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A fundamental study of the correlations between ion energy, substrate temperature, and plasma density with hydrogen content, percent sp2 bonding, optical gap, and refractive index of hydrogenated amorphous carbon (a-C) films is presented. A strong dependency between the ion energy used during deposition and the film’s microstructure is shown. Moreover, it is revealed that the optical properties of the a-C films are controlled by the concentration and size of sp2 clusters in the film. Through N2 mixing in the source gas, room-temperature nitrogen doped polymeric-like a-C films were demonstrated for the first time. X-ray Photoelectron Spectroscopy revealed an increase in the Fermi level of these films with increased nitrogen content. A proof-of-concept a-C based transparent heat mirror (THM) was demonstrated. It was shown that a-C acts as an oxygen-free protective barrier and anti-reflective coating for Ag films in the THM, increasing the transmission in the visible region by 10-20%.

A fundamental study of the correlations between ion energy, substrate temperature, and plasma density with hydrogen content, percent sp2 bonding, optical gap, and refractive index of hydrogenated amorphous carbon (a-C) films is presented. A strong dependency between the ion energy used during deposition and the film’s microstructure is shown. Moreover, it is revealed that the optical properties of the a-C films are controlled by the concentration and size of sp2 clusters in the film. Through N2 mixing in the source gas, room-temperature nitrogen doped polymeric-like a-C films were demonstrated for the first time. X-ray Photoelectron Spectroscopy revealed an increase in the Fermi level of these films with increased nitrogen content. A proof-of-concept a-C based transparent heat mirror (THM) was demonstrated. It was shown that a-C acts as an oxygen-free protective barrier and anti-reflective coating for Ag films in the THM, increasing the transmission in the visible region by 10-20%.

No description available.

Semiconductor circuitry feature miniaturization continues in response to Moore 's Law pushing the limits of aluminum and forcing the transition to Cu due to its lower resistivity and electromigration. Copper diffuses into silicon dioxide under thermal and electrical stresses, requiring the use of barriers to inhibit diffusion, adding to the insulator thickness and delay time, or replacement of SiO2 with new insulator materials that can inhibit diffusion while enabling Cu wetting. This study proposes modified amorphous silicon carbon hydrogen (a-Si:C:H) films as possible diffusion barriers and replacements for SiO2 between metal levels, interlevel dielectric (ILD), or between metal lines (IMD), based upon the diffusion inhibition of previous a-Si:C:H species expected lower dielectric constants, acceptable thermal conductivity. Vinyltrimethylsilane (VTMS) precursor was condensed on a titanium substrate at 90 K and bombarded with electron beams to induce crosslinking and form polymerized a-Si:C:H films. Modifications of the films with hydroxyl and nitrogen was accomplished by dosing the condensed VTMS with water or ammonia before electron bombardment producing a-Si:C:H/OH and a-Si:C:H/N and a-Si:C:H/OH/N polymerized films in expectation of developing films that would inhibit copper diffusion and promote Cu adherence, wetting, on the film surface. X-ray Photoelectron Spectroscopy was used to characterize Cu metallization of these a-Si:C:H films. XPS revealed substantial Cu wetting of a-Si:C:H/OH and a-Si:C:H/OH/N films and some wetting of a-Si:C:H/N films, and similar Cu diffusion inhibition to 800 K by all of the a-:S:C:H films. These findings suggest the possible use of a-Si:C:H films as ILD and IMD materials, with the possibility of further tailoring a-Si:C:H films to meet future device requirements.

Orientador: Elidiane Cipriano Rangel / Banca: José Daniel Biasoli de Mello / Banca: Lúcia Vieira Santos / Banca: Roberto Martins de Souza / Banca: Steven Frederick Durrant / O programa de Pós graduação em Ciência e Tecnologia de Materiais, PosMat, tem carater institucional e integra as atividades de pesquisa em materiais de diversos campi da UNESP / Resumo: Neste trabalho foi investigado o efeito protetivo produzido pela deposição de um filme de Carbono Amorfo Hidrogenado (a-C;H) sobre a a superfície de uma ferramenta de conformação coberta com Nitreto de Titânio (TiN). A força necessária para conformar o material é relativamente alta, em torno de algumas toneladas. Os Filme de a-C;H foram aplicados com o objetivo de reduzir o atrito entre as superfícies da ferramentas de conformação e do material a ser conformado, podendo também gerar um ganho pela redução ou eliminação da lubrificação aplicada na fita na forma de fosfato de zinco ou de óleo de repuxo. As amostras foram construídas a partir do aço Ferramenta AISI M2, através dos processos de usinagem mole, tratamento térmico, retifica a lapidação com subseqûente aplicação da camada de TiN através do processo PVD (Physical Vapor Deposition). Também foi utilizado como subtrato discos de aço AISI M2 sem a camada TiN. As amostras foram inicialmente limpas em um processo de lavagem po ultra-som e subseqüentemente por uma procedimento a plasma. Os filmes foram depositados utilizando-se plasmas de baixas temperaturas de misturas de hidrocarbonetos e gases nobres. Foi utilizada a técnica híbrida de implantação iônica e deposição por imersão em plasmas (IIDIP), aplicando-se pulsos de alta tensão negativa à amostras para promover a deposição mediante a implantação iônica. Neste caso, o acetileno (C2H2) diluído em argônio foi utilizado como mistura precursora da formação do filme. Foi investigado o efeito da amplitude dos pulsos de polarização e da pressão dos gases do plasma nas propriedades dos filmes. As espectroscopias no infravermelho e Raman foram empregadas para se avaliar a composição química e a microestrutura dos filmes. Verificou-se nos espectros de infravermelho que... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this study, the protective effect by the application of a Hydrogenated Amorphous Carbon (a-C;H) film on the surface of a forming tool containing a titanium nitrite (TiN) layer was investigated. The required force to forming the material is relatively high, around a few tons. The a-C;H films were applied to reduce the friction coefficient between the surface of the forming tool and the raw material, also generating the possibility of the reduction or olimination of the lubrication applied to the tape surface in the form of zinc phosphate and drawing oil. The samples were produced from AISI M2 steel, using soft machining processes, heat treatment, grinding and polishing with subsequent application of the IiN layer by PVD (Physical Vapor Deposition). To permit comparison, AISI M2 steel without the TiN layer was also used as a substrate. The samples were initially cleaned in ultrasonic baths ans subsequently by plasma ablation. Low temperature plasmas of hydrocarbon and noble gas mixtures were used to deposit the films. The hibrid technique of plasma immersion ion implantation and deposition (PIIID) was used, applying high voltage negative pulses to the samples to promote deposition under ion bombardment. Acetylene (C2H2) diluted in argon was used as the gas mixture for film formation. The effect of the pulse magnitude and plasma pressure on the properties of the films, were studied. Infrared and Raman spectroscopies were employed to evaluate the film chemical composition and microstructure. Via the infrared spectra was observed a decrease in the C-H and O-H band intensities with increasing pulse magnitude, but a rise in the gas pressure caused the intensity of C-H bands to increase. Raman spectra of all the films exhibited strong photoluminescence, indicating a significant hydrogen content. The receptivity on the films to water... (Complete abstract click electronic access below) / Mestre

There is an every increasing need to develop more durable and higher performing coatings for use in a range of products including tools, devices and bio-implants. Nano-structured coatings either in the form of a nanocomposite or a multilayer is of considerable interest since they often exhibit outstanding properties. The objective of this thesis was to use advanced plasma synthesis methods to produce novel nano-structured coatings with enhanced properties. Coatings consisting of combinations of aluminum (Al), aluminum nitride (AlN) and amorphous carbon (a-C) were investigated. Cathodic vacuum arc deposition and unbalanced magnetron sputtering were used to prepare the coatings. By varying the deposition conditions such as substrate bias and temperature, coatings with a variety of microstructures were formed. A comprehensive range of analytical methods have been employed to investigate the stoichiometry and microstructure of the coatings. These include Transmission Electron Microscopy (TEM), Scanning Transmission Electron Microscopy (STEM), Electron Energy Loss Spectroscopy, Auger Electron Spectroscopy, X-ray diffraction and Raman spectroscopy. In addition to the investigation of microstructure, the physical properties of the coatings were measured. Residual stress has been recognized as an important property in the study of thin film coatings since it can greatly affect the quality of the coatings. For this reason, residual stress has been extensively studied here. Hardness measurements were performed using a nano indentation system, which is sensitive to the mechanical properties of thin films. This thesis undertook the most comprehensive investigation of the Al/AlN multilayer system. A major finding was the identification of the conditions under which layers or nanocomposite form in this system. A model was developed based on energetics and diffusion limited aggregation that is consistent with the experimental data. Multilayers of a-C and Al were also found to form nanocomposites. No hardness enhancement as a function of layer thickness or feature size was observed in either the Al/AlN or a-C/a-C systems. It was found that the most important factor which determines hardness is the intrinsic stress, with films of high compressive stress exhibiting the highest hardness. Nano-structured multilayers of alternating high and low density a-C were investigated. For a-C multilayers prepared using two levels of DC bias, evidence of ion beam induced damage was observed at the interfaces of both the low and high density layers. In addition, the structure of the high density (ta-C, known as tetrahedral amorphous carbon) layers was found to be largely unchanged by annealing. These results extend our understanding of how a-C form from energetic ion beams and confirms the thermal stability of ta-C in a multilayer. This thesis also presented the first attempt to synthesis a-C multilayered films with a continuously varying DC bias in sinusoidal pattern. The resulting films were shown to have a structurally graded interface between layers and verified that ion energy and stress are the most important factors which determine the structure of a-C films.

Novel carbon materials such as carbon onions, nanotubes and amorphous carbon (a-C) are technologically important due to their useful properties. Normally synthesised using plasmas, their growth mechanisms are not yet fully understood. For example, the growth mechanism of the high density phase of a-C, tetrahedral amorphous carbon (ta-C), has been a subject of debate ever since its discovery. The growth mechanism of carbon nanostructures such as carbon onions and nanotubes is also not well known. The aim of this thesis is two-fold. Firstly, to provide insight into the growth of carbon films, in particular, the driving force behind the formation of diamond-like bonding in a-C which leads to ta-C. Secondly, to investigate the growth of carbon onions and other sp2 bonded carbon nanostructures such as nanotubes. To achieve the first aim, carbon thin films were deposited using cathodic arc deposition at a range of ion energies, substrate temperatures and Ar background gas pressures. These films were characterised using electron microscopy techniques to examine their microstructure, density and sp3 content. It was found that the formation of the ta-C is due to a stress-induced transition whereby a critical stress of 6.5±1.5 GPa is needed to change the phase of the film from highly sp2 to highly sp3. Within this region, a preferentially oriented phase with graphitic sheets aligned perpendicular to the substrate surface was found. By investigating the role of elevated temperatures, the ion energy-temperature

Made available in DSpace on 2014-06-11T19:30:19Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-07-22Bitstream added on 2014-06-13T19:47:02Z : No. of bitstreams: 1 martinatti_jf_me_bauru.pdf: 2350679 bytes, checksum: a1dd65245ad53ffe2624e08e4b7e9587 (MD5) / Neste trabalho foi investigado o efeito protetivo produzido pela deposição de um filme de Carbono Amorfo Hidrogenado (a-C;H) sobre a a superfície de uma ferramenta de conformação coberta com Nitreto de Titânio (TiN). A força necessária para conformar o material é relativamente alta, em torno de algumas toneladas. Os Filme de a-C;H foram aplicados com o objetivo de reduzir o atrito entre as superfícies da ferramentas de conformação e do material a ser conformado, podendo também gerar um ganho pela redução ou eliminação da lubrificação aplicada na fita na forma de fosfato de zinco ou de óleo de repuxo. As amostras foram construídas a partir do aço Ferramenta AISI M2, através dos processos de usinagem mole, tratamento térmico, retifica a lapidação com subseqûente aplicação da camada de TiN através do processo PVD (Physical Vapor Deposition). Também foi utilizado como subtrato discos de aço AISI M2 sem a camada TiN. As amostras foram inicialmente limpas em um processo de lavagem po ultra-som e subseqüentemente por uma procedimento a plasma. Os filmes foram depositados utilizando-se plasmas de baixas temperaturas de misturas de hidrocarbonetos e gases nobres. Foi utilizada a técnica híbrida de implantação iônica e deposição por imersão em plasmas (IIDIP), aplicando-se pulsos de alta tensão negativa à amostras para promover a deposição mediante a implantação iônica. Neste caso, o acetileno (C2H2) diluído em argônio foi utilizado como mistura precursora da formação do filme. Foi investigado o efeito da amplitude dos pulsos de polarização e da pressão dos gases do plasma nas propriedades dos filmes. As espectroscopias no infravermelho e Raman foram empregadas para se avaliar a composição química e a microestrutura dos filmes. Verificou-se nos espectros de infravermelho que... / In this study, the protective effect by the application of a Hydrogenated Amorphous Carbon (a-C;H) film on the surface of a forming tool containing a titanium nitrite (TiN) layer was investigated. The required force to forming the material is relatively high, around a few tons. The a-C;H films were applied to reduce the friction coefficient between the surface of the forming tool and the raw material, also generating the possibility of the reduction or olimination of the lubrication applied to the tape surface in the form of zinc phosphate and drawing oil. The samples were produced from AISI M2 steel, using soft machining processes, heat treatment, grinding and polishing with subsequent application of the IiN layer by PVD (Physical Vapor Deposition). To permit comparison, AISI M2 steel without the TiN layer was also used as a substrate. The samples were initially cleaned in ultrasonic baths ans subsequently by plasma ablation. Low temperature plasmas of hydrocarbon and noble gas mixtures were used to deposit the films. The hibrid technique of plasma immersion ion implantation and deposition (PIIID) was used, applying high voltage negative pulses to the samples to promote deposition under ion bombardment. Acetylene (C2H2) diluted in argon was used as the gas mixture for film formation. The effect of the pulse magnitude and plasma pressure on the properties of the films, were studied. Infrared and Raman spectroscopies were employed to evaluate the film chemical composition and microstructure. Via the infrared spectra was observed a decrease in the C-H and O-H band intensities with increasing pulse magnitude, but a rise in the gas pressure caused the intensity of C-H bands to increase. Raman spectra of all the films exhibited strong photoluminescence, indicating a significant hydrogen content. The receptivity on the films to water... (Complete abstract click electronic access below)

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