Title: Stability of plasma polymers under various conditions. Author: Jindřich Matoušek Department/Institute: Department of Macromolecular Physics/Charles University in Prague Supervisor of the doctoral thesis: prof. RNDr. Hynek Biederman, DrSc., Department of Macromolecular Physics Abstract: The depositions of plasma polymer thin films were carried out using plasma polymerization depostition. The working gas mixture consisted of argon and monomer vapours. The source monomers used were n-hexane and terthiophene. The depositions of nanocomposite thin films Sn/pp n-hexane by means of magnetron sputtering in a working gas mixture of argon and n-hexane were done. The resulting thin films were characterized by XPS, FTIR, AFM, SEM, TEM, optical microscope and elipsometry. The influence of deposition parameters on the resulting thin film propertires was studied. The ageing of the thin films in humidity and distilled water was studied. The current-voltage characteristics of selected thin films were measured. Keywords: plasma polymer, nanocomposite, ageing.

The diploma thesis deals with characterization of adhesion of plasma polymer films deposited on silicon wafers. The samples included organosilicon thin films based on tetravinylsilane monomer prepared by plasma-enhanced chemical vapour deposition. Scratch test was used to characterize film adhesion employing nanoindentation measurements. Adhesion of plasma polymer films of different mechanical properties and film thickness was analyzed by normal and lateral forces, friction coefficient, and scratch images obtained by scanning probe microscope working in atomic force microscopy mode.

The diploma thesis is aimed at coating of glass fibers using tetravinylsilane as a monomer by Plasma-Enhanced Chemical Vapor Deposition (PECVD). The surface modified fibers were used as reinforcements for unsaturated polyester resin to form composites of controlled interphase. Chemical and mechanical properties of thin films were controled by the effective power. Determination of fiber-matrix adhesion and an influence of polymer-interface on mechanical properties of composites were characterized by Scanning Electron Microscopy (SEM) and microindentation technique using Interfacial Testing System (ITS) enabling to measure the interfacial shear strength.

The doctoral thesis deals with the study of morphology and mechanical properties of thin plasma polymer films based on tetravinylsilane monomer and its mixtures with oxygen and argon. Thin films were prepared by plasma-enhanced chemical vapour deposition on silicon and glass substrates. Atomic force microscopy was used for characterization of thin film surface and for depiction of composite interphase with functional interlayer. Mechanical properties of thin films, namely Young’s modulus and hardness, were studied by cyclic nanoindentation technique. Nanoindentation device was also used to carry out scratch test, which was helpful to describe adhesion of films to substrate. In this thesis the influence of deposition conditions on surface and mechanical properties of thin films prepared in continual and pulse wave on planar substrates is discussed. Also, the suitability of few atomic force microscopy techniques for depiction of composite interphase was reviewed.

In this work we study the deposition of hydrophobic fluorocarbon coatings by magnetron sputtering of polymeric PTFE target. We show what is the influence of the conditions of the deposition process - the pressure in the chamber, the RF power - on the properties of the resulting CFx thin films (their chemical composition, morphology, wettability, barrier and optical properties, stability and possible bio-aplications). In this work we use a novel way to control the morphology and the chemical composition of the surface of thin films independently by using nano-particles, both metal (Pt, Cu, Al) and polymeric (C:H, Nylon). With nano-particles we can control the hydrophobicity of thin films and we can prepare super-hydrophobic films. Work has an experimental character.

Title: Preparation of Nanocomposites TiOx/Plasma Polymer and Study of Their Properties Author: Mgr. Martin Drábik Department: Department of Macromolecular Physics Supervisor: Prof. RNDr. Hynek Biederman, DrSc. Supervisor's e-mail address: bieder@kmf.troja.mff.cuni.cz Abstract: This thesis concerns a study of nanocomposite films TiOx/plasma polymer prepared by various deposition techniques using different organic precursors. Processes of deposition of the films were diagnosed in-situ by means of OES and measuring the deposition rate by QCM. Properties of the nanocomposite films were studied by various characterization techniques. Wettability of the films was described by means of the contact angle of water. Morphology of the nanocomposites was characterized by AFM, TEM and SEM. Elemental analysis and chemical composition of the films were studied by XPS, RBS, SIMS and FTIR. Crystal structure of TiO2 films was identified by XRD. Optical characterization of the prepared films was done by UV-Vis spectroscopy. Electrical properties of the samples were characterized by I-V and SPV measurements. In the end, 'wet' chemical processes were utilized for preparation of both TiO2 nanostructures and organic films for comparison with vacuum deposition techniques and plasma polymer composite films. Keywords: nanocomposite...

Title: XPS analysis of plasma polymers and nanocomposite films without breaking vacuum Author: Anna Artemenko Institute: Charles University in Prague, Department of Macromolecular Physics Supervisor of the doctoral thesis: Prof. RNDr. Hynek Biederman, DrSc., Charles University in Prague, Department of Macromolecular Physics. Abstract: Plasma polymers and metal/ plasma polymer nanocomposites have been widely used for various biomedical proposes. Naturally, surface properties of the coatings such as high wettability, stability on the open air and in aqueous media, resistance towards different sterilization processes and cells adhesion are required for bioapplications. This thesis is mainly dedicated to the investigation of chemical composition of deposited coatings using XPS analysis. Nylon-like plasma polymer, PEO-like coatings, fluorocarbon plasma polymer (PTFE) films and Au/PEO-like, Ag/C:H, Al/C:H nanocomposites were chosen as the subject material. In addition, results of XPS measurements were used for the computer simulation for calculation of filling factor of metal/ plasma polymer nanocomposites. These results were in a good agreement with experimental data. Keywords: plasma polymer, nanocomposite, XPS analysis, bioapplication, simulation.

Submitted by FELIPE VICENTE DE PAULA KODAIRA null (kodaira.felipe@gmail.com) on 2016-04-04T21:50:29Z No. of bitstreams: 1 Dissertacao-Submetida.pdf: 3356414 bytes, checksum: bf8e73cb2a050bd0ecb4f444cd28e58c (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-04-06T16:24:59Z (GMT) No. of bitstreams: 1 kodaira_fvp_me_guara.pdf: 3356414 bytes, checksum: bf8e73cb2a050bd0ecb4f444cd28e58c (MD5) / Made available in DSpace on 2016-04-06T16:24:59Z (GMT). No. of bitstreams: 1 kodaira_fvp_me_guara.pdf: 3356414 bytes, checksum: bf8e73cb2a050bd0ecb4f444cd28e58c (MD5) Previous issue date: 2016-02-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Filmes finos poliméricos depositados a plasma são de grande utilidade em diversas aplicações industriais e científicas, em áreas como eletrônica, mecânica, revestimentos, biomateriais, entre outras, devido a propriedades interessantes como: boa adesão ao substrato, estrutura entrelaçada, espessura nanométrica, homogeneidade, entre outros. Neste trabalho, filmes finos poliméricos foram depositados utilizando-se a técnica de implantação iônica por imersão em plasma e deposição a partir das misturas entre o monômero hexametildisilazano e os gases argônio, hélio e nitrogênio. Foram variadas as concentrações gás/monômero nestas misturas e a potência de deposição. Os filmes obtidos passaram por caracterizações de ângulo de contato, energia de superfície, dureza, espessura, índice de refração e estrutura molecular. Para todas as condições avaliadas, o filme apresentou-se transparente, com valores para o índice de refração variando entre 1,56 e 1,70. Os filmes poliméricos também se mostraram hidrofóbicos, com valores para o ângulo de contato próximos a 100 graus. Os valores para a dureza foram de 0,7 a 2,6 GPa. A espessura dos filmes para diferentes condições variaram entre, aproximadamente, 100 e 200 nm. A análise da estrutura molecular permitiu observar que os mesmos grupos funcionais estão presentes em todos os filmes depositados, porém a variação dos parâmetros favorece o aumento de determinados grupos em detrimento de outros. A partir destas caracterizações, foi possível observar que variações nos parâmetros do plasma interferem diretamente nos filmes resultantes. / Polymeric thin films deposited by plasma technique are very attractive for many industrial and scientific applications in areas such as electronics, mechanics, coatings, biomaterials, among others, due to favorable properties such as good adhesion to the substrate, high crosslinking, nanomectric thickness, homogeneity, etc. In this work, polymeric thin films were deposited by Plasma Immersion Ion Implantation and Deposition (PIIID) technique from mixtures between hexamethyldisilazane and the gases argon, helium and nitrogen. The gas/monomer concentration in these mixtures and deposition power were varied. The grown films were characterized by their contact angle, surface energy, hardness, thickness, refractive index and molecular structure. For all the evaluated conditions, the film showed itself transparent, with refractive index values ranging from 1.56 to 1.70. The polymeric films were also hydrophobic, with contact angle values around 100 degrees. The hardness values ranged from 0.7 to 2.6. The thickness for different conditions of PIIID, ranged from 100 to 200 nm. The molecular structure analysis showed that the same functional groups were present in all the deposited films; however the parameter variation favored the growth of certain groups over others. From these characterizations, it was possible to observe that changes in the plasma parameters interfere directly in the produced films.

Les nanostructures de polymères suscitent un grand intérêt grâce à leurs propriétés uniques comme le facteur de forme important. Cette propriété est essentielle pour l’utilisation dans des domaines où les interactions de surface sont mises en jeu. Un exemple d’une telle application est la détection de gaz. La polyaniline (PANi) s’est montrée prometteuse pour l’utilisation dans les capteurs d’ammoniac. La synthèse conventionnelle (chimique ou électrochimique) de nanofibres de PANi a été largement décrite dans la littérature mais cette voie possède de nombreux inconvénients. Parmi eux, figurent plusieurs étapes de synthèse (la synthèse, la purification, le dépôt sur le substrat) et l’utilisation de produits chimiques (oxydants, acides) peu respectueux de l’environnement. La polymérisation assistée par plasma froid (PECVD) permet de s’en affranchir car seul le monomère est utilisé qui se polymérise directement sur le substrat. Ainsi, ce travail de thèse a pour objectif d’élaborer des nanostructures de polyaniline plasma tout en conservant au mieux l’unité monomère dans le polymère. Le paramètre essentiel qui détermine le processus de nanostructuration est la puissance de décharge. A forte puissance, des films fortement structurés sont obtenus mais les molécules de monomère sont totalement fragmentées. En revanche, une faible puissance conduit à des films avec conservation de l’entité monomère mais sans structure morphologique particulière. Nous avons développé une méthode permettant de combiner les avantages de chaque régime : ce procédé dit « bottom-up » est réalisé en variant la puissance au cours du dépôt selon deux ou trois étapes. Les paramètres qui influencent les structures chimique et morphologique sont déterminés et les procédés à deux et trois étapes sont comparés. Par ailleurs, la synthèse « top-down » de nanostructures par gravure de la couche mince de PANi est également étudiée en fonction des paramètres du plasma (puissance et temps de décharge, débit du gaz de gravure et polarisation du substrat). Finalement, nous avons synthétisé, en phase plasma, des nanocomposites associant les nanostructures de PANi et des particules métalliques de Pd déposées par pulvérisation. La structure chimique des films de PANi est caractérisée par les spectroscopies UV-Vis, IR-TF et XPS. Pour mettre en évidence la nanostructuration des couches minces, les microscopies MEB et AFM sont utilisées. Cette dernière permet également de calculer la valeur de rugosité ainsi que la surface spécifique de la PANi. La spectroscopie EDX est utilisée pour mettre en évidence et pour quantifier le palladium dans les films synthétisés. Les couches obtenues sont finalement caractérisées sous gaz par mesures de variation d’absorbance afin de déterminer leur sensibilité et leur temps de réponse à l’ammoniac. / Polymer nanostructures are of great interest due to their unique properties such as high shape factor. This property is essential for applications where surface interactions are involved. One example of such an application is the gas detection. Polyaniline (PANi) has been shown as a promising material for ammonia detection. Conventional synthesis (chemical orelectrochemical) of PANi nanofibers has been widely described in the literature but this way has many drawbacks. They include several steps (synthesis, purification, deposition on the substrate) and the use of chemicals (oxidants, acids) which are not environmentally friendly. The polymerization assisted by cold plasma (PECVD) allows overcoming it, as only themonomer is used and is directly polymerized on the substrate. This thesis work aims to develop plasma polyanilinenanostructures while retaining the monomer unit in the polymer. The key parameter that determines thenanostructuring process is the discharge power. At high power, highly structured films are obtained but the monomer molecules are totally fragmented. On the contrary, low power allows conservation of the monomer unit but no surface structuring is observed. We developed a method which combines the advantages of each regime. This "bottom-up" process consists to vary the input power during deposition in two or three stages. Parameters influencing the chemical and morphological structures are determined and the two and three steps methods are compared. Furthermore, the "top-down" synthesis of nanostructures by etching the PANi layer is also studied according to the plasma parameters (power and discharge time, etching gas flow rate and substrate bias). Finally, in plasma phase, we synthesized nanocomposite by combining PANi nanostructures and sputtered Pd particles. The chemical structure of the PANi films is characterized by UV-Vis spectroscopy, FT-IR and XPS. In order to highlight the nanostructuring of thin films, SEM and AFM microscopy areused. The latter one allows also the calculation of the roughness and specific surface of the PANi. EDX spectroscopyis used to bring out the presence of palladium and to quantify it. Finally, the obtained layers are characterized under gas byabsorbance variation measurements in order to determine their sensitivity and response time to ammonia.

Presented work is focused on the deposition and characterization of thin and ultrathin plasma polymer films, then also on the preparation of nanocomposites metal/plasma polymer. The characterization of plasma polymer films was partly done in-situ without exposing the samples to the atmosphere. The thickness of prepared films was measured by spectral ellipsometry, the chemical composition was measured by XPS. The morphology and optical properties of deposited films were measured ex-situ. It is shown that during the initial stages of growth the properties of plasma polymer films depend on their thickness and also on the material of the substrate. Many interesting applications were explored for prepared nanocomposites metal/plasma polymer. They can be used as superhydrophobic coatings, gradient coatings, substrates for Raman spectroscopy or as antibacterial coatings. Moreover, special optical properties of prepared nanocomposites were studied in detail. Presented work has an experimental character.