The effects of direct plasma chemistries on carbon removal from silicon nitride (SiNx) and oxynitride (SiOxNy ) surfaces and Cu have been studied by x-photoelectron spectroscopy (XPS) and ex-situ contact angle measurements. The data indicate that O2,NH3 and He capacitively coupled plasmas are effective at removing adventitious carbon from silicon nitride (SiNx) and Silicon oxynitride (SiOxNy ) surfaces. O2plasma and He plasma treatment results in the formation of silica overlayer. In contrast, the exposure to NH3 plasma results in negligible additional oxidation of the SiNx and SiOxNy surface. Ex-situ contact angle measurements show that SiNx and SiOxNy surfaces when exposed to oxygen plasma are initially more hydrophilic than surfaces exposed to NH3 plasma and He plasma, indicating that the O2 plasma-induced SiO2 overlayer is highly reactive towards ambient corresponding to increased roughness measured by AFM. At longer ambient exposures (>~10 hours), however surfaces treated by either O2, He or NH3 plasma exhibit similar steady state contact angles, correlated with rapid uptake of adventitious carbon, as determined by XPS. Surface passivation by exposure to molecular hydrogen prior to ambient exposure significantly retards the increase in the contact angle upon the exposure to ambient. The results suggest a practical route to enhancing the time available for effective bonding to surfaces in microelectronics packaging applications.

In-situ x-ray photoemission (XPS) and ex-situ FTIR studies of nanoporous organosilicate glass (OSG) films point to the separate roles of radicals vs. VUV photons in the carbon abstraction. The studies indicate that reaction with O2 in presence of VUV photons (~123 nm) result in significant carbon abstraction within the bulk and that the kinetics of this process is diffusion-limited. In contrast, OSG exposed to atomic O (no VUV) results in Si-C bond scission and Si-O bond formation, but this process is self-limiting after formation of ~1 nm thick SiO2 surface layer that inhibits further diffusion. Therefore, the diffusion-dominated kinetics of carbon abstraction observed for OSG exposed to O2 plasma is definitively attributed to the diffusion of O2 down OSG nanopores, reacting at photo-activated sites, rather than to the diffusion of atomic O. Pretreatment of OSG by 900 eV Ar+ ion bombardment also results in formation of 1 nm thick SiO2-like surface overlayer that inhibits O2 diffusion, inhibiting VUV+O2 and O2 plasma-induced reactions, and that the effectiveness of this treatment increases with ion kinetic energy. On the contrary, organosilicate glass (OSG) films with backbone carbon (-Si-R-Si-) exhibit significantly enhanced resistance to carbon loss upon exposure to O2 plasma, radicals and VUV+O2 compared to films with terminal methyl groups (Si-CH3). Films incorporating backbone carbon chains (-Si-R-Si-) were deposited from 1,2 bis (triethoxysilyl) ethane (BTESE) precursor by ebeam or plasma cross-linking. The radical effects on BTESE film indicates negligible carbon loss or Si oxidation, combined with C-O bond formation, under conditions where OSG films with terminal methyl groups exhibit > 80% carbon loss within the surface region of the film. C-O bond formation is never observed for terminal CH3 groups. Further, backbone carbon (-Si-R-Si-) films exposed to VUV+O2 exhibit self-limiting, minimal net carbon loss. This indicates that plasma-induced Si-C bond rupture still occurs in the linking unit, but with a low probability of simultaneous rupture of both Si-C bonds required for abstraction of an in-line methylene bridging group. The data thus demonstrate that OSG films containing backbone carbon groups exhibit greatly reduced rates of carbon loss in the presence of O2 plasma, radicals or VUV+O2 compared to films with terminal carbon groups due to fundamentally different patterns of Si-C bond scission. The results demonstrate the potential of backbone carbon low-k films to resist plasma induced damage.

L'atmosphère terrestre a subi, au cours de son histoire précoce, de très violents changements dans sa composition chimique. L'émergence des premiers êtres vivants photosynthétique a provoqué la mise en place et la modification des grands cycles biogéochimiques. L'usage des isotopes comme traceurs des processus physico-chimiques actifs pendant ces périodes s'est développé depuis les années 80. L'observation de compositions isotopiques anormales dans certaines molécules atmosphériques (ozone notamment), similaires à celles observées dans les météorites par Clayton (1973), pose question. De nombreuses hypothèses ont été proposées pour expliquer ce phénomène "anormal". L'objectif principal de cette thèse de doctorat est de développer, par l'expérimentation, l'étude d'un certain nombre de réactions en phase plasma du point de vue isotopique. Seront particulièrement étudiées des réactions appelées réactions à trois corps de formation de l'ozone, où la formation d'un complexe intermédiaire excité entre en jeu dans les mécanismes de génération de ces fractionnements isotopiques anormaux. / The Earth's atmosphere has undergone, during its early history, very violent changes in its chemical composition. The emergence of the first photosynthetic living beings has led to the establishment and modification of major biogeochemical cycles. The use of isotopes as tracers of active physico-chemical processes during these periods has been developed since the 1980s. The observation of abnormal isotopic compositions in certain atmospheric molecules (ozone in particular), similar to those observed in meteorites by Clayton (1973), raises questions. Many hypotheses have been proposed to explain this "abnormal" phenomenon. The main objective of this doctoral work is to develop, through experimentation, the study of plasma reactions from an isotopic point of view. In particular, ozone formation third-body reactions, where the formation of an excited intermediate complex is involved in the mechanisms of generating these abnormal isotopic fractionations, will be studied.

Encore jamais été observé, le rayonnement infrarouge moyen et lointain consécutif aux sprites a été prédit et serait lié à l’excitation des états vibrationnels de CO2. En sciences de l’atmosphère, la composition chimique peut être retrouvée par des méthodes de télédétection infrarouge. Pour la Défense, les émissions infrarouges naturelles peuvent causer de fausses alarmes à travers les systèmes de veille optronique satellitaires ou aéroportés. C’est pourquoi il est nécessaire de caractériser les émissions infrarouges des sprites. Pour cela, un modèle de cinétique plasma-vibrationnelle a été développé et couplé à un modèle de transfert radiatif atmosphérique. Celui-ci permet de simuler les effets énergétiques et chimiques consécutifs à la perturbation électrique des streamers, éléments constitutifs des sprites. Les signatures infrarouges évaluées devraient être détectables pour un observateur situé dans la stratosphère ou dans l’espace. Par ailleurs, les effets des incertitudes sur les principaux paramètres du modèle ont été quantifiés à travers une étude de sensibilité. Enfin, ces travaux ont permis de définir certaines spécifications instrumentales pour la mission HALESIS (High Altitude Luminous Events Studied by Infrared Spectro-imagery), qui aura pour but d’observer les sprites et autres phénomènes lumineux de moyenne atmosphère dans l’infrarouge. / Even if it hasn’t been observed yet, the existence of emissions in the middle and far infrared following a sprite is suspected and could be related to vibrational excitation of CO2. In atmospheric sciences, the chemical composition can be retrieved through different remote sensing methods. For the Defense, natural infrared emissions could cause false alarms through airborne and spaceborne optronic detection systems. That is why it is necessary to characterize the infrared emissions of sprites. To do so, a plasma-vibrational kinetic model has been developed and coupled to an atmospheric radiative transfer model. This model allows evaluating the energetic and chemical effects following the electrical perturbation caused by the propagation of streamers, main constituent elements of sprites. The evaluated signatures could be detectable for an observer situated in the stratosphere or in space. Otherwise, the effects of the uncertainties on the principal parameters of the model have been quantified through a sensitivity analysis. Finally, this work allowed defining instrumental specifications for the future mission HALESIS (High Altitude Luminous Events Studied by Infrared Spectro-imagery), which will record hyperspectral infrared images of sprites and other middle atmosphere luminous events.

Paper and cellulosic materials hold a good promise of being candidates for flexible packaging materials provided suitable barrier properties such as water repellence and grease resistance are imparted to them. One of the methods to achieve these objectives is to surface modify paper/cellulose by applying thin fluorocarbon coatings on the surface. Fluorocarbon thin films produced by plasma enhanced chemical vapor deposition (PECVD) offer several advantages over the films produced by conventional polymerization means. Plasma deposited films are pinhole-free, chemically inert, insoluble, mechanically tough, thermally stable and highly coherent and adherent to variety of substrates. In this work, we investigate the use of PECVD technique to produce barrier films on paper and cellulosic materials. These films, with composition and properties not much different from PTFE, repel water and act as a good barrier to lipophilic materials. Two different monomers, pentafluoroethane (PFE; CF3CHF2) and octafluorocyclobutane (OFCB; C4F8), were investigated and compared in terms of deposition rates and final film properties. Various analytical techniques (XPS, FT-IR, SEM, Ellipsometry, Contact Angle Goniometry, etc.) were used to characterize the fluorocarbon films. The fluorocarbon coated paper exhibited hydrophobic character as evidenced by high water contact angles. Although the films allow water vapor diffusion, the films are hydrophobic and are not wetted when liquid water contacts these layers. Based on various thickness of these films deposited on surface of cellulose, there was a minimum PFE film thickness required to achieve a stable hydrophobic behavior. The fluorocarbon films investigated in this work also exhibited good resistance to lipophilic materials (e.g. oils, fatty acids, etc.). While techniques such as oleic acid penetration and TAPPI "oil-kit" test are commonly used in paper industry to qualitatively test the grease barrier properties of paper/cellulose, this work attempts to quantify the grease barrier properties of fluorocarbon coated paper using techniques such as magnetic resonance imaging (MRI) and quartz crystal microbalance (QCM). Finally, the feasibility of deposition of dual layer films by PECVD was investigated using PFE and n-isopropylacrylamide (NIPAAM) as precursors for applications in barrier packaging and printing.

Orientadores: Jayr de Amorim Filho, Marco Aurélio Pinheiro de Lima / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-24T21:57:52Z (GMT). No. of bitstreams: 1 Ridenti_MarcoAntonio_D.pdf: 6265448 bytes, checksum: 384897ffe1b8b10a23a0ab7c3b206b76 (MD5) Previous issue date: 2014 / Resumo: Neste trabalho plasmas não térmicos gerados em pressão atmosférica e sustentados por ondas de superfície em micro-ondas, tendo o argônio como gás de alimentação, foram estudados experimentalmente e teoricamente tendo em vista aspectos pouco compreendidos de suas propriedades físicas e aplicações voltadas ao tratamento de biomassa. Medições da composição elementar e dos parâmetros físicos foram realizados por meio de técnicas de diagnóstico baseadas em espectrometria de massa e espectroscopia óptica de emissão. O sistema físico foi modelado por meio das equações de continuidade das espécies neutras e carregadas, da equação do calor e da equação de Boltzmann dos elétrons, que foram acopladas utilizando um procedimento auto-consistente. Uma vez obtido o quadro geral das propriedades do plasma, foi estabelecida a condição de operação adequada ao tratamento das amostras derivadas de biomassa. O tratamento foi realizado sobre quatro tipo de amostras: lignina, xilana, celulose e bagaço de cana-de-açúcar. Dentre as contribuições importantes deste trabalho podem ser destacadas: (i) a verificação experimental do papel dos íons moleculares do argônio no processo de contração da descarga; (ii) a determinação do perfil axial no plasma dos principais íon positivos e negativos, da densidade e temperatura eletrônicas, da temperatura do gás e da densidade do estado metaestável Ar(1s5); (iii) verificação da seletividade do tratamento a plasma, tendo sido observada uma alteração significativa dos espectros de absorção no infravermelho nos casos da lignina e da xilana, mas não no caso da celulose. Esse último resultado sugere uma rota inusitada para novas tecnologias de deslignificação e síntese de novos materiais a partir de biomassa / Abstract: In this work non-thermal argon plasmas produced at atmospheric pressure and sustained by microwave surface waves were theoretically and experimentally studied in view of their non understood aspects and also the applications aimed at biomass treatment. Measurements of elemental composition and physical parameters were carried by means of plasma diagnostic techniques such as mass spectrometry and optical emission spectroscopy. Plasma modelling based on the self-consistent solution of the continuity equations of the neutral and charged species, the heat equation and the electron Boltzmann equation was developed to describe the plasma properties. Once a complete picture of the plasma behaviour was obtained, a promising condition for plasma treatment was established. Four types of biomass derived material were plasma treated: lignin, cellulose, xylan and sugarcane bagasse. Among the important contributions of this work one may highlight the following: (i) the experimental verification of the crucial role of argon molecular ions in the discharge contraction; (ii) axial profile determination of the main positive and negative ions, the electronic temperature and density, the gas temperature and the metastable state Ar(1s5) density; (iii) important modification of the infrared absorption spectra after plasma treatment in the cases of lignin and xylan, but not in the case of cellulose, suggesting a unexpected route for delignification and new materials synthesis from biomass / Doutorado / Física / Doutor em Ciências

In this thesis, we focused on the understanding of the synthesis and texturization processes of hydrophobic and (super)hydrophobic fluorinated surfaces by atmospheric plasmas.<p><p>First, we focused on the surface modifications of a model surface, the polytetrafluoroethylene (PTFE), by the post-discharge of a radio-frequency plasma torch. The post-discharge used for the surface treatment was characterized by optical emission spectroscopy (OES) and mass spectrometry (MS) as a function of the gap (torch-sample distance), and the helium and oxygen flow rates. Mechanisms explaining the production and the consumption of the identified species (N2, N2+, He, O, OH, O2m, O2+, Hem) were proposed. <p><p>The surface treatment was then investigated as a function of the kinematic parameters (from the motion robot connected to the plasma torch) and the gas flow rates. Although no change in the surface composition was recorded, oxygen is required to increase the hydrophobicity of the PTFE by increasing its roughness, while a pure helium plasma leads to a smoothing of the surface. Based on complementary experiments focused on mass losses, wettability and topography measurements coupled to the detection of fluorinated species on an aluminium foil by XPS, we highlighted an anisotropic etching oriented vertically in depth as a function of the number of scans (associated to the treatment time). Atomic oxygen is assumed to be the species responsible for the preferential etching of the amorphous phase leading to the rough surface, while the highly energetic helium metastables and/or VUV are supposed to induce the higher mass loss recorded in a pure helium plasma.<p><p>The second part of this thesis was dedicated to the deposition and the texturization of fluorinated coatings in the dielectric barrier discharge (DBD). The effects of the nature of the precursor (C6F12 and C6F14), the nature of the carrier gas (argon and helium), the plasma power, and the precursor flow rate were investigated in terms of chemical composition, wettability, topography and crystallinity by SIMS, XPS, WCA, AFM and XRD. We showed that hydrophobic surfaces with water contact angles (WCA) higher than 115° were obtained only in the presence of argon and were assumed to be due to the roughness created by the micro-discharges. Plasma-polymerized films in helium were smooth and no WCA higher than 115° was observed. We also studied the impact of the deposition rate and the layer thickness in the hydrophobic properties as well as the polymerization processes through the gas phase characterization.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

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This work is focused on modelling of atmospheric pressure high frequency (HF) discharges operated at relatively low power densities. Two types of devices are considered – the radio frequency capacitively coupled atmospheric pressure plasma jet and the microwave discharge sustained by surface electromagnetic waves. They are addresses as the plasma shower and the surface-wave discharge (SWD). Both of the considered devices operate in argon at atmospheric pressure (p = 1 bar). However, the difference in the frequency of the power coupling mechanism induces a big difference in plasma properties. This implies also that different modelling approaches have to be employed. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

The focused laser beam delivered by the high-power laser system PALS was used for laboratory simulation of high-energy-density events in a planetary atmosphere. Several model gas mixtures were prepared to mimic the mildly reducing early Earth's atmosphere (CO-N2-H2O) as well as the atmosphere of Saturn's moon Titan and the strongly reducing early Earth's atmosphere (CH4-N2-H2O). In situ investigation of transient species generated by the laser-induced dielectric breakdown in the gaseous mixtures was performed by optical emission spectroscopy (OES). Final products of laser-plasma initiated chemical reactions were identified and determined by advanced mass-spectrometry (SIFT-MS) and absorption FT-IR spectroscopy. High-power laser system SOFIA was utilized to simulate in our laboratory a high-velocity impact into the icy satellites of the outer planets of the Solar system. OES was engaged in probing the plasmas produced by the SOFIA beam focused on ice surfaces (water, methanol, formamide), while final products were analyzed by means of gas chromatography (GC/MS) and mass-spectrometry (SIFT-MS).