtering for the introduction of the dopants. Four elements have been tested with various amounts in the DLC: aluminium, copper, molybdenum and niobium. The physico-chemical properties of the films have been characterized by XPS (chemical composition and bonding) and Raman spectroscopy (structure). Hardness, friction and wear in both dry and lubricated conditions, and surface energy have also been determined. Two in situ studies under temperature have been conducted by Raman spectroscopy for deposited thin films. Compared to a pure DLC, doping led to a modification of the structure resulting in a decrease in hardness. However, except for copper doping, a significant reduction of friction and wear in dry conditions is observed. Despite this promising result, the impact of doping on lubricated tribological behaviour is limited and strongly dependent on the composition of the lubricant itself. Finally, the industrial transfer of DLC metallic doping has been studied and validated.

Optical properties (transmission and refractive index) and chemical structure (XPS) of diamond-like coating (DLC) film before and after focused ion beam milling (FIBM) process, were investigated in this paper. It is shown by our FIBM experiment that influence of FIBM on Optical properties and chemical structure of the DLC film is not apparent, especially in near-infra region. The film still can be used for optical applications. As an application example, diffractive optical element (DOE) was directly fabricated on the film by use of FIBM. Measured diffraction efficiency of the DOE is 73%, which is acceptable for conventional use. / Singapore-MIT Alliance (SMA)

Since the diamond like carbon features include high hardness and high wear resistance, low friction coefficient, chemical inertness, high resistance, low dielectric constant, the IR Transparency and field emission. The process of Diamond carbon film was usually by CVD or PVD techniques. However, high substrate temperature or low deposition rate and the can not make large area of films leads to limit the applications of diamond like film. Electrodeposition method is an innovative method to prepare DLC film and it meets these demands such as: equipment cheap, high deposition rate and larger area coatings. In this paper, ITO substrate was used for electrodeposition the diamond-like carbon films and to evaluate the possibility for the large area of DLC films.For the process of electrical deposition, the electrolyte consists of acetic acid and DI water mixed in different proportions. The deposition process were conditioned as: electrolyte concentration between 0.01% and 0.8%; voltage from 2.1V to 50V; growth temperature in the range of 300C ~ 850C. In addition, by using the control variables method, the deposition parameters including voltage, deposition temperature and solution concentration of electrolyte were varied to evaluate the characteristics and quality of diamond-like carbon films. The n & k film analyzer (n & k Analyze), X ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) were used to characterize the surface morphology, microstructure and compositional analysis. The reflectivity, transmittance, and refractive index of DLC Films were revealed by the n & k analyzer. Hence, the best conditions used for anti-reflective layer and projections Eopg can be achieved. For SEM analysis, the DLC film with uniformity surface structure can be found. Additionally, the current - time graph can be used to predict the properties of film varied with the applied voltage, percent of concentrations, growth temperature etc.. The microstructure of DLC film was investigated by the XPS measurement; the sp2 / sp3 ratio varies from the growth parameters changes. The hydrogen content of DLC films was obtained by FTIR measurements, the contents decrease as the operating voltage, electrolyte concentration and the substrate temperature increase. As for the DLC deposited on ITO glass as an anti-reflective layer, the experimental results showed that DLC film can reduce the reflectivity from 40% to 70%. Finally, the results obtained show a reasonable match for various measurements. T he characteristics of DLC films also shows that it very depends on the deposited parameters and the relationship beteen them was discussed in detailed. Some of the advance study will be investigated in future.

In this study, DLC thin films were electrodeposited at low DC potential using a mixture of acetic acid and DI water with different ratio. The parameters of DLC thin film deposition include the DC potential, deposition temperature, concentration of electrolyte solution, were correlated to the growth mechanism. The amount of nitrogen incorporated into DLC thin films were varied with the deposited temperature. The characteristics of DLC films by various measurements such as : the I-t curves of DLC film growth, SEM, AFM, FTIR, XPS, Raman and N&K spectroscopy, were investigated in detail. Experimental results showed that the surface roughness decreased, and sp3/sp2+sp3 value of DLC increased with the deposition temperature and deposition time. Optical properties showed that the refractive index, optical energy gap increased with the deposition temperature. For SEM cross-section measurement, it showed that the thickness of DLC films decreased due to the erosion process. However, the N-DLC films become graphitization. According to our study, we find that the surface morphology of the N-DLC films are homogeneous and compact. However, with the increase of the deposition temperature, the ratio of sp3-C-N bonds increase and the ratio of sp2-C-C bonds decrease, and these lead to the increase of refractive index and optical energy gap.

Diamond-Like Carbon (DLC) films have been deposited on ITO glass substrate. DLC thin film was electrodeposited at low DC potential using a mixture of acetic acid and DI water. The DLC film deposition parameters include DC potential, deposited temperature, the concentration of electrolyte were used to study the characteristics of DLC film measured by the Ellipsometer, XPS, SEM and Raman spectroscopy in detail. The Raman spectra shows two peaks located near 1358cm-1 and 1580cm-1 assigned as the characteristics peaks of DLC films. That is an evidence for DLC film deposited successfully on ITO glass. Scanning electron microscopy (SEM) can make insight into accurately the surface morphology and uniformity of DLC films so as used to grow the best quality of DLC films. From the variations of the I-t curve and the surface morphology observed by SEM, the properties of DLC film depend on a verity of growth parameters such as applied voltage, the concentration of electrolyte and deposition temperature. The shift of G-peak increase with the applied voltage, and the sp2/sp3 ratio of the content C1s decreases with the applied voltage. Finally, based on the I-t curve and results of SEM, XPS, Raman, and Ellipsometer for n, k coefficients measured, we obtain a deeply understanding for the growth conditions of DLC films and their surface morphology. We achieve the consistent results between various measurements. Finally, the optimizing growth of DLC film is to be studied and discussed in future

Diamond-like carbon (DLC) thin films were produced by pulsed laser deposition (PLD) on silicon, fused silica, and silicon nitride substrates. The films produced were either undoped, made using a pure graphite target, or doped, using multi-component targets made from a combination of graphite and silicon, silicon nitride, titanium dioxide, or silicon monoxide. These films were evaluated for their potential use in biomedical applications, including coatings for artificial joints, heart stents, and bronchoscopes. The films were characterized by Raman spectroscopy, atomic force microscopy, ball-on-flat tribometry, contact angle measurements, and spectrophotometry. Film thickness was determined by optical profilometry. Film adhesion was checked by soaking the films in simulated body fluid (SBF) and monitoring the quality of the film surface at varying time intervals using an optical microscope. DLC coatings were produced with a root mean square surface roughness of less than 1 nm and a 0.08 lubricated coefficient of friction. Contact angles of water on the undoped films varied with deposition conditions, ranging from 65 to 88 degrees. Contact angles as low as 25 degrees were achieved by incorporating silicon monoxide dopant. DLC coatings were produced on fused silica having high transparency and showing no delamination after forty-three weeks of immersion in SBF. These results indicate that these films have potential as biomedical coatings.

Biomateriais metálicos devem apresentar uma combinação de propriedades como resistência à corrosão, biocompatibilidade e resistência mecânica. Os aços inoxidáveis austeníticos, especialmente do tipo AISI 316L, aliam estas propriedades com a possibilidade de fabricação a um baixo custo. No entanto, são susceptíveis à corrosão nos fluidos fisiológicos e seus produtos de corrosão podem causar reações alérgicas ou infecciosas nos tecidos vizinhos ao implante. No presente trabalho, a aplicação de revestimentos obtidos por processos de deposição física de vapor (PVD) sobre um aço inoxidável austenítico do tipo AISI 316L foi realizada a fim de aumentar sua resistência à corrosão e biocompatibilidade. Os filmes depositados foram de nitreto de titânio (TiN), carbonitreto de titânio (TiCN) e de carbono tipo diamante (DLC). Estes materiais têm alta dureza e resistência ao desgaste, além de biocompatibilidade intrínseca, características altamente desejáveis para aplicações biomédicas. A caracterização do comportamento eletroquímico do aço com os três tipos de revestimentos mostrou que a presença de defeitos na superfície das camadas depositadas exerce uma influência negativa sobre a resistência à corrosão do substrato. A presença dos defeitos foi evidenciada por microscopia eletrônica de varredura. Foi proposto um mecanismo, com base nos dados obtidos por espectroscopia de impedância eletroquímica, para explicar a evolução do comportamento eletroquímico do aço com os diferentes revestimentos ao longo do tempo de imersão. Foram também empregados dois tratamentos de passivação da superfície do aço em soluções de ácido sulfúrico e ácido nítrico, a fim de aumentar a resistência à corrosão do substrato. Os resultados indicaram que os tratamentos utilizados não foram eficientes para melhorar esta característica, mas podem ser modificados visando um desempenho superior. As propriedades eletrônicas dos filmes passivos formados, tanto sobre o aço sem tratamento de passivação como sobre o aço passivado, foram estudadas utilizando a abordagem de Mott-Schottky. Os filmes apresentaram um caráter duplex, mostrando comportamento de um semicondutor altamente dopado acima e abaixo do potencial de banda plana. A concentração de dopantes no filme passivo foi associada à resistência à corrosão do material. Os três revestimentos PVD investigados apresentaram comportamento não citotóxico. Considerando a diminuição do coeficiente de atrito do aço 316L, os revestimentos de TiCN e o DLC foram os mais eficientes. Estas características, aliadas ao fator custo, sugerem que a aplicação comercial destes materiais sobre implantes ortopédicos pode ser viável. No entanto, a resistência à corrosão, conforme a avaliação realizada no presente estudo, não foi adequada quando comparada ao desempenho do aço sem nenhum tipo de revestimento. Ao final do texto, são apresentadas algumas sugestões a fim de conseguir um desempenho superior para a capacidade protetora dos revestimentos PVD. / Metallic biomaterials must present a combination of properties such as corrosion resistance, biocompatibility and mechanical resistance. Austenitic stainless steels, especially AISI 316L combine these properties with the easy of fabrication at low cost. However, they are prone to corrosion in physiological solutions. Furthermore, their corrosion products may lead to infectious ou allergenic reactions in the tissues around the implant device. In the present work, coatings produced by physical vapour deposition (PVD) methods have been applied on the surface of a 316L stainless steel to increase its corrosion resistance and biocompatibility. Three thin films were tested: titanium nitride (TiN), titanium carbonitride (TiCN) and diamond-like carbon (DLC). These materials present high hardness, wear resistance and intrinsic biocompatibility that are key features when considering biomedical applications. The characterization of the electrochemical behavior of the stainless steel coated with the three different films showed that the presence of surface defects are deleterious to the corrosion resistance of the substrate. These defects were observed using scanning electron microscopy. The evolution of the electrochemical behavior of the coated steel was explained through a mechanism based on the experimental results obtained using electrochemical impedance spectroscopy. Two different passivation treatments were carried out on the stainless steel surface, either in sulfuric or nitric acid solutions, to increase its corrosion resistance. The results suggested que these treatments were not efficient, but may be modified to improve its performance. The electronic properties of the passive films of the non-passivated and passivated stainless steel were studied using the Mott-Schottky approach. The films presented a duplex character. Below the flatband potential the behavior is typical of a highly doped type-p semiconductor. Above the flatband potential is typical of a highly doped type-n semiconductor. The doping concentration in the passive film was determined and associated with the corrosion resistance of the substrate. All PVD coatings investigated showed non-cytotoxic behavior. DLC and TiCN coatings decreased the friction coefficient of the stainless steel substrate. These properties allied with the stainless steel low cost recommend their commercial use for implants materials purposes. Nevertheless the corrosion resistance presented by the coated-steel was inferior to that of the bare steel and should be improved. At the end of the present text, some suggestions are proposed in order to improve the corrosion protection performance of the PVD coatings.

Nas últimas décadas, questões sobre o controle de emissões em motores à combustão interna e sobre a redução de consumo de combustível vêm sendo debatidas globalmente, com claros desdobramentos em especificações de controles mais restritos, a fim de permitir a comercialização de novos motores à combustão interna a consumidores mais exigentes, que presam pela qualidade de vida e meio ambiente. Mesmo com a introdução de novas tecnologias, os motores ainda apresentam uma grande perda da energia gerada por conta do atrito mecânico. Com base neste contexto, os projetos dos novos motores visam uma melhor eficiência térmica e mecânica, com auxílio de soluções de engenharia que possam beneficiar o desempenho dos motores, resultando em uma melhor queima do combustível e menor atrito. Um dos contribuintes mais relevantes para o atrito num motor é o sistema pistão-anel de pistão-camisa de cilindro que é o foco de muitos trabalhos em busca da redução das perdas por atrito. As propriedades dos filmes à base de carbono tipo diamante (Diamond-Like Carbon - DLC) são bem conhecidas por apresentam alta resistência ao desgaste e baixo coeficiente de atrito, tornando-se adequados para diferentes aplicações tribológicas. O presente trabalho discute a viabilidade técnica de se aplicar um filme DLC amorfo hidrogenado, com gradiente de composição química, sobre a superfície interna brunida de camisas de cilindro para redução do atrito. A metodologia aborda duas espessuras de filme: 2,5 e 12,5 μm, depositadas pelo processo de deposição química em fase vapor assistida por plasma (PACVD), como alternativa para redução do atrito do motor e, consequentemente, redução no consumo específico de combustível, e ainda na redução do desgaste dos anéis de pistão e da superfície de trabalho da camisa de cilindro. Comparando camisas de cilindro com mesma rugosidade na superfície interna, denominadas camisas de referência (sem revestimento interno) e camisas recobertas com filme DLC, testes de bancada com movimento recíproco de contato mostraram redução do coeficiente de atrito (COF) em até 19%. Testes de motor ciclo Otto e Diesel em banco de prova com dinamômetro conferiram, respectivamente, uma redução da pressão média efetiva de atrito (FMEP) do motor em até 12% e consumo específico de combustível (BSFC) em até 2,5% em rotações de 1000 a 1400 rpm. / In the last few decades questions about emissions level control for internal combustion engines as well as fuel consumption reduction have been debated in a global bases with clear deployments in more restricted control specifications to allow the commercialization of new internal combustion engines to more restrictive markets that look for a better life quality and environment. Even with the introduction of new technologies the engines still present a significant loss of energy due to the mechanical friction. With base in this context, the new development projects seek for high mechanical-thermal efficiency linked with engineer that can benefit the engine performance with a better combustion process and reduced friction as well. One of the most relevant contributors for the friction in an engine is the piston-piston ring-cylinder liner system which has been the focus of many research works with focus on reduce engine friction losses. The properties of Diamond-Like Carbon films (DLC) are well-known such as superior wear resistance and low friction coefficients that makes suitable for many different tribology applications. This work evaluates the application of a graded hydrogen amorphous DLC film with applied over cylinder liner running surface. The methodology approach two coating thickness: 2.5 and 12.5 μm, deposited by the plasma assisted chemical vapor deposition process (PACVD) as the alternative solution for engine friction reduction and thus a reduction on brake specific fuel consumption (BSFC), and a improved wear resistance behavior of the piston rings and cylinder liner contact surfaces as well. By using baseline parts without inner DLC coating and DLC coated parts with similar running roughness surfaces, comparative reciprocating bench tests showed a tendency of coefficient of friction (COF) reduction in up to 19%. In a same trend, fired gasoline and diesel engine tests showed a friction mean effective pressure reduction (FMEP) in to 12% and small brake specific fuel consumption (BSFC) in up to 2.5% at low engine speed range respectively.