A high throughput proteomic analysis method is described here that uses more economically favorable, easily manufactured probe surface that can be directly incorporated on the MALDI target. On-Probe Affinity Capture (OPAC) MALDI is a method that uses the RF pulsed plasma modified target surfaces for the protein purification, separation and identification all on the same single probe and one of the highest advantage of this method is the number of different experiments that can be carried out simultaneously using the intelligent design of the probe. The new design of the OPAC probe presented in this dissertation gives the ability to perform about 100 different experiments on one single MALDI target. These OPAC probes can be used for the fractionation and analysis of proteins from complex biologically derived samples. The separated proteins can be identified on the OPAC probe using it directly as the MALDI target and selecting a proper elution solution that depends on the chemistry of the OPAC probe, the surface bound proteins can be eluted and incorporated into the matrix crystal. This dissertation focuses mainly on developing this method for analysis of different samples. A tryptic digest of a single protein was separated and identified by submitting the peak lists to MASCOT database search and the sequence coverage obtained before and after fractionation has been compared. Then a mixture of tryptic peptides of five different known proteins were fractionated on OPAC surfaces and the identification of proteins obtained was compared before and after fractionation. Further developing this technique, biologically derived mixtures of proteins from two different well studied sources have been analyzed using OPAC-MALDI. Escherichia coli bacterial proteome was digested and fractionated and the peptides were studied using De Novo sequencing method and their affinity fractionation behavior is confirmed by calculating the iso electric point (pI) and the hydrophobicity of the predicted peptide sequence. Synechosystis sp PCC 6803 was cultured and the protein extracts were prepared for the OPAC studies. The clear fractionated of this mixture was observed and the amount of information derived after fractionation is found to be significantly higher than the unfractionated sample. Taking a slightly different approach, a phosphoprotein binding OPAC probe was prepared using commercially available poly(methyl methacrylate) (PMMA) film. The hydrolyzed PPMA films were reacted with CuCl2 solution to incorporate metal ions on the surface by electrostatic interaction, which then facilitates the phosphoprotein binding on the OPAC probe. This was demonstrated using a binary mixture of commercially available peptides and fractionating the mixture on Cu-impregnated PMMA film. Finally, in a collaborative work, the possibility of increased surface binding capacity was explored by using a synthetic organic nanosponge surface that expands and collapses due to change of pH. These brush polymers were prepared by Dyer group and a binary mixture of peptides were fractionated and analyzed by MALDI MS.

Du fait de la réduction des dimensions en microélectronique, les procédés de gravure par plasmas ne peuvent plus satisfaire aux exigences de l'industrie. De nouvelles stratégies sont en cours de développement. Ce travail consiste en l'étude de plasmas pulsés de HBr/O2 comme une alternative pour la gravure du silicium. Divers diagnostics dans un réacteur industriel 300 mm sont utilisés pour caractériser le plasma tandis que la gravure du silicium est étudiée par XPS et par microscopie électronique. Lorsque le plasma est pulsé à faible rapport cyclique, sa température et sa dissociation sont fortement réduits. Le flux de Br radicalaire par rapport à la période ON du plasma augmente tandis que l'influence du radical O diminue, ce qui conduit à une amélioration de la sélectivité par rapport au SiO2 et à une gravure plus homogène. Les profils des structures gravées peuvent être contrôlés par la formation de la couche de passivation sur les flancs dépendant également du rapport cyclique. / The continuous downscaling in microelectronics imposes increasing demands on the plasma processes and traditional ways for process optimization reach their limits. New strategies are needed and innovations in the field of plasma processes are being developed: e.g. the use of pulsed plasmas. In this thesis, a pulsed HBr/O2 etch plasma is studied. Various in-situ diagnostics are used to characterize pulsed plasmas in an industrial 12” etch reactor. The silicon etching is investigated by XPS and electron microscopy. We show that the plasma dissociation and temperature are reduced if the plasma is pulsed at low duty cycles. The Br radical flux with respect to the on-time of the plasma is increased and the influence of the O radical is decreased, leading to enhanced time compensated silicon etch rates, a higher selectivity towards SiO2 and a more homogeneous etching. The pattern profiles can be controlled via the sidewall passivation layer formation that is closely linked to the duty cycle.

Interactions between flames and thermal phenomena are the guiding thread of this work. Flamesproduce heat indeed, but can also be affected by it. Large Eddy Simulations (LES) are used hereto investigate these interactions, with a focus on two main topics: wall heat transfer andcombustion control. In a first part, wall heat transfer in a rocket engine sub-scale CH4/O2 burner isstudied. In the context of launchers re-usability and cost reduction, which are major challenges,new propellant combinations are considered and wall heat fluxes have to be precisely predicted.The aim of this work is to evaluate LES needs and performances to simulate this kind ofconfiguration and provide a computational methodology permitting to simulate variousconfigurations. Numerical results are compared to experimental data provided by the TechnischeUniversität München (Germany). In a second part, combustion control by means of NanosecondRepetitively Pulsed (NRP) plasma discharges is studied. Modern gas turbine systems use indeedlean combustion with the aim of reducing fuel consumption and pollutant emissions. Lean flamesare however known to be prone to instabilities and combustion control can play a major role in thisdomain. A phenomenological model which considers the plasma discharges as a heat source isdeveloped and applied to a swirl-stabilized CH4/Air premixed lean burner. LES are performed inorder to evaluate the effects of the NRP discharges on the flame. Numerical results are comparedwith experimental observations made at the King Abdulla University of Science and Technology(Saudi Arabia).

"The ablative Teflon pulsed plasma thruster (PPT) is an onboard electromagnetic propulsion enabling technology for small spacecraft missions. The integration of PPTs onboard spacecraft requires the understanding and evaluation of possible thruster/spacecraft interactions. To aid in this effort the work presented in this thesis is directed towards the development and application of Langmuir probe techniques for use in the plume of PPTs. Double and triple Langmuir probes were developed and used to measure electron temperature and density of the PPT plume. The PPT used in this thesis was a laboratory model parallel plate ablative Teflon® PPT similar in size to the Earth Observing (EO-1) PPT operating in discharge energies between 5 and 40 Joules. The triple Langmuir probe was operated in the current-mode technique that requires biasing all three electrodes and measuring the resulting probe currents. This new implementation differs from the traditional voltage-mode technique that keeps one probe floating and requires a voltage measurement that is often susceptible to noise in the fluctuating PPT plume environment. The triple Langmuir probe theory developed in this work incorporates Laframboise’s current collection model for Debye length to probe radius ratios less than 100 in order to account for sheath expansion effects on ion collection, and incorporates the thin-sheath current collection model for Debye length to probe radius ratios greater than 100. Error analysis of the non-linear system of current collection equations that describe the operation of the current-mode triple Langmuir probe is performed as well. Measurements were taken at three radial locations, 5, 10, and 15 cm from the Teflon® surface of the PPT and at angles of 20 and 40 degrees to either side of the thruster centerline as well as at the centerline. These measurements were taken on two orthogonal planes, parallel and perpendicular to the PPT electrodes. A data-processing software was developed and implements the current-mode triple Langmuir probe theory and associated error analysis. Results show the time evolution of the electron temperature and density. Characteristic to all the data is the presence of hot electrons of approximately 5 to 10 eV at the beginning of the pulse, occurring near the peak of the discharge current. The electron temperature quickly drops off from its peak values to 1-2 eV for the remainder of the pulse. Peak electron densities occur after the peak temperatures. The maximum electron density values on the centerline of the plume of a laboratory PPT 10 cm from the Teflon® surface are 6.6x10^19 +/- 1.3x10^19 m^-3 for the 5 J PPT, 7.2x10^20 +/- 1.4x10^20 m^-3 for the 20 J PPT, and 1.2x10^21 +/- 2.7x10^20 m^-3 for the 40 J PPT. Results from the double Langmuir probe taken at r=10 cm, theta perpendicular=70 degrees and 90 degrees of a laboratory PPT showed good agreement with the triple probe method."

A pulsed-plasma jet (called a "spark-jet" by other researchers), is a high-speed synthetic jet that is generated by striking an electrical discharge in a small cavity. The gas in the cavity pressurizes owing to the heating and is allowed to escape through a small orifice. A series of experiments were conducted to determine the characteristics of the pulsed-plasma jet issuing into stagnant air at a pressure of 45 Torr. These results show that typical jet exit velocities of about 250 m/s can be induced with discharge energies of about 30 mJ per jet. Furthermore, the maximum pulsing frequency was found to be about 5 kHz, because above this frequency the jet begins to misfire. The misfiring appears to be due to the finite time it takes for the cavity to be recharged with ambient air between discharge pulses. The velocity at the exit of the jet is found to be primarily dependent on the discharge current and independent of other discharge parameters such as cavity volume and orifice diameter. Temperature measurements are made using optical emission spectroscopy and reveal the presence of considerable non-equilibrium between rotational and vibrational modes. The gas heating efficiency was found to be 10% and this parameter is shown to have a direct effect on the plasma jet velocity. These results indicate that the pulsed-plasma jet creates a sufficiently strong flow perturbation that is holds great promise as a supersonic flow actuator. An experimental study is conducted to characterize the performance of a pulsed-plasma jet for potential use in supersonic flow control applications. To obtain an estimate of the relative strength of the pulsed-plasma jet, the jet is injected normally into a Mach 3 cross-flow and the penetration distance is measured by using schlieren imaging. These measurements show that the jet penetrates 1.5 [delta], where [delta] is the boundary layer thickness, into the cross-flow and the jet-to-crossflow momentum flux ratio is estimated to be 0.6. An array of pulsed-plasma jets was issued from different locations upstream of a 30-degree compression ramp in a Mach 3 flow. Furthermore, two different jet configurations were used: normal injection and pitched and skewed injection. The pitched and skewed configuration was used to see if the jets could act as high-bandwidth pulsed vortex generators. The interaction between the jets and the separation shock was studied using phase-locked schlieren imaging. Results show that the plasma jets cause a significant disturbance to the separation shock and clearly influence its unsteadiness. While all plasma jet configurations tested caused an upstream motion of the separation shock, pitched and skewed plasma jets caused an initial downstream shock motion before the upstream motion, demonstrating the potential use of these plasma jets as vortex generator jets. The effect of the plasma jet array on the separation shock unsteadiness is studied in a time-resolved manner by using 10 kHz schlieren imaging and fast-response wall pressure measurements. An array of three pulsed-plasma jets, in a pitched and skewed configuration, is used to force the unsteady motion of the interaction formed by a 24° compression ramp in a Mach 3 flow. The Reynolds number of the incoming boundary layer is Re[theta]=3300. Results show that when the pulsed jet array is placed upstream of the interaction, the jets cause the separation shock to move in a quasi-periodic manner, i.e., nearly in sync with the pulsing cycle. As the jet fluid convects across the separation shock, the shock responds by moving upstream, which is primarily due to the presence of hot gas and hence the lower effective Mach number of the incoming flow. Once the hot gases pass through the interaction, the separation shock recovers by moving downstream, and this recovery velocity is approximately 1% to 3% of the free stream velocity. With forcing, the low-frequency energy content of the pressure fluctuations at a given location under the intermittent region decreases significantly. This is believed to be a result of an increase in the mean scale of the interaction under forced conditions. Pulsed-jet injection are also employed within the separation bubble, but negligible changes to the separation shock motion were observed. These results indicate that influencing the dynamics of this compression ramp interaction is much more effective by placing the actuator in the upstream boundary layer. / text

L'industrie de la microélectronique s'appuie sur l'évolution constante de la miniaturisation des transistors. D'ici 2016, cette industrie atteindra le nœud technologique 16 nm dans lequel il faudra être capable de graver des structures de dimensions nanométrique ayant de très forts facteurs d'aspect. Cependant, les procédés de gravure actuels montrent de sérieuses limitations en termes de contrôle des profils et des dimensions critiques lorsqu'il faut graver de telles structures. Les problèmes rencontrés sont liés d'une part à des limitations intrinsèques des procédés plasmas et d'autre part à l'apparition de nouveaux phénomènes lorsque la dimension des structures à graver devient nanométrique. Dans le cadre de cette thèse, un nouveau mode de fonctionnement des sources à plasma est étudié pour développer des procédés de gravure adaptés aux prochaines générations de circuits intégrés : les plasmas modulés en impulsions courtes. Les premiers travaux réalisés s'appuient sur de puissantes techniques d'analyses du plasma (spectroscopie d'absorption VUV, sonde de flux ionique, analyseur électrostatique) dans le but de mettre en évidence l'impact des paramètres de la modulation en impulsion du plasma sur ses caractéristiques physicochimiques (flux et énergie des radicaux et des ions). Ces diagnostics ont tout d'abord permis de définir très clairement les conséquences de la modulation en impulsion du plasma sur les flux de radicaux réactifs qui bombardent le substrat : le rapport de cycle est LE paramètre clé pour contrôler la chimie du plasma car il permet de contrôler le taux de fragmentation du gaz par impact électronique. Dans un second temps, nous avons également démontré que dans les plasmas électronégatifs et pour une puissance RF de polarisation donnée, l'énergie des ions augmente lorsque le rapport de cycle diminue. Fort de ces connaissances fondamentales sur les plasmas, des analyses des surfaces (XPS, MEB, Raman…) ont permis de comprendre les mécanismes mis en jeux lors de l'interaction plasma- surface. Ainsi, il a été possible de développer des procédés de gravure pulsés pour plusieurs étapes de la grille de transistor (prétraitement HBr, gravure du Si-ARC, gravure du pSi). Les prétraitements HBr sont incontournables pour réduire la rugosité de bord de ligne de transistor. Lors de cette étape, une couche riche en carbone limite l'effet bénéfique des UV du plasma sur la diminution de la rugosité. Grâce à l'utilisation des plasmas pulsés, l'origine de cette couche a été mise en évidence : elle résulte du dépôt sur les motifs d'espèces carbonées non volatiles issues de la photolyse de la résine qui sont relâchées dans le plasma. Dans ce système bicouche, les contraintes de la couche carbonée dure vont se relaxer dans le volume mou de la résine par phénomène de « buckling » qui se traduit par une hausse de la rugosité de bord de ligne. Nous avons montré que cela peut être évité en minimisant l'épaisseur de cette couche, ce qui peut être obtenu notamment en pulsant le plasma. La gravure de la couche anti-réflective Si-ARC qui sert de masque dur et celle de la grille en poly Silicium reposent sur l'utilisation de plasmas fluorocarbonés. Mais dans ce type de plasma, la production de précurseurs pour la polymérisation est diminuée quand le plasma est pulsé, conduisant à une perte de sélectivité et d'anisotropie. Les plasmas synchronisés pulsés ne sont donc pas de bons candidats pour les étapes de gravure considérées. Pour pallier à ce problème, un autre mode de polarisation a été étudié : les plasmas pour lesquels seule la puissance de polarisation est pulsée. Dans le cas de la gravure du Si-ARC, il est possible d'obtenir des profils très anisotropes avec une sélectivité vis-à-vis de la résine nettement améliorée. Pour la gravure du Silicium, les effets d'ARDE ont pu être diminués tout en améliorant la sélectivité. Ces résultats sont très encourageants. / Microelectronics industry is based on the continuous transistor downscaling. By the year 2016, the 16nm technological node would be achieved, so that structures with nanometric dimensions and high aspect ratio would have to be etch. However, traditional etching processes shows major limitations in terms of pattern profiles control and critical dimensions when such structures have to be etch. The encountered problems are related directly to intrinsic limitations of plasmas processes but also to the emergence of new phenomena’s when the dimensions of structures to etch become nanometric. In the framework of this thesis, a new strategy to produce plasma has been evaluated to develop etching plasmas processes adapted to next integration circuit generations: the pulsed plasmas. Over a first phase, the impact of plasma pulsing parameters (frequency and duty cycle) on the plasma physico-chemical characteristics has been highlight. This has been achievable thanks to advanced plasma analyse techniques (VUV broad band absorption spectroscopy, ion flux probe, retarding electrical field analyser…) developed to allow time resolved measurements. For the neutral flux, diagnostics have revealed that duty cycle is THE key control knob to tune the plasma. Indeed, a low duty cycle leads to reduced parent gas fragmentation and thus a reduced chemical reactivity. On the other hand, in electronegative plasmas and for constant RF power, we have demonstrated that ion energy is considerably increased when the ions flux is decreased (i.e. when the duty cycle is decreased). Then, surface analyses (XPS, SEM, Raman spectroscopy…) brought out the mechanisms involved during the plasma-surface interaction. Deeper comprehension of impact of pulsing parameters enables to develop pulsed plasmas processes more easily. These works are focused on the top of the transistor gate and deal with the following steps: HBr cure, Si-ARC etching, poly-silicon etching. HBr cure is an essential pre-treatment of the 193 nm photoresist to decrease the Line Width Roughness (LWR) of transistor gate. During this step, a carbon rich layer is formed on the surface of the resist pattern and degrades the beneficial action of UV plasma light on LWR reduction. Thanks to use of pulsed plasmas, the origin of this carbon rich layer has been highlight: UV induced modifications in polymer bulk lead to outgassing of volatiles carbon-based products in the plasma. These carbon containing moieties are fragmented by electron impact dissociation reaction in the plasma, which create sticking carbon based precursors available for re-deposition on the resist patterns. The impact of this layer on the LWR and resist pattern reflow is studied, and a possible mechanical origin (i.e. buckling instabilities) is highlighted. Finally, we showed that the use of pulsed HBr curing plasma allows to reduce and control the thickness of the graphite-like layer and to obtain LWR reduction that are comparable to VUV treatment only. The Si-ARC layer, used as hard mask, and the poly-silicon gate etching are based on the use of fluorocarbon plasmas. However, in these plasmas, the production of radicals enable for the polymerisation is decreased when the duty cycle is reduced. It leads to loss of both anisotropy and selectivity. Synchronised pulsed plasmas are then not adapted to such etching processes. To overcome this problem, a new way to produce plasma has been studied: the ICP source power is maintained constant and only the bias power is pulsed. Regarding Si-ARC etching, very anisotropic profiles are obtained and the Si-ARC to resist selectivity is enhanced while pulsing the rf bias to the wafer. In the case of poly-silicon etching, the ARDE effects are significantly reduced while the selectivity regarding the oxide is improved. These results are very promising for the development of polymerising plasmas processes.

Le travail de la thèse est focalisé sur l’ élaboration plasma d’un revêtement multicouches avec une couche supérieure anti-brouillard et une couche inférieure dite barrière sur un polycarbonate. L’ensemble des travaux est divisé en 3 parties: élaborations des deux monocouches barrière ou antibuée puis dépôt de la multicouche barrière - antibuée. La polymérisation plasma de la couche barrière est effectuée à partir d’un mélange de dioxygène et d’un précurseur organosilicié : l’hexaméthyledisiloxane ou le 2,4,6,8-tétraméthylcyclotétrasiloxane ou bien encore le triéthoxyfluorosilane. La caractérisation des couches minces obtenues repose sur la spectroscopie Infrarouge à Transformée de Fourier , la spectroscopie de photoélectrons X et la microscopie à force atomique. L’influence des conditions de dépôt plasma comme la puissance, la proportion monomère/dioxygène, le temps du dépôt sur la structure chimique et l’hydrophobicité de la surface des différents types de couches organosiliciées est étudiée. Les résultats de la perméation avec l’eau liquide ou le dioxygène montrent que la propriété barrière des couches organosiliciées non fluorées est meilleure que pour la couche fluorée. L’élaboration de copolymères anti-buée repose sur l’utilisation de combinaisons entre deux précurseurs hydrophile et hydrophobe en voie plasma pulsé. Les précurseurs tels que le 2-(diméthylamino)éthyl méthacrylate ou l’acide acrylique sont choisis pour leur hydrophile alors que le 1H,1H,2H-perfluoro-1-décène représente la partie oléophobe. La propriété anti-brouillard et sa stabilité à long terme après un vieillissement thermique ou en milieu humide est dépendante de leurs structure et morphologie. / The PhD work is focused on the deposition of a multilayer coating with an anti-fog top layer obtained thanks to the plasma copolymerization of hydrophilic and hydrophobic monomers and an intermediate barrier layer, also obtained by plasma deposition on polycarbonate. The work is divided into 3 parts: the independently preparations of the two monolayers, barrier and anti-fogging ones, then the barrier-antifog multilayer deposition. The characterization of the thin films obtained is based on Fourier Transform Infrared Spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy.The barrier plasma-layer is issued from by the mixture of dioxygen and one of these three organosilicon precursors : hexamethyledisiloxane ; 2,4,6,8-tetramethylcyclotetrasiloxane ; triethoxyfluorosilane. The influence of the plasma conditions such as discharge power, monomer/dioxygen ratio, deposition duration on the chemical structure and the hydrophobicity of the different types of the organosilicon layers was studied. The results of permeation with liquid water or dioxygen show that the barrier property of the organosilicon layer is more efficient than that of the fluorinated layer. Anti-fog plasma-copolymer is synthetized from two hydrophilic and hydrophobic precursors deposited by pulsed plasma mode. The precursors such as 2-(dimethylamino) ethyl methacrylate and acrylic acid were selected for the hydrophilic part while the 1H, 1H, 2H-perfluoro-1-decene will be associated to the oleophobic part. The dependence of the chemical structure and the morphology of the anti-fog layers is studied according to the hydrophilic/oleophobic distribution and the deposition time.

No description available.

No description available.

<p>  </p> <p>  </p> <p>An approach to modify surface flashover of insulators in vacuum by limiting duration of its high-current stage responsible for the damaging effects of a classic flashover was developed. The flashover assembly was made by TorrSeal-gluing copper electrodes (10 x 10 x 0.5 mm) to both side of an alumina ceramic sheet (0.635 mm thick). The modified flashover, referred to as low energy surface flashover (LESF), was achieved by utilization of a high voltage (HV) nanosecond pulser or addition of a resistor in series with the LESF assembly when HV DC was utilized. The duration of LESF was visualized by ICCD fast photography to be 100 – 200 ns accompanying electrical characteristics measurements, which gave insight of a way to control the flashover duration by inserting additional capacitor in parallel with the LESF assembly to increase the stored energy prior to breakdown. The LESF assembly was tested for > 1.5 million consecutive pulses and remained operational, while operation in high energy regime with parallel capacitor (4nF) lead to significant damage after 200 pulses.</p> <p>The igniting capabilities of LESF assembly was demonstrated via successful triggering of vacuum arc and a prototype pulsed plasma accelerator. The plasma plume propagation speed and angular distribution was measured via Langmuir probes. Efforts were made for temporally resolved spectroscopy measurements. </p> <p>The LESF assembly was improved by replacing TorrSeal-gluing with direct bonding of copper to alumina ceramic and changing the configuration from parallel plate to coaxial. The improved assembly was demonstrated to be operational throughout and after an extended test of 10 million pulses. A higher resolution ICCD photography revealed finer LESF discharge features including initial bright line across the insulator developing into a double-jet plasma plume propagating at around 10⁵m/s and later-on point-like attachment of the discharge column to the electrodes. The composition of the plasma and erosion pattern on the LESF assembly was studied via SEM/EDX analysis, which supported the predominant ceramic erosion over copper electrodes erosion.</p>