O presente trabalho avalia a deposição de filmes de TiN com caráter decorativo sobre substratos de AISI 304. Os filmes produzidos neste estudo são compostos por uma intercamada de Ti entre o substrato e o filme de TiN, produzindo assim um sistema substrato/Ti/TiN. Foram estudados os efeitos da tensão de polarização aplicada ao substrato durante a deposição da intercamada de Ti e a influência da temperatura de deposição do filme, com variação de temperatura entre 25°C e 200°C. Os filmes foram depositados através da tecnologia PVD por arco catódico em um processo de deposição reativa em escala industrial, partindo de cátodos de Ti e gases argônio e nitrogênio. Os filmes tiveram sua composição química analisada através da técnica de espectroscopia por descarga luminescente, as fases cristalinas foram determinadas por difração de raios-X e a microestrutura e espessura das camadas foram avaliadas através de microscopia eletrônica de varredura (MEV). Também foi medida a dureza em nanoescala dos filmes e, como forma de complementar os resultados obtidos, a carga crítica para início de deformação plástica dos filmes foi medida através de ensaios de esclerometria linear. Os resultados mostraram que ambos os parâmetros de processos analisados exercem influência significativa nas propriedades e características dos filmes formados, principalmente no teor de contaminação por oxigênio presente nos filmes e na carga crítica para deformação plástica. Além disso, também se observou que o filme depositado à 200°C apresenta uma mudança significativa na sua orientação cristalográfica e composição química em comparação com os depositados em temperaturas inferiores. Como resultado do trabalho, pôde-se determinar os parâmetros ideais para a deposição de filmes finos de TiN decorativos, possibilitando o desenvolvimento e a aplicação da tecnologia em escala industrial. / Conselho Nacional de Desenvolvimento Científico e Tecnológico.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior. / This work studies the deposition of titanium nitride (TiN) thin films on stainless steel AISI 304 substrate for decorative applications. The films studied here are composed of a layer of Ti working as an interlayer between the substrate and the TiN thin film, creating a system substrate/Ti/TiN. The BIAS applied on the substrate during the deposition of the Ti interlayer and the deposition temperature of the films between 25°C and 200°C were studied. The films were deposited by a PVD cathodic arc evaporation technique in a reactive deposition process, working with Ti cathodes and argon and nitrogen as gases. The equipment utilized for these depositions was an industrial PVD coating equipment. The chemical composition of the TiN films was analyzed by glow-discharge optical emission spectroscopy technique (GD-OES) and the crystalline structure by X-ray diffraction (XRD) and the microstructure and thickness by scanning electron microscopy (SEM). Also, the hardness at the nanoscale of the films was measured and scratch analyses were made to determine the critical load for the beginning of plastic deformation of the films. The results show that both analyzed process parameters significantly affect the properties and characteristics of the films, especially on the oxygen contamination content and the critical load for plastic deformation. Furthermore, it was also observed that the film deposited at 200°C presents a significant change on its crystallographic orientation and chemical composition compared with those deposited at lower temperatures. As a result of this research, it was possible to determine the optimized process conditions for the deposition of TiN thin films for decorative purposes, enabling the development and application of this technology in industrial scale.

Orientador: Jacobus Willibrordus Swart / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação / Made available in DSpace on 2018-08-24T14:49:15Z (GMT). No. of bitstreams: 1 Garcia_AlissonSoares_M.pdf: 5063750 bytes, checksum: 2502df6540499f8d119aa5b993966ec5 (MD5) Previous issue date: 2014 / Resumo: Filmes ultrafinos (espessuras inferiores a 20 nm) de nitreto de titânio (TiN) para serem usados como eletrodos de porta para tecnologia CMOS (Complementary Metal Oxide Semicon-duc-tor) foram obtidos. Estes filmes ultrafinos foram obtidos através da evaporação por feixe de elétrons de camadas ultrafinas (de 1 ou 2 nm de espessura) de titânio (Ti) com posterior ni-tretação por plasma ECR (Electron Cyclotron Resonance) de nitrogênio (N2). Após a deposição e nitretação do titânio, a fim de evitar a oxidação dos filmes, no mesmo reator ECR da nitreta-ção, executou-se a deposição CVD (Chemical Vapor Deposition) de filmes de a-Si:H (silício amorfo hidrogenado) usando plasma de SiH4/Ar. Estes filmes de a-Si:H foram implantados com fósforo (P+) e recozidos por processamento térmico rápido para torná-los dopados n+ e policris-talinos. Assim, foram formados eletrodos de porta (Metal Gate) MOS com estruturas Poli-Si n+/TiN e esta dissertação apresenta as seguintes contribuições científicas: ¿ Obtenção de eletrodos de porta Poli-Si n+/TiN que suportam processos RTA em alta tempe-ratura de 1000 ºC. Esta característica foi observada por análises Raman, que identificaram picos relativos ao TiN dos modos TA (~195 cm-1) e LA (~315 cm-1) e ao Si cristalino (~ 521 cm-1); ¿ Obtenção de filmes ultrafinos de TiN, com espessuras menores que 20 nm e contínuos. Qua-tro amostras apresentaram espessuras menores que 10 nm, que é um valor desejado para ob-ter eletrodos de porta MOS que caibam nos dispositivos fabricados para nós tecnológicos com dimensões menores que 22 nm. Esta característica foi identificada por imagens SEM (microscopia eletrônica de varredura); ¿ Obtenção de eletrodos de porta Poli-Si n+/TiN do tipo midgap, pois os valores de VFB estão entre -0,31 V e -0,48 V. Estas características foram extraídas de medidas de Capacitância¿Tensão (C-V); Portanto, eletrodos de Poli-Si n+/TiN do tipo midgap, com espessuras menores que 10 nm, resistentes a processos de alta temperatura e que podem ser usados em dispositivos fabrica-dos para nós tecnológicos com dimensões menores que 22 nm, foram obtidos / Abstract: Ultrathin films (thickness of less than 20 nm) of titanium nitride (TiN) to be used as gate electrodes for CMOS (Complementary Metal Oxide Semiconductor) technology were obtained. These ultrathin films were obtained by electron beam evaporation of ultrathin layers (1 or 2 nm thick) of titanium (Ti) followed by ECR (Electron Cyclotron Resonance) plasma nitriding of nitrogen (N2). After deposition and nitriding of the titanium, in order to prevent oxidation of the films, in the same nitriding ECR reactor, a-Si:H (hydrogenated amorphous silicon) films were deposited by CVD (Chemical Vapor Deposition) using SiH4/Ar plasma. These films of a-Si:H were implanted with phosphorus (P+) and annealed by rapid thermal annealing to turn them n+ dopped and polycrystalline. Thus, MOS metal gate electrodes were formed with Poly-Si n+/TiN structures and this dissertation presents the following scientific contributions: ¿ Gate electrodes of Poly-Si n+/TiN that support RTA processes in high temperature of 1000 ºC were obtained. This characteristic was observed by Raman analysis, that identified peaks associated to TiN at TA mode (~195 cm-1) and LA mode (~315 cm-1), and related to the crys-talline Si at (~ 521 cm-1); ¿ Ultrathin films of TiN, less than 20 nm thick and continuous, were obtained. Four samples were less than 10 nm thick, which represents a thickness that is desirable to obtain MOS gate electrodes that fit devices manufactured for technological nodes with dimensions smaller than 22 nm. This feature was identified by SEM images (Scanning Electron Micros-copy); ¿ Midgap metal gate electrodes Poly-Si n+/TiN were obtained, as VFB values are between -0.31 V and -0.48 V. These features were extracted from measurements of capacitance-voltage (C-V); Therefore, midgap electrodes of Poly-Si n+/TiN, less than 10 nm thick, resistant to high temperature processes and that can be used in devices manufactured for technological nodes with dimensions smaller than 22 nm were obtained / Mestrado / Eletrônica, Microeletrônica e Optoeletrônica / Mestre em Engenharia Elétrica

Orientador: Fernando Alvarez / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-19T11:28:04Z (GMT). No. of bitstreams: 1 MoralesCorredor_Monica_M.pdf: 2275286 bytes, checksum: d91a17b2e37d2c4976aa37dc6d5d5026 (MD5) Previous issue date: 2011 / Resumo: Dado o interesse nas propriedades e aplicações dos nanotubos de carbono devidas às suas características morfológicas, este trabalho tem como objetivo principal o estudo da influência do substrato no crescimento dos nanotubos de carbono. Com este objetivo em mente foram preparados filmes de nitreto de titânio, com o intuito de ser usados como suporte para a deposição dos nanotubos de carbono. Os nanotubos foram crescidos por decomposição térmica de acetileno, usando partículas de níquel como precursor catalisador. Os filmes finos não estequiométricos de TiNx foram depositados sobre silício cristalino utilizando a técnica de Deposição por Feixe de Íons (IBD). Análise composicional dos substratos mostrou a presença de Ti, N e O. Distintas concentrações destes elementos permitiram a variação na estrutura e dureza dos substratos. Nos filmes bem caracterizados, partículas de níquel e nanotubos de carbono foram crescidos sequencialmente. Os carpetes de nanotubos obtidos no substrato mostraram diferentes densidades populacionais (nanotubos por unidade de área) e diâmetro. Este comportamento está associado com a presença do oxigênio, elemento que inibe o fenômeno conhecido como Ostwald ripening. O efeito de Ostwald ripening55 causa a coalescência do níquel formando partículas maiores a expensas das menores, um estado final mais favoravelmente energético. A presença do oxigênio impede a difusão do níquel na superfície, interferindo no processo de coalescência. Consequentemente, uma grande densidade de partículas catalisadoras por unidade de área é mantida levando a maior densidade de nanotubos assim como modificações morfológicas das nanoestruturas. Portanto, estes resultados indicaram que filmes finos de TiNx, além de atuar como barreira difusora entre as partículas catalisadoras e o substrato de silício, também influencia a cinética dos nanotubos de carbono / Abstract: Given the increasing interest in the properties and applications of carbon nanotubes due to their morphological characteristics, this work has as main objective the study of the influence of substrate on the growth properties of carbon nanotubes. With this main goal in mind were first prepared titanium nitride films in order to be used as substrate support for carbon nanotubes deposition. The nanotubes were growth by thermal decomposition of acetylene using nickel particles as catalyst precursors. The thin films non-stoichiometric TiNx were deposited on crystalline silicon by ion beam deposition (IBD) technique. Compositional analysis of the substrates showed the presence of Ti, N and O. The different concentrations of these elements led to the variation in the structure and hardness of the coating. On the well characterized substrate coating, nickel particles and nanotubes growth were sequentially deposited. The quite well organized carpets of nanotubes obtained on the substrate show different population density (nanotubes per unit of area) and diameter. This behavior is associated with the presence of oxygen, element inhibiting the phenomenon known as ¿Ostwald ripening?. The Ostwald ripening effect55 causes the coalescence of nickel by forming bigger nickel particles at expenses of smaller ones, a more energetic favorable final state. The presence of oxygen prevents the nickel surface diffusion and thus interfering on the coalescence process. Consequently, a larger density of relatively small catalyst nickel islands per unit of area is preserved leading to higher nanotubes density as well as morphology modifications of the nano structures. Therefore, these results indicate that thin films of TiNx, besides acting as diffusion barrier between the catalyst particles and the silicon substrate also influences the kinetics of growth of carbon nanotubes / Mestrado / Mestra em Física

The behaviour of mould fluxes used in continuous casting of two Ti-stabilised stainless steels was investigated in terms of the level of titanium pick-up by the flux and the effect of this absorption of titanium on the viscosity of the fluxes. The two fluxes considered are respectively used for the casting of a ferritic steel (type 409) and an austenitic steel (type 321). Concerning the titanium pick-up (expressed as Ti02), the Ti02 content of the flux stabilised at about 3-4% for the mould flux of the ferritic steel and at about 6% for the mould flux of the austenitic steel after 20 minutes of casting. At the same time due to the reduction of Si02 in the molten flux by TiN and Ti in the steel the basicity of the mould flux of the ferritic steel increased from 0.8 to 0.9 while it increased from 0.95 to 1.2 for the mould flux of the austenitic steel. The SEM/EDS analysis of the sampled flux during casting showed only some spherical metallic droplets in the case of the mould flux of the ferritic steel but for the mould flux of the austenitic steel apart from the metallic droplets, some precipitates rich in Ca, Ti and O were identified in the glassy phases. Rotational viscometry carried out on the two fluxes showed that there is a decrease in the viscosity of the fluxes with the absorption of Ti02, Ti2O3 and Ti3O5 in the range of 2 to 10 wt%, for temperatures from 1400°C to 1200°C. The effect of Ti02 and Ti2O3 has been tested with the mould flux of the austenitic steel at a basicity of 1.2 to match the basicity which arises during casting. For temperatures of 12500C and below, the apparent viscosity of the flux increased markedly with the absorption of 10 % of Ti02 or Ti2O3. In both cases precipitation of perovskite (Ca2 Ti2O6 or Ca2 Ti2O5) was found to be responsible for the increase of the apparent viscosity of the flux of the austenitic steel. / Dissertation (M Eng (Metallurgical Engineering))--University of Pretoria, 2006. / Materials Science and Metallurgical Engineering / unrestricted

The Thesis described within the scope of the Master Program is focused on cermets, which belong among cutting materials. The introductory portion of the Thesis presents the characteristics of cermets from the perspective of production, physical-mechanical characteristics, marking and usage in cutting. The core portion of the Thesis focuses on the role of cermets in the category of leading world producers of tools and instrumental materials, cutting evaluation, and the suggested working conditions of cermets in lathing operations. The working conditions are prepared for steel and cast iron. The conclusion of the Thesis focuses on a technical-economical analysis of cermets.

The Council for Scientific and Industrial Research (CSIR) in South Africa is developing a process to produce titanium tetrachloride from a low-grade material such as ilmenite. Titanium tetrachloride can then be used as feed material for titanium metal or pigment-grade titanium dioxide production. Titanium tetrachloride is commercially produced by chlorinating synthetic rutile (<92% TiO2) or titanium dioxide slag (<85% TiO2) at ~900 ˚C. A drawback of chlorination at this temperature is that any constituents other than TiO2 will end up as hazardous waste material. A characteristic step in the CSIR’s proposed process is to nitride titanium dioxide contained in the feed material before it is sent for chlorination. The chlorination of the resulting titanium nitride is achieved at a much lower temperature (~200 ˚C) than that of the existing titanium dioxide chlorination reaction. An added advantage of the low-temperature chlorination reaction is that chlorine is selective mostly towards titanium nitride and metallic iron, which means that any other constituents present are not likely to react with the chlorine. The result is reduced chlorine consumption and less hazardous waste produced. The nitrided ilmenite must, however, be upgraded by removing all iron before it can be sent for chlorination. Commercial ilmenite upgrading processes, called synthetic rutile production, also require the removal of iron and other transition metals before chlorination. A literature review of existing ilmenite upgrading processes revealed four possible process options that could remove iron from nitrided ilmenite. Two of these process options, the Becher and Austpac ERMS SR processes, are proven process routes. The other two are novel ideas – one to passivate iron contained in the nitrided ilmenite against chlorination and the other to use ammonium chloride (as used in the Becher process) as a stoichiometric reactant to produce a ferrous chloride solution. A preliminary experimental evaluation of these process options indicated that the Austpac ERMS SR process is the most viable option for removing iron from nitrided ilmenite. The Austpac ERMS SR process was therefore selected as a template for further process development. A detailed Austpac ERMS SR process review found that two process units in the Austpac ERMS SR process could be used in a process that separates iron from nitrided ilmenite. These are the Enhanced Acid Regeneration System and the Direct Reduced Iron process units. The review also concluded that another leach unit would have to be developed. It was therefore necessary to further investigate the dissolution of nitrided ilmenite in hydrochloric acid. A detailed experimental evaluation of nitrided ilmenite dissolution in hydrochloric acid found that hydrochloric acid could be used as the lixiviant to selectively remove iron from nitrided ilmenite. The dissolution of metallic iron in 90 ˚C hydrochloric acid reached levels of at least 96% after only 60 minutes. An average “combined resistance” rate law was found that could be used to describe this dissolution reaction. The observed activation energy and Arrhenius pre-exponential factor were found to be equal to 9.45 kJ.mol-1 and 30.8 s-1 respectively. The Austpac ERMS SR process review and experimental results described above were then combined and used to propose a process that could be employed to remove iron from nitrided ilmenite. The proposed process was modelled using the Flowsheet Simulation module in HSC Chemistry 7.0 / Dissertation (MEng (Chemical Engineering))--University of Pretoria, 2010. / Chemical Engineering / MEng (Chemical Engineering) / unrestricted

Due to recent advances in computational hardware and code accessibility, state-of-the-art calculations are currently employed to investigate materials at the nanoscale with varying levels of accuracy. As such, this dissertation highlights a series of materials ranging from one-dimensional wires, to reactive surfaces, to bulk crystals. Initial characterizations for all considered materials are carried out using density functional theory where additional approximations are utilized to obtain more complex quantities. For Millon's salt, first-principles calculations confirm a quasi-one-dimensional description where the metallic backbone influences electronic properties while hydrogen-bonding between ligands results in structural stability. We show that valence band dispersion can be controlled via strain or ligand substitution, pointing to tunable hole-carrier possibilities. Optical properties are also addressed with respect to experimental and theoretical findings. Our focus then shifts to titanium dioxide, a popular and promising photocatalyst. Specific nitrogen doping on the anatase (001) surface introduces intra gap states accessible for photoactivation in the visible. The additional presence of a fluorine dopant or oxygen vacancy enhances the density of these particular states available for transitions. Titanium dioxide also has experimentally displayed involvement in carbon dioxide reduction mechanisms. From first-principles calculations, anatase (001) surfaces containing an oxygen vacancy exhibit an increased potential for carbon dioxide to undergo reduction due to an exposed titanium atom in comparison to the pristine case. Other binding configurations on both types of surfaces suggest the existence of alternative conversion pathways. As a recently realized plasmonic material, titanium nitride proves advantageous in relation to more traditional materials, e.g., gold or silver; one of the main factors stems from its tunable permittivity. We investigate this aspect by theoretically incorporating defects into titanium nitride, which introduces a systematic approach to control plasmonic activity over a broad frequency range. Finally, lifetimes of hot-electrons, originating from plasmonic decay, for instance, possess finite lifetimes in titanium nitride, as well as in other similar materials, that are described by electron-electron interactions through the electron self-energy. Average lifetimes resemble those obtained with a free electron gas model while details of the band structure influence lifetime behavior. Calculations exploring factors affecting these lifetimes are presented.

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No description available.

In the past few years, the demands for high speed semiconductor integrated circuits have warranted new techniques in their fabrication process which will meet the ever-shrinking dimensions. The gaseous plasma assisted etching is one of these revolutionary processes. However, the plasma and the etch process are very complex in nature. It has been very difficult to understand various species present in the plasma and their role in the etch reaction. In addition, the submicron geometries also require interconnect materials which will satisfy the necessary properties such as thermal stability and low electrical resistance. Titanium (Ti) and titanium nitride (TiN) are widely used as barriers between aluminum (Al) and silicon (Si) to prevent the destructive intermixing of these two materials. The process of patterning of the interconnect containing Ti and TiN along with Al has been a challenge to the semiconductor process engineers. Therefore, complete characterization of the plasma etch process of Ti and TiN films and development of mathematical models to represent the responses such as the etch rate and uniformity is necessary for a good understanding of the etching process. A robust and well controlled metal etch process usually results in good die yield per wafer and hence can translate into higher profits for the semiconductor manufacturer. The objective of this dissertation is to characterize the plasma etch processes of Ti and TiN films in chlorine containing plasmas such as BCl₃ and Cl₂/N₂ and to develop mathematical models for the etch processes using statistical experimental design and analysis technique known as Response Surface Methodology (RSM). In this work, classical experiments are conducted on the plasma etch process of Ti and TiN films by varying the process parameters, such as gas flow, radio frequency (RF) power, reaction pressure, and temperature, one parameter at a time, while maintaining the other parameters constant. The variation in the etch rate with the change in the process parameter of the film is studied and the results were explained in terms of the concepts of plasma. These experiments, while providing very good understanding of the main effects of the parameters, yield little or no information on the higher order effects or interaction between the process parameters. Therefore, modern experimental design and analysis techniques using computerized statistical methods need to be employed for developing mathematical models for these complex plasma etch processes. The second part of this dissertation concentrates on the Design and Analysis of Experiments using Response Surface Methodology (RSM) and development of models for the etch rate and the etch uniformity of the Ti and TiN films in chlorine-containing plasmas such as Cl₂/N₂ and Cl₂/N₂/BCl₃. A complete characterization of the plasma etch process of Ti and TiN films is achieved with the RSM technique and a well fitting and statistically significant models have been developed for the process responses, such as the etch rate and the etch uniformity. These models also provide a means for quantitative comparison of main effects, which are also known as first order effects, second order effects and two factor interactions. The models, thus developed, can be effectively used for an etch process optimization, prediction of the responses without actually conducting the experiments, and the determination of process window. This dissertation work has achieved a finite study of the plasma etch process of Ti and TiN films. There is tremendous potential and scope for further research in this area, limited only by the available resources for wafer processing. A few of the possibilities for further research is discussed in the next few sentences. The optimized process derived from the RSM technique needs to be implemented in the actual production process of the semiconductor ICs and its effects on the wafer topography, etch residue and the resulting die yield have to be studied. More research studies are needed to examine the effect of process parameters such as temperature, the size and shape of the etch chamber, the quality of the film being etched, among other parameters. It is worth emphasizing in this respect that this dissertation marks beginning of research work into the ever-increasing complexities of gas plasma. / Ph. D.