HMDSO plasma polymerization and thin film optical properties

Thin films were deposited from hexamethyldisiloxane (HMDSO) in a glow discharge supplied with radiofrequency (rf) power. Actino-metric optical emission spectroscopy was used to follow trends in the plasma concentrations of the species SiH (414.2 nm), CH (431.4 nm), CO (520.0 nm), and H (656.3 nm) as a function of the applied rf power (range 5 to 35 W). Transmission infrared spectroscopy (IRS) was employed to characterize the molecular structure of the polymer, showing the presence of Si-H, Si-O-Si, Si-O-C and C-H groups. The deposition rate, determined by optical interferometry, ranged from 60 to 130 nm/min. Optical properties were determined from transmission ultra violet-visible spectroscopy (UVS) data. The absorption coefficient α, the refractive index n, and the optical gap E04 of the polymer films were calculated as a function of the applied power. The refractive index at a photon energy of 1 eV varied from 1.45 to 1.55, depending on the rf power used for the deposition. The absorption coefficient showed an absorption edge similar to other non-crystalline materials, amorphous hydrogenated carbon, and semiconductors. For our samples, we define as an optical gap, the photon energy E04 corresponding to the energy at an absorption of 104 cm-1. The values of E04 decreased from 5.3 to 4.6 as the rf power was increased from 5 to 35 W. © 1995.

Avaliação das características de superfície e formação de biofilmes em materiais odontológicos tratados em plasmas de HMDSO

Pós-graduação em Reabilitação Oral - FOAR

XPS investigation of plasma-deposited polysiloxane films irradiated with helium ions

This work describes an XPS investigation of plasma-deposited polysiloxane films irradiated with 170 keV He+ ions at fluences, Phi, ranging from 1 x 10(14) to 1 x 10(16) cm(-2). Modifications in the atomic concentrations of the surface atoms with (D were revealed by changes in the [O]/[Si], [O]/[C] and [C]/[Si] atomic ratios. Surface chemical structure modifications were evidenced by the increasing C1s peak width and asymmetry as Phi was increased, due to the formation of ether and carboxyl functionalities. Moreover, structural transformations were indicated by the positive binding energy shift of the Si2p peaks, due to the increasing Si oxidation. Correlations of the XPS data with other results from previous work on polysiloxanes illustrate the role of ion beam-induced bond breaking on the structural modifications.

Estudo das propriedades de barreira de filmes depositados a plasma sobre a liga de alumínio 2024

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Características estruturais de aerogéis hidrofílicos e hidrofóbicos de sílica modificados com Dodecil Sulfato de Sódio

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Abscheidung und Charakterisierung von Plasmapolymerschichten auf Fluorkohlenstoff- und Siloxan-Basis

In dieser Arbeit wurden Fluorkohlenstoff-basierte und siliziumorganische Plasmapolymerfilme hergestellt und hinsichtlich ihrer strukturellen und funktionalen Eigenschaften untersucht. Beide untersuchten Materialsysteme sind in der Beschichtungstechnologie von großem wissenschaftlichen und anwendungstechnischen Interesse. Die Schichtabscheidung erfolgte mittels plasmachemischer Gasphasenabscheidung (PECVD) an Parallelplattenreaktoren. Bei den Untersuchungen zur Fluorkohlenstoff-Plasmapolymerisation stand die Herstellung ultra-dünner, d. h. weniger als 5 nm dicker Schichten im Vordergrund. Dies wurde durch gepulste Plasmaanregung und Verwendung eines Gasgemisches aus Trifluormethan (CHF3) und Argon realisiert. Die Bindungsstruktur der Schichten wurden in Abhängigkeit der eingespeisten Leistung, die den Fragmentationsgrad der Monomere im Plasma bestimmt, analysiert. Hierzu wurden die Röntgen-Photoelektronenspektroskopie (XPS), Rasterkraftmikroskopie (AFM), Flugzeit-Sekundärionenmassenspektrometrie (ToF-SIMS) und Röntgenreflektometrie (XRR) eingesetzt. Es zeigte sich, dass die abgeschiedenen Schichten ein homogenes Wachstumsverhalten und keine ausgeprägten Interfacebereiche zum Substrat und zur Oberfläche hin aufweisen. Die XPS-Analysen deuten darauf hin, dass Verkettungsreaktionen von CF2-Radikalen im Plasma eine wichtige Rolle für den Schichtbildungsprozess spielen. Weiterhin konnte gezeigt werden, dass der gewählte Beschichtungsprozess eine gezielte Reduzierung der Benetzbarkeit verschiedener Substrate ermöglicht. Dabei genügen Schichtdicken von weniger als 3 nm zur Erreichung eines teflonartigen Oberflächencharakters mit Oberflächenenergien um 20 mN/m. Damit erschließen sich neue Applikationsmöglichkeiten ultra-dünner Fluorkohlenstoffschichten, was anhand eines Beispiels aus dem Bereich der Nanooptik demonstriert wird. Für die siliziumorganischen Schichten unter Verwendung des Monomers Hexamethyldisiloxan (HMDSO) galt es zunächst, diejenigen Prozessparameter zu identifizieren, die ihren organischen bzw. glasartigen Charakter bestimmen. Hierzu wurde der Einfluss von Leistungseintrag und Zugabe von Sauerstoff als Reaktivgas auf die Elementzusammensetzung der Schichten untersucht. Bei niedrigen Plasmaleistungen und Sauerstoffflüssen werden vor allem kohlenstoffreiche Schichten abgeschieden, was auf eine geringere Fragmentierung der Kohlenwasserstoffgruppen zurückgeführt wurde. Es zeigte sich, dass die Variation des Sauerstoffanteils im Prozessgas eine sehr genaue Steuerbarkeit der Schichteigenschaften ermöglicht. Mittels Sekundär-Neutralteilchen-Massenspektrometrie (SNMS) konnte die prozesstechnische Realisierbarkeit und analytische Quantifizierbarkeit von Wechselschichtsystemen aus polymerartigen und glasartigen Lagen demonstriert werden. Aus dem Intensitätsverhältnis von Si:H-Molekülen zu Si-Atomen im SNMS-Spektrum ließ sich der Wasserstoffgehalt bestimmen. Weiterhin konnte gezeigt werden, dass durch Abscheidung von HMDSO-basierten Gradientenschichten eine deutliche Reduzierung von Reibung und Verschleiß bei Elastomerbauteilen erzielt werden kann.

HMDSO和TFM混合气体等离子体聚合膜的结构与性能

在钟罩式内极反应器中进行了六甲基二硅氧烷(HMDSO)和四氟化碳(TFM)混合气体等离子体聚合。用IR、XPS、X射线对聚合膜结构进行了表征。等离子体共聚合膜中含有Si和F,聚合膜中元素组成依赖于起始混合气体单体的比,Si/C元素比随着混合气体中TFM浓度增加而减小,而F/C比增大。测定了复合膜的气体透过性,等离子体共聚合方法是制备气体分离膜的可行方法。同时,还测定了等离子体聚合膜的接触角,并计算了表面能。

Plasma polymerized hexamethyldisiloxane: Discharge and film studies

Films were grown in hexamethyldisiloxane (HMDS)-argon mixtures in a diode sputtering system with a gold cathode. Quantitative optical emission spectroscopy (OES)-actinometry revealed that the electron density or mean electron energy (or both) increased with increasing Ar concentrations in the gas feed. Increasing concentrations of Ar produced greater sputtering of the cathode and hence greater plasma A u concentrations. Fragmentation of the HMDS molecule resulted in species such as CH, Fl, and Si which were detected by OES. Film deposition rate, as determined by optical interferometry, was found to be increased by the inclusion of Ar in the gas feed. Transmission electron microscopy revealed particles, probably of Au, embedded in the polymer films. Actinometric measurements of Au in the discharge and electron probe microscopy of the deposited material showed that film Au concentrations increase with increasing concentrations of Au in the plasma. A relatively low fragmentation of HMDS molecules in the de plasma was revealed by the very small Si-HIR absorption band which is usually prominent in spectra of plasma polymerized HMDS films.

Caracterização de filmes finos obtidos por deposição de vapor químico assistido a plasma (PECVD) e deposição e implantação iônica por imersão em plasma (PIIID)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Enhancement of Corrosion Resistance AISI 304 Steel by Plasma Polymerized Thin Films

The purpose of this work is the deposition of films in order to increase the corrosion resistance of AISI 304 steel, which is a material used to construct the reactors for bioethanol production. This deposition inhibits the permeation of corrosive species to the film-metal interface. Thin films were prepared by radio-frequency plasma enhanced chemical vapor deposition (RF-PECVD) method using plasmas of hexamethyldisiloxane/argon/oxygen mixtures excited by signals of different powers. The plasma was generated by the application of RF power of 13.56 MHz to the sample holder while keeping grounded the topmost electrode and the chamber walls. The effect of the RF power on the properties of the samples was investigated by perfilometry, X-ray photoelectron spectroscopy (XPS), contact angle, and electrochemical impedance spectroscopy (EIS). The results of the corrosion resistance tests of the AISI 304 steel were interpreted in terms of the energy delivered to the growing layer by plasma excitation power.

Correlation Between the Electrical and Optical Properties of an Atmospheric Pressure Plasma During Siloxane Coating Deposition

The effect of varying process parameters on atmospheric plasma characteristics and properties of nanometre thick siloxane coatings is investigated in a reel-to-reel deposition process. Varying plasma operation modes were observed with increasing applied power for helium and helium/oxygen plasmas. The electrical and optical behaviour of the dielectric barrier discharge were determined from current/voltage, emission spectroscopy and time resolved light emission measurements. As applied power increased, multiple discharge events occurred, producing a uniform multi-peak pseudoglow discharge, resulting in an increase in the discharge gas temperature. The effects of different operating modes on coating oxidation and growth rates were examined by injecting hexamethyldisiloxane liquid precursor into the chamber under varying operating conditions. A quenching effect on the plasma was observed, causing a decrease in plasma input power and emission intensity. Siloxane coatings deposited in helium plasmas had a higher organic component and higher growth rates than those deposited in helium/oxygen plasmas.

Etude spectroscopique d’un plasma micro-onde à la pression atmosphérique et son application à la synthèse de nanostructures

L’objectif de ce mémoire de maîtrise est de caractériser la distribution axiale des plasmas tubulaires à la pression atmosphérique créés et entretenus par une onde électromagnétique de surface ainsi que d’explorer le potentiel de ces sources pour la synthèse de matériaux et de nanomatériaux. Un précédent travail de thèse, qui avait pour objectif de déterminer les mécanismes à l’origine de la contraction radiale du plasma créé dans des gaz rares, a mis en lumière un phénomène jusque-là inconnu dans les plasmas d’onde de surface (POS). En effet, la distribution axiale varie différemment selon la puissance incidente ce qui constitue une différence majeure par rapport aux plasmas à pression réduite. Dans ce contexte, nous avons réalisé une étude paramétrique des POS à la pression atmosphérique dans l’Ar. À partir de nos mesures de densité électronique, de température d’excitation et de densité d’atomes d’Ar dans un niveau métastable (Ar 3P2), résolues axialement, nous avons conclu que le comportement axial de l’intensité lumineuse avec la puissance n’est pas lié à un changement de la cinétique de la décharge (qui est dépendante de la température des électrons et de la densité d’atomes d’Ar métastables), mais plutôt à une distribution anormale de dissipation de puissance dans le plasma (reliée à la densité d’électrons). Plus précisément, nos résultats suggèrent que ce dépôt anormal de puissance provient d’une réflexion de l’onde dans le fort gradient de densité de charges en fin de colonne, un effet plus marqué pour de faibles longueurs de colonnes à plasma. Ensuite, nous avons effectué une étude spectroscopique du plasma en présence de précurseurs organiques, en particulier le HMDSO pour la synthèse de matériaux organosiliciés et l’IPT pour la synthèse de matériaux organotitaniques. Les POS à la PA sont caractérisés par des densités de charges très élevées (>10^13 cm^-3), permettant ainsi d’atteindre des degrés de dissociation des précurseurs nettement plus élevés que ceux d'autres plasmas froids à la pression atmosphérique comme les décharges à barrière diélectrique. Dans de tels cas, les matériaux synthétisés prennent la forme de nanopoudres organiques de taille inférieure à 100 nm. En présence de faibles quantités d’oxygène dans le plasma, nous obtenons plutôt des nanopoudres à base d’oxyde de silicium (HMDSO) ou à base de titanate de silicium (IPT), avec très peu de carbone.

Fluoride Intake from Meals Served in Daycare Centres in Municipalities with Different Fluoride Concentrations in the Water Supply

Purpose: The aim of this study was (1) to determine the fluoride content in the meals served to children aged up to 36 months in daycare centres of two municipalities with different levels of fluoride in the water supply, (2) to calculate the mean fluoride ingested daily by the children when consuming those meals and (3) to analyse the contribution of this consumption to the development of dental fluorosisMaterials and Methods: Samples of the meals served to the children were collected during a whole week. The fluoride content of the samples of solid foods and milk was analysed using an ion-specific electrode combined with reference electrode after diffusion facilitated by hexamethyldisiloxane Samples of beverages were buffered with an equal volume of total ionic strength adjustment buffer and analysed using a combined electrode. The results were compared using the Mann Whitney testResults: Mean fluoride contents of the meals were of 0.204 +/- 0 179 and 0.322 +/- 0.242 mu g F/mL (P < 0.05), respectively, in the municipalities with low and adequate fluoride content. Daily fluoride intake in the former was 0.013 +/- 0.003 mg/kg body weight/day and in the latter was 0.012 +/- 0 001 mg/kg body weight/day (P > 0 05)Conclusions: The children were not exposed to dental fluorosis in the daycare centres However, the risk cannot be ignored, considering the meals and the use of fluoridated dentifrices at home may also contribute to fluoride intake.

Characterization of Si : O : C : H films fabricated using electron emission enhanced chemical vapour deposition

Silicon-based polymers and oxides may be formed when vapours of oxygen-containing organosilicone compounds are exposed to energetic electrons drawn from a hot filament by a bias potential applied to a second electrode in a controlled atmosphere in a vacuum chamber. As little deposition occurs in the absence of the bias potential, electron impact fragmentation is the key mechanism in film fabrication using electron-emission enhanced chemical vapour deposition (EEECVD). The feasibility of depositing amorphous hydrogenated carbon films also containing silicon from plasmas of tetramethylsilane or hexamethyldisiloxane has already been shown. In this work, we report the deposition of diverse films from plasmas of tetraethoxysilane (TEOS)-argon mixtures and the characterization of the materials obtained. The effects of changes in the substrate holder bias (Vs) and of the proportion of TEOS in the mixture (XT) on the chemical structure of the films are examined by infrared-reflection absorption spectroscopy (IRRAS) at near-normal and oblique incidence using unpolarised and p-polarised, light, respectively. The latter is particularly useful in detecting vibrational modes not observed when using conventional near-normal incidence. Elemental analyses of the film were carried out by X-ray photoelectron spectroscopy (XPS), which was also useful in complementary structural investigations. In addition, the dependencies of the deposition rate on Vs and XT are presented. (c) 2007 Elsevier B.V. All rights reserved.