Innerhalb der Arbeit wurden mit Hilfe eines DC-Glimmplasmas im Vakuumbereich zwischen 100 und 400 Pa auf kathodisch geschalteten, metallischen Substraten mittels silicium- und bororganischen Verbindungen Schichten abgeschieden. Unter den gewählten Bedingungen war eine Abscheidung von amorphen Hartstoffschichten bei niedriger Substrattemperatur (ca. 200–450 °C), geringem apparativen Aufwand und hohen Abscheideraten (bis zu 2.5 µm min-1) möglich. Anhand der Abscheidung mit Hexamethyldisilazan (HMDSN) und unterschiedlichen Arbeitsgasen (Wasserstoff, Argon, Stickstoff, Ammoniak, Sauerstoff, bzw. ohne Arbeitsgas) wurde der grundlegende Einfluss der Beschichtungsparameter (Plasmaleistung, Prozessdruck, Precursorfluss und Substratgröße) auf unterschiedliche Schichteigenschaften (Mikrostruktur, Ele-mentgehalt, optische und mechanische Eigenschaften) sowie auf die Abscheiderate untersucht und diskutiert. Zudem wurde das Abscheideverhalten von zwei weiteren siliciumorganischen, zwei borsiliciumorganischen und einer bororganischen Verbindung untersucht. Um Aussagen zum Wachstumsmechanismus treffen zu können, wurden mit Hilfe der differentiell gepumpten Massenspektroskopie quantitative Untersuchungen an den Reaktionsprodukten durchgeführt. Weiterhin wurde ein Beitrag zur Anwendung der IR-Spektroskopie in Reflexion zur Charakterisierung der auf nichttransparenten Substraten abgeschiedenen Schichten geleistet. Mittels einer numerischen Simulation der Spektren konnte die Schichtdicke, die Brechzahl sowie das Spektrum der Absorptionskonstante zur quantitativen, strukturellen Charakterisierung der abgeschiedenen Schichten ermittelt werden.

Amorphous, hydrogenated carbon films (a-C:H) have been prepared in a PECVD device from methane and ethine as the source gases.The aim was to deposit films at high growth rates while keeping high hardness (25 ± 3 GPa). Hardness, hydrogen content and surface roughness were investigated dependent on the process conditions. Further investigation showed, that the mechanical properties of the a-C:H films are determined by the energy of the ions and the ratio between the film forming ion and the film forming neutral fluxes. On the basis of the collected data the optimal deposition conditions were determined and suggestions for further improvement of the deposition were made. / Amorphe, wasserstoffhaltige Kohlenstoffschichten (a-C:H) wurden mittels PECVD-Verfahren abgeschieden, wobei Methan und Ethin als Quellgase verwendet wurde. Ziel war dabei die Abscheidung der Schichten mit hohen Aufwachsraten unter Beibehaltung hoher Härten (25 ± 3 GPa). Härte, Wasserstoffgehalt und Oberflächenrauhigkeit der Schichten wurden in Abhängigkeit von den Prozeßbedingungen untersucht. Weitere Untersuchungen zeigten, daß die mechanischen Eigenschaften der a-C:H Schichten von der Energie der Ionen und dem Verhältnis der schichtbildenden Ionen- und Neutralteilchenflüsse bestimmt werden. Auf der Grundlage der gewonnenen Daten können die optimalen Abscheidebedingungen festgelegt, und Vorschläge zur weiteren Verbesserung der Schichtabscheidung gemacht werden.

Die vorliegende Dissertation befasst sich mit der Bewertung eines Mehrfachschichtmodells für Permeationsbarrieren auf Basis einer detaillierten Charakterisierung der zugrunde liegenden Einzelschichten. Diese sind reaktiv gesputterte Oxidschichten als Barriereschicht und mittels Magnetron-PECVD abgeschiedene siliziumhaltige Plasmapolymerschichten zur Verwendung als Zwischenschicht. Zunächst werden die verschiedenen gesputterten Oxidschichten charakterisiert und verglichen. Die untersuchten Materialien sind Zinkoxid, Siliziumoxid, Zink-Zinn-Oxid, Aluminiumoxid und Titanoxid. Die wirkenden Permeationsmechanismen und die Ursachen für teils deutliche Unterschiede zwischen verschiedenen Materialien werden diskutiert. Während die Sauerstoffpermeation immer durch Punktdefekte in den Schichten bestimmt wird, muss bei der Wasserdampfpermeation von weiteren Permeationsmechanismen ausgegangen werden. Am Beispiel des Zink-Zinn-Oxids und des Aluminiumoxids wird anschließend die Abhängigkeit der Permeationseigenschaften von wesentlichen Prozessparametern wie Sputterleistung, Prozessdruck oder reaktiver Arbeitspunkt untersucht. Im zweiten Teil der Arbeit werden die Plasmapolymerschichten hinsichtlich ihrer Struktur- und Permeationseigenschaften charakterisiert und mit gesputtertem Siliziumoxid verglichen. Die Abhängigkeit der Permeationseigenschaften vom Kohlenstoffgehalt in den Schichten wird untersucht. Anhand der gewonnenen Ergebnisse werden abschließend sowohl die Sputterschichten als auch die mittels Magnetron-PECVD abgeschiedenen Schichten hinsichtlich ihrer Eignung für ein Barrieremehrfachschichtsystem bewertet. / The aim of this PhD-thesis is to evaluate a concept for a multilayer permeation barrier by a detailed characterization of the different constituent of the layer stack. The multilayer concept is based on reactively sputtered permeation barrier layers and an interlayer that is deposited by using a magnetron based plasma enhanced chemical vapor deposition (Magnetron-PECVD) process. In the first part of this thesis, different sputtered oxide layers are characterized and compared regarding their structural and surface properties as well as their water vapor and oxygen permeability. These oxide layers include the materials zinc oxide, silicon oxide, zinc-tin oxide, aluminum oxide and titanium oxide. The permeation mechanisms and reasons for significant differences in the water vapor and oxygen transmission rates in the different materials are evaluated and discussed. Oxygen permeation thereby is always dominated by defects in the layers. In contrast to that, additional permeation mechanisms can be assumed for water vapor permeation. The dependence of the gas permeation on sputter process parameters like plasma power, process pressure and reactive sputtering mode is evaluated for zinc-tin oxide and aluminum oxide layers. In the second part of this thesis, plasma polymer layers that are deposited using the Magnetron-PECVD process are characterized regarding their structure and surface roughness. Their water vapor and oxygen permeability is compared to the permeation through reactively sputtered silicon oxide layers. The dependence of the gas permeation on the atomic composition, in particular on the carbon concentration, is evaluated. Finally, both the sputtered oxide layers and the Magnetron-PECVD plasma polymer layers are evaluated regarding their usability in a multilayer stack for high permeation barrier applications.

The significance of the radioxenon memory effect in the context of the International Monitoring System of the Comprehensive Nuclear-Test-Ban Treaty is introduced as motivation for the project. Existing work regarding xenon memory effect reduction and thin film diffusion barriers is surveyed. Experimental techniques for radioxenon production and exposure, as well as for thin film deposition on plastic by plasma enhanced chemical vapor deposition (PECVD), are detailed. A deposition rate of 76.5 nm min⁻¹ of SiO₂ is measured for specific PECVD parameters. Relative activity calculations show agreement within 5% between identically exposed samples counted on parallel detectors. Memory effect reductions of up to 59±1.8% for 900 nm SiO₂ films produced by plasma enhanced chemical vapor deposition and of up to 77±3.7% for 50 nm Al₂O₃ films produced by atomic layer deposition are shown. Future work is suggested for production of more effective diffusion barriers and expansion to testing in operational monitoring stations. / text

This study is focused on the fabrication of plasma polymerized ultrathin films and the elucidation of their unique properties with an emphasis on the solvent-less, dry polymerization process to introduce post-deposition functionality, robustness, and shape preservation. Two major classes of materials are the subject of this study: biological monomers, specifically the amino acids tyrosine and histidine and synthetic organic and inorganic monomers including acrylonitrile, 2-hydroxyethyl methacrylate, N-isopropylacrylamide, titanium isopropoxide and ferrocene. The unique chemical and physical properties of highly cross-linked ultrathin plasma polymerized amino acid and synthetic polymer films are demonstrated along with their functional response and robustness on both planar and complex surface structures. The work emphasizes the facile ability of plasma polymerization to create unique, tailored ultrathin coatings. Chemical functionality retention (OH, NH₂) of the tyrosine and histidine amino acids is demonstrated by the subsequent mineralization of gold or titania nanoparticles on the plasma polymerized ultrathin films using a wet chemical approach. Inorganic nanoparticle mineralization is further investigated as a method to modify the optical properties of composite nanocoatings. Plasma co-polymerization of tyrosine and synthetic monomers is used to create nanocomposite coatings with unique surface functionalities, responsive behavior, optical characteristics and a high level of integration between monomers. The fabrication of novel plasma polymerized Janus microspheres, micropatterned substrates and free-standing films also demonstrate numerous plasma polymerized materials which exhibit unique structural properties. Overall, facile plasma polymerization of novel, functional ultrathin films and complex topological coatings having potential biocompatible and optical applications is established.

Vertically aligned Multiwalled Carbon Nanotubes (MWCNTs) were grown in the pores of Anodized Aluminum Oxide (AAO) templates and investigated for resistive sensor applications. High Sensitivity of 23% to low concentration (100 ppm) of ammonia was observed. An equivalent circuit model was developed to understand the current flow path in the resistive sensor. This helped us in achieving high sensitivities through amorphous carbon (a-C) layer thickness tailoring by employing post-growth processing techniques like plasma etching. A simulation model in MATLAB was developed to calculate the device resistance and the change in the sensitivity as a function of device parameters. The steady state response and transient response of the model to the number of ammonia molecules and its adsorption rate were studied. Effects of oxygen plasma, argon plasma and water plasma etch on thinning of the a-C layer were studied. In order to enhance the sensitivity, the top and bottom a-C layers were replaced by a more conductive metal layer. This also helped in understanding the current flow in the device and in the estimation of the resistivity of the a-C layer.

Compared to wafer based solar cells, thin film solar cells greatly reduce material cost and thermal budget due to low temperature process. Monolithically manufacturing allows large area fabrication and continuous processing. In this work, several photovoltaic thin films have been developed by rf-PECVD including a-Si:H and μc-Si, both intrinsic and doped on Corning 4 inch glass substrate at low temperature. The conductivity of n type and p type μc-Si at 180ºC was 17S/cm and 7.1E-2S/cm, respectively. B dopants either in a-Si:H or μc-Si films require higher plasma power to get active doping. The B2H6-to-SiH4 flow ratio for p type μc-Si lies from 0.01 to 0.025. Chamber conditions have critical effect on film quality. Repeatable and superior results require a well-established cleaning passivation procedure. Moreover, μc-Si films have been deposited from pure silane on glass substrate by modified rf-ICP-CVD. The deposition rate has been dramatically increased to 5Å/s due to little H2 dilution with crystalline fraction was around 69%, and 6.2Å/s with crystalline fraction 45%. Microstructure started to form at 150ºC with a thin incubation layer on the glass substrate, and became fully dense conical conglomerates around 300nm where conductivity and crystallinity saturated. Additionally, a-SiGe:H films have been developed by modified rf-ICP-CVD. The optical band gaps have been varied from 1.25 to 1.63eV by changing SiH4-to-GeH4 ratio. Also high temperature resulted in low bandgap. Cross-section TEM showed some microcrystllites appeared near interface region. Heterojunction solar cells on p type c-Si wafer have been fabricated using films developed in this thesis. Interference fringes in EQE disappeared on either textured substrate or cells with lift-off contacts. Maximum EQE was 87% around 700nm. I-V curves have also been studied where the interesting kink suggests a counter-diode has formed between emitter region and contacts.

New Generation Lithographic (NGL) techniques have been recently investigated in order to overcome the limitations of the long-used UV lithography. Several techniques have been proposed during the last decades, but the continued improvement of UV lithography rendered them useful only for a limited number of applications. More recently, nanoimprint lithography (NIL), invented in the nineties, has been considered as the new NGL due to its extreme simplicity and high resolution. Thermal NIL consists in the deformation of a thermoplastic under pressure and temperature by a nanostructured mold, while UV-NIL consists in the polymerization by UV light of a monomer at room temperature and under a lower pressure than Thermal NIL. One of the main problems of this technique is mold-polymer separation after the process. This problem is especially important for UV-NIL, because the working treatments for Thermal NIL degrade with UV light. In order to assess this problem, thin diamond-like amorphous carbon films (DLC) have been proposed as an alternative to existing treatments for their low chemical reactivity and the possibility to incorporate other chemical elements to further reduce their surface energy. Amorphous carbon exists in different forms, depending on how it is grown. Its mechanical properties range from polymer or graphite-like to almost as resistant as diamond. Besides the excellent mechanical properties of DLC (high hardness, elasticity and wear resistance, and low dry friction), amorphous carbon has also been found useful in applications requiring inert and/or biocompatible surfaces. The project DPI2007-61349 of the Science and Innovation Department of Spain, named “Amorphous carbon molds for micro and nanoimprint of polymeric surfaces”, aims to study the effect of the incorporation of different elements in DLC films for the improvement of NIL molds. This thesis has focused on a series of objectives of this project: - Design and construction of a very high vacuum reactor for deposition processes and ionic etch - Incorporation of fluorine to amorphous carbon films and subseqüent characterization by different surface, mechanical and tribological techniques, as well as spectroscopy for the characterization of the plasma used for the process. - Set up and optimization of a deep ion etch technique with ion beam for the production of molds. - The use of different lithographic techniques oriented to the production in large scale of nanometric patterns. - The exploration of mold coating to increase its durability and antisticking properties in nanoimprint processes. The incorporation of fluorine in DLC films has demonstrated to be useful in the improvement of the properties of NIL molds, because it avoids the use of the current surface treatments, which in addition to being less durable, can react with polymers in presence of UV light. In this thesis, the influence of fluorine incorporation in the films has been studied. Fluorinated amorphous carbon films have been deposited by pulsed-DC plasma enhanced chemical vapor deposition, by progressively replacing methane by trifluoromethane. The experimental device used for deposition has been designed and built to allow a number of multiple processes in the same reactor. The results of the study demonstrate the feasibility of this technique, of easy industrial implementation, for the deposition of this type of coatings. The characterization of both the active species in the plasma and the groups incorporated into the deposited films has helped to understand the process of fluorine incorporation, as well as the change in the surface properties that it entails. / La dificultad de extender el uso de la litografía de luz ultravioleta (UV) a los cada vez más estrictos requisitos de resolución, llevaron desde hace ya un par de décadas, a plantearse la necesidad de buscar técnicas litográficas llamadas de “Nueva Generación” (NGL) que las superasen. Son diversas las técnicas se han ido proponiendo durante estos años, pero la mejora de la litografía UV las ha ido relegando fuera del ámbito industrial. Más recientemente, la litografía por nanoestampación (NIL), ha tomado fuerza como la nueva NGL por su extrema sencillez y por su demostrada elevada resolución. La NIL térmica (T-NIL) consiste en la deformación de un termoplástico bajo presión y temperatura por un molde con estructuras nanométricas, mientras que la NIL por UV (UV-NIL) consiste en la polimerización de un monómero a temperatura ambiente con menor presión ejercida por un molde transparente al UV. Uno de los principales problemas de esta técnica es la separación de molde y polímero, una vez finalizado el proceso. Como alternativa a los tratamientos existentes, se han propuesto los recubrimientos de carbono amorfo tipo diamante (DLC) por su baja reactividad química, elevada dureza y posibilidad de incorporación de otros elementos químicos a fin de reducir su energía superficial. El proyecto del Ministerio de Ciencia e Innovación DPI2007-61349, “Moldes de carbono amorfo para micro y nanograbado de superficies poliméricas”, en el cuál se ha enmarcado esta tesis, pretende estudiar los efectos de la incorporación de diferentes elementos en capas de DLC para la mejora de los moldes de NIL. La incorporación de flúor en capas de DLC ha demostrado recientemente ser útil en la mejora de las propiedades de los moldes de NIL, porque evita el uso de los actuales tratamientos superficiales (por ejemplo siloxanos), los cuales, además de ser menos duraderos, pueden reaccionar con los polímeros en presencia de luz UV. Así, en esta tesis se ha estudiado la influencia de la incorporación de flúor a capas de DLC en la composición y en las propiedades de superfície obtenidas.

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No. of bitstreams: 1 CAMARGO_Janine_2017.pdf: 19878018 bytes, checksum: 517c1918bf6801b10fe87b0d806d8a50 (MD5) Previous issue date: 2017-03-14 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Cellulose is a biopolymer available in abundance in nature, which presents very interesting properties mainly for the textile, packaging and paper industry. However, due to its strongly hydrophilic character, resulting from the presence of a large number of free hydroxyl groups in its molecule, its use in certain areas becomes limited. In order to promote the modification of the wetting characteristic of the cellulose, and make it superhydrophobic, samples of this material were submitted to plasma processes performed in two steps: ablation and film deposition. Initially, the effect of variation of ablation time on the creation of adequate surface topography was studied. For this, the samples were exposed to the oxygen plasma at a pressure of 13 Pa and power of 150 W, varying the treatment time from 5 to 60 minutes. Then, the treated samples were submitted to the process called PECVD (Plasma Enhanced Chemical Vapor Deposition), in which a film was deposited on the surface from the precursor hexamethyldisiloxane (HMDSO) in the presence of argon, in a ratio of 70 e 30%, respectively. The deposition time was set to 30 minutes and the power applied was 150 W. In a second investigation, the effect of the thickness of the deposited film was studied. In this case, the cellulose samples were previously exposed to the oxygen ablation plasma for 60 minutes and then led to the PECVD process, with the deposition time varying from 5 to 30 minutes. In a third investigation, the duration of the ablation and deposition steps was reduced to 30 and 1 minute, respectively, in order to optimize the methodology. The samples were characterized by Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), Fourier Transform Infrared Spectroscopy (FTIR), profilometry, static contact angle measurements and hysteresis and sliding angle measurements. The results demonstrated that longer exposure times for the ablation step provide a significant modification in the material, through the creation of nanoscale structures on the surface of the fibers. The deposition step promoted the formation of films with organosilicon character on the cellulose surface, with thicknesses varying between 144 and 910 nm. The combination of the topography created after 30 minutes of ablation with the thin film resulting from the deposition step for 1 minute provided a surface with low receptivity for both polar (? = 150°) and nonpolar (? ~ 120°) liquids, whose wettability property remained stable with treatment aging time. The low values obtained for hysteresis (9°) and sliding angle (7°) confirm the creation of a superhydrophobic roll-off surface. / A celulose é um biopolímero disponível em abundância na natureza e que possui propriedades bastante interessantes principalmente para a indústria têxtil, de embalagens e papel. No entanto, devido ao seu caráter fortemente hidrofílico, proveniente da presença de um grande número de grupos hidroxila livres em sua molécula, sua utilização em determinadas áreas se torna limitada. Com o objetivo de promover a modificação da característica de molhabilidade da celulose, de modo a torná-la superhidrofóbica, amostras deste material foram submetidas a processos a plasma realizados em duas etapas: ablação e deposição de filme. Inicialmente, estudou-se o efeito da variação do tempo de ablação na criação da topografia adequada da superfície. Para isto, as amostras foram expostas ao plasma de oxigênio a uma pressão de 13 Pa e 150 W de potência, variando-se o tempo de tratamento de 5 a 60 minutos. Em seguida, as amostras tratadas foram submetidas ao processo denominado PECVD (Plasma Enhanced Chemical Vapor Deposition), no qual foi depositado um filme sobre a superfície das mesmas, a partir do precursor hexametildisiloxano (HMDSO) na presença de argônio, numa proporção de 70 e 30%, respectivamente. O tempo de deposição foi fixado em 30 minutos e a potência aplicada foi de 150 W. Numa segunda investigação, foi estudado o efeito da espessura do filme depositado. Neste caso, as amostras de celulose foram previamente expostas ao plasma de ablação com oxigênio durante 60 minutos e posteriormente ao processo de PECVD, variando-se o tempo de deposição de 5 a 30 minutos. Numa terceira investigação, o tempo de duração das etapas de ablação e deposição foi reduzido para 30 e 1 minuto, respectivamente, com o intuito de otimizar a metodologia. As amostras foram caracterizadas por Microscopia Eletrônica de Varredura (MEV), Espectroscopia de Energia Dispersiva (EDS), Espectroscopia de Absorção no Infravermelho por Transformada de Fourier (FTIR), perfilometria, medição de ângulo de contato estático e medição de histerese e ângulo de deslizamento. Os resultados demonstraram que maiores tempos de exposição à etapa de ablação proporcionam uma modificação significativa no material, por meio da criação de estruturas em nanoescala na superfície das fibras. A etapa de deposição promoveu a formação de filmes de caráter organosilicone sobre a superfície da celulose, com espessuras variando entre 144 e 910 nm. A combinação entre a topografia criada após 30 minutos de ablação e o filme de menor espessura resultante da etapa de deposição durante 1 minuto, possibilitaram a obtenção de uma superfície de baixa receptividade tanto a líquidos polares (? =150°) quanto apolares (? ~120°), cuja propriedade de molhabilidade se manteve estável com o tempo de envelhecimento. Os baixos valores de histerese (9°) e ângulo de deslizamento (7°) obtidos confirmam a criação de uma superfície superhidrofóbica do tipo “roll-off”.

abstract: Cubic boron nitride (c-BN) has potential for electronic applications as an electron emitter and serving as a base material for diodes, transistors, etc. However, there has been limited research on c-BN reported, and many of the electronic properties of c-BN and c-BN interfaces have yet to be reported. This dissertation focused on probing thin film c-BN deposited via plasma enhanced chemical vapor deposition (PECVD) with in situ photoelectron spectroscopy (PES). PES measurements were used to characterize the electronic properties of c-BN films and interfaces with vacuum and diamond. First, the interface between c-BN and vacuum were characterized with ultraviolet PES (UPS). UPS measurements indicated that as-deposited c-BN, H2 plasma treated c-BN, and annealed c-BN post H2 plasma treatment exhibited negative electron affinity surfaces. A dipole model suggested dipoles from H-terminated N surface sites were found to be responsible for the NEA surface. Then, Si was introduced into c-BN films to realize n-type doped c-BN. The valence structure and work function of c-BN:Si films were characterized with XPS and UPS measurements. Measurements were unable to confirm n-type character, and it is concluded that silicon nitride formation was the primary effect for the observations. Finally, XPS measurements were employed to measure the band offsets at the c-BN/diamond interface. Measurements indicated the valence band maximum (VBM) of c-BN was positioned ~0.8 eV above the VBM of diamond. / Dissertation/Thesis / Doctoral Dissertation Physics 2016