The goal of this research was to observe the changes in thickness and chemical characteristics that occur in Kapton® , a type of polyimide film, when exposed to heated solvents commonly used in cleaning and processing of these materials. Interference fringes present in transmission infrared spectra were used to calculate the thickness changes of the film, and attenuated total reflection infrared spectroscopy (ATR) was used to observe spectral shifts of the polymer film. Pieces of Kapton® film were immersed in heated solvents of n-methyl pyrrolidinone (NMP) and dimethylsulfoxide (DMSO) resulting in a rapid initial increase of film thickness by about 2.5 um during the first 20 minutes. After the initial increase and throughout the remainder of the 2 hour exposure, the film thickness varied little in the NMP solvent at all temperatures, 67, 95, and 125 oC. However, in DMSO, the behavior was more varied and this behavior was only observed in the 95 oC bath. The change in film thickness throughout the course of the experiment was about 1 μm less in the 125 oC as compared to the 95 oC, perhaps due to dissolution of the film by the solvent. When the film is exposed to heated solvents, a significant shift in the vibrational frequency of the asymmetric carbonyl stretch absorption to higher wavenumbers, as compared to the unexposed film, is observed. This indicates that there is some interaction between the Kapton® film and the solvent such that the strength of the carbonyl bond is lessened. Interactions could disrupt the intra- and intermolecular electron sharing and hinder the formation of the charged resonance form. / Introduction and background -- Preliminary experiments and method development -- Swelling studies on Kapton. / Department of Chemistry

This thesis focuses on the study of solvent degradation on polyimide films. Polyimides spun on silicon and freestanding polyimide films were exposed to solvents as a function of time at a constant temperature. The polyimide spun on silicon was immersed in dimethyl sulfoxide (DMSO) at 90oC for 30, 90, 270, and 450 min. Infrared spectra were obtained via multiple-bounce attenuated total reflection (ATR) and reflection-absorption (RA) spectroscopy. Thickness calculations were made using interference fringes obtained from RA spectra for each time interval. A reduction of thickness was observed with a total difference of 1.5 μm suggesting film degradation as a function of solvent exposure. Spectral changes in the symmetric and asymmetric carbonyl stretching modes were observed in both the ATR and RA sampling, which could be attributed to further curing of the polymer. Two experiments were performed on the freestanding polyimide film. The first experiment exposed the film to DMSO and the second to n-methyl pyrollidinone (NMP). In both instances, the freestanding film was immersed in the solvent at 98oC for 30, 90, 270, and 450 min. Infrared spectra were obtained via single-bounce ATR and transmission spectroscopy. No noticeable differences in spectra were observed. Thickness calculations were made using interference fringes obtained from transmission spectra. After immersion in DMSO, the thickness of the film increased initially, but then no significant changes in thickness occurred after 30 min. The initial increase in thickness may be due to solvent being trapped inside the film. After immersion in NMP, the thickness calculations showed no change in film thickness. However, our data as well as past researchers suggested some increase in thickness must occur due to solvent absorption. We propose that film degradation may be occurring in the NMP at approximately the same rate as swelling, thus no net decrease in thickness could be observed. This hypothesis is supported by the fact that a yellow coloration was visually observed to be in the solvent after immersion of the freestanding film. A subtraction of a spectrum of fresh NMP solvent from the spectrum of the yellow–colored solvent showed bands consistent with polyamic acid, a starting material for the freestanding film, which could have been formed from a hydrolysis reaction. / Literature review and introduction -- Evaluation of sampling techniques -- Film degradation studies on freestanding films. / Department of Chemistry

No description available.

Cette thèse présente la conception et la microfabrication d’une toute nouvelle configuration de pile à combustible en convection naturelle destinée à l’alimentation des appareils électroniques portables qui ne requiert aucun élément d’emballage externe (Pile à combustible sans emballage ou PLFC). On présente aussi les impacts majeurs de l’intégration d’un système de gestion d’eau complet (SGD) qui draine l’eau en surplus à la cathode pour la redistribuer vers l’anode et vers une surface d’évaporation imitant un réservoir d’hydrogène à base d’hydrures. La PLFC est constituée d’une membrane composite combinant un support mécanique de polymère (polyimide – Kapton®) et des chemins de conduction protonique (Nafion®), de collecteurs de courant métalliques et de couches catalytiques poreuses à base de nanoparticules de Pt/C. Le tout est intégré dans un seul feuillet de 50µm d’épaisseur sur une surface de 1cm[indice supérieur 2]. Des méthodes pour manipuler et graver le Kapton ainsi que pour intégrer le Nafion dans des procédés de microfabrication ont dû être développées. Un modèle analytique décrivant les résistances internes de la PLFC a aussi été réalisé. Ce modèle, combiné aux limites de dimensionnement causées par les méthodes de fabrication, a permis d’établir un processus de conception et de dimensionnement. La PLFC développée a démontré une importante augmentation de puissance volumique d’au moins 97% par rapport aux systèmes existants avec des emballages microfabriqués ou non. L’intégration d’un système de drainage de l’eau par des chemins hydrophiles à la cathode combinée à une redistribution d’eau vers l’anode et une surface d’évaporation a permis de doubler la puissance surfacique de la PLFC tout en stabilisant son fonctionnement. Finalement, on démontre dans cette thèse que dans les piles à combustible fonctionnant en convection naturelle, l’assèchement de l’anode joue un rôle prépondérant et que celle-ci doit être humidifiée, même lorsque la cathode est en surplus d’eau. De plus, en utilisant ce surplus pour alimenter un générateur d’hydrogène à base d’hydrures, on pourrait doubler la densité énergétique du système de pile à combustible.

The work presented involved simulation and experimental studies aimed at improving the methodology of positron annihilation lifetime spectroscopy (PALS), and applied PALS to gain a better understanding of doping mechanisms in ABO3 perovskite oxide materials. Reliable decomposition of PALS spectra requires an accurate description of the instrument resolution function (IRF) and the extrinsic, source component, annihilation events. The source terms include annihilations with the crystallites of the radionuclide and in the thin foil normally used to support the source. In principle both the IRF and the source correction terms can accurately be determined if samples exhibiting a true single lifetime component are measured. A series of annealing studies was performed on commercially available high purity polycrystalline metal samples to reduce the defect concentration below the approximate 0.1 ppm detection limit of PALS. The study showed that despite the numerous reports in literature it was not possible to reproduce the results with similar annealing conditions or sample purity. The possibility of utilising two-lifetime materials to enable the extraction of source correction terms is analysed using simulations, and by experiments on commercially available pure polycrystalline metals. The positron source is commonly deposited on, and supported by, a thin Kapton foil. As part of this work variable energy PALS (VE-PALS) performed at the Munich Research Reactor FRMII on Kapton foils were analysed. This enabled one of the source correction terms to be unambiguously determined. In consequence, the source correction terms for a Kapton supported positron source were extracted from measurements using annealed nickel exhibiting two positron lifetime components. PALS was applied to a study on donor doping of PbTiO3 ceramics using a series of lanthanide-ions. It has been proposed that the smaller Ln-ions may act as amphoteric dopants substituting either on the A-site as a donor, or on the Bsite as an acceptor. In this study Ln-ions in size from La down to Er were studied. A systematic variation in the average positron lifetime was observed where the value was constant from La to Gd and then reduced for the smaller ions. The decrease in average lifetime provides evidence for a reduction in the fraction of trapping to A-site related vacancy defects. The onset of a reduction in the average lifetime between Gd and Dy provides evidence for a change in the doping mechanism resulting in a relative reduction in the fraction of A-site vacancy positron trapping. In contrast to PbTiO3, donor doping of SrTiO3 normally results in electron charge compensation. Recently this has been very clearly demonstrated for La3+ doped SrTiO3 thin films grown by molecular beam epitaxy (MBE) which exhibit exceptional electron mobilities. A series of MBE films grown at University of California Santa Barbara were measured by VE-PALS at FRMII and have been analysed here. Strontium vacancies were identified, and a reduced bulk lifetime component was also observed. This enabled bulk lifetime values to be obtained from two of the films which were in good agreement with the previously obtained values from single crystal samples. A PALS study was also performed on a series of B-site donor, Nb, doped SrTiO3 crystals. High intensity reduced bulk components were observed and enabled measurements of the bulk lifetime. The highest Nb doping level samples showed the most intense reduced bulk lifetime but also clearly demonstrated the presence of Sr vacancies. The observation of A-site vacancy defects for both Nb-doped and La-doped SrTiO3 suggest that formation of these defects is preferred and are independent of the site of incorporation of the donor ion. Studies were also performed on acceptor doped SrTiO3. PALS measurements were made on a series of Fe-doped SrTiO3 ceramic samples, and VE-PALS measurements on pulsed laser deposition of Fe-doped SrTiO3 thin film samples were analysed. The positron lifetime measurements on the ceramic samples showed a dominant 166(3) ps component, a value less than the Ti-vacancy lifetime. It is proposed that the component contains a contribution from positrons trapping at oxygen vacancy substitutional Fe impurity complexes with a local charge that is neutral or negative. The measurements on the series of Fe-doped PLD SrTiO3 films suggest a complex relation between the vacancy defect content of a film and both the Fe-doping and PLD growth conditions. Films grown with higher laser fluence values contained Sr vacancy defects, in contrast to previous studies of acceptor doped perovskites. Films grown with low laser fluence or with high Fe-content showed dominant trapping to Ti-vacancy related defects.

L'émergence des nouvelles applications dans le domaine de la micro et nanotechnologie requière de faibles coûts de fabrication et la caractérisation de dispositifs électroniques ayant des propriétés telles que la flexibilité, la portabilité, la légèreté, et des matériaux de faibles coûts. Les méthodes traditionnelles de fabrication impliquent de longues étapes de production, et des procédés de fabrication impliquant des étapes avec des produits chimiques. Le but de cette thèse est d'étudier la conception et la caractérisation de capteurs d'ammoniac et d'ozone sur support souple fabriqués par des processus de photolithographie et de gravure laser. Le support flexible est composé de Kapton avec des électrodes interdigitées de Ti/Pt pour la détection de gaz et un microchauffage. Les motifs du circuit ont été réalisés par photolithographie et gravure laser. L'utilisation de gravure laser sur support souple permet de réduire les coûts liés au temps de fabrication, aussi représente une excellente alternative aux processus chimiques. Des nanoparticles de ZnO déposées par gouttes ont été utilisées comme matériaux sensibles en raison de leurs excellentes propriétés dans la détection de gaz. Les conditions de détection de gaz ont été étudiées pour différentes concentrations d'ozone et d'ammoniac. Afin de tester une méthode de dépôt utilisée dans la production industrielle à grande échelle, un dépôt par spray ultrasonique a été effectué. Les capteurs réalisés montrent une large gamme de détection de 5 ppb à 500 ppb à 200 °C pour l'ozone et de 5 ppm à 100 ppm à 300 °C pour l'ammoniac avec une bonne reproductibilité, stabilité et de rapides temps de réponse et de retourn. / Nowadays the emerging of new applications in the micro and nanotechnology field required to reduce fabrication costand to improve electronic devices with properties such as flexibility, portability, lightweight, and low cost. Traditional methods involve expensive and long production steps, and chemical vapor deposition. The purpose of this work is to present the conception and characterization of flexible ammonia and ozone sensors fabricated by photolithography and laser ablation processes. The flexible platform is composed of Kapton substrate with interdigitated Ti/Pt electrodes for gas detection and a micro-heater device. The circuit patterns were realized by photolithography and laser ablation. Photolithography is a well-known and reliable patterning process used on rigid substrate. The application of laser ablation process not only reduces fabrication time, but also represents an excellent viable alternative instead of chemical processes. ZnO thin films deposited by drop coating have been used as sensitive materials due to their excellent properties in the gas detection. The gas sensing condition and the performances of the devices are investigated for ozone and ammonia at different gas concentrations and different thin film thicknesses. In order to test a deposit methodology used in large scale industrial production, an ultrasonic spray deposition was done. The sensor provides a wide range of detection from 5 ppb to 500 ppb for ozone and from 5 ppm to 100 ppm for ammonia. Their best sensibilities were obtained at 200°C for ozone and 300 °C for ammoniac with good repeatability, stability and fast response/recovery time.

Cette thèse fait partie des efforts de recherche pour étudier l’intégration hétérogène sur le substrat souple des nœuds de communicants pour les réseaux de capteurs sans fil dans la bande à 60GHz. Le System in Package (SiP) devrait avoir une consommation d'énergie très faible et être faible coût pour répondre aux exigences des applications telles que la Surveillance de Santé de Structure (Structure Health Monitoring - SHM en anglais) dans le domaine aéronautique par exemple. Chaque nœud est composé des nano-capteurs, des transceivers et des antennes d’émission et de réception. Les nanotechnologies ont permis le développement de nano-capteurs ultra-sensibles à base de nanoparticules. Les transceivers deviennent de plus en plus miniaturisés et donc permettre la possibilité de les reporter sur le substrat flexible. Les antennes peuvent être intégrés sur le substrat flexible avec les nano-capteurs développés et émetteurs miniaturisés, ce qui est l'approche très innovante. Dans cette thèse, nous présenterons les procédés technologiques adaptés pour réaliser les différents circuits passifs (résonateurs, antennes, rectennas, etc…) sur le substrat souple en utilisant la photolithographie conventionnelle. La technique de la puce retournée a été choisie pour l’intégration des transceivers à 60 GHz, la formation des bosses d’interconnexion en or directement sur le substrat souple par les dépôts électrolytiques est présentée ici pour la première fois. La concordance entre les mesures expérimentales et les simulations numériques démontre la fiabilité et la reproductibilité des procédés choisis. De plus, pour une application à volume élevé comme les réseaux de capteurs sans fil, le coût de fabrication par nœud peut être considérablement réduit, et devient comparable avec l’impression jet d'encre qui est un procédé à faible coût. / This thesis is part of research effort to develop a 3D heterogeneous integration of wireless sensor node on flexible substrate for the unlicensed 60GHz band. The System in Package (SiP) should have a very low power consumption and very low cost to meet the requirements of applications like Wireless Sensor Networks (WSNs) for Structure Health Monitoring (SHM). Using a flexible substrate for wireless sensor node integration can offer the advantage of being localized in areas with access difficulty especially in non-planar area. Each node is composed of nano-sensors, transceivers and TX/RX antenna. Nanotechnologies made it possible the development of ultra-sensitive nano-sensors based on nanoparticles deposition. Transceivers become more and more miniaturized and hence enable the possibility of postpone them onto flexible substrate. The antennas can be integrated on the flexible substrate along with the developed nano-sensors and miniaturized transceivers, which is the very innovative approach. In this work, we propose customized photolithography processes to manufacture the passive element circuits (resonators, antennas, rectennas, etc…) on flexible substrate. The technique of flip-chip was used for the integration of 60 GHz transceivers, a novel technique to form Au interconnection bump directly onto the flexible substrate by using electrodeposition process is also presented here for the first time. The concordance between the simulations and the measurements is observed, which proves the reliability and reproducibility of such process technique. Furthermore, for a high-volume application like the node deployment of WSNs, wafer cost reductions can significantly lower the total cost per node and became comparable to a low-cost inkjet printing process.

No description available.

The electrostatic ion beam trap (EIBT) was designed by D. Zajfman during the previous decade. This ion trap combines many properties of the Fourier-transform ion cyclotron resonance (FTICR) mass analyzer and time-of-flight (TOF) mass analyzer. There are several advantages for the electrostatic ion beam trap. First, large mass-to-charge particles in an electrostatic field could be easier to analyze. Second, there is a folded flight path, which could make the mass analyzer smaller compared to conventional TOF mass analyzer. This principle of operation of this ion trap is analogous to an optical resonator. The ions are trapped in a voltage valley and oscillate between the two parallel sets of mirror electrodes with high voltages. In this thesis, I first describe a new type of miniaturized electrostatic ion beam trap mass analyzer that consists of two printed circuit boards (PCBs). The facing surfaces of these boards are imprinted with copper electrodes. The center of the boards is field free and at ground potential with ion mirrors and Einzel lenses on either side. A charge detector is attached to the center for recording the time-dependant motion of the ions in the field. The PCB-based EIBT design is easier to construct than the original EIBT mass analyzer. The electrostatic fields are optimized by adjusting the potential on the mirror electrodes as well as the geometry of the electrodes. Although nondestructive charge detection is much less sensitive for small ions, this detection is ideal for analysis of large ions. The planar electrostatic ion beam trap is inexpensive, small, and simple to operate. The PCB EIBT device was designed, built, and tested using metal samples such as copper and nickel. The electric field of the PCB EIBT is not the same as that of the original EIBT. Unfortunately, there were no ion signals captured in image charge detector. Another new type of miniaturized electrostatic ion beam trap was made by depositing electrodes onto Kapton film. Seven thin tin/copper traces (1 mm wide by 0.015 mm thick) were deposited onto each side of a flat, flexible circuit board substrate (Kapton film 0.15 mm thickness). The film was rolled to form a cylinder. The flexible EIBT is small (4.5 cm × 8 cm), and lightweight (~1 g). This device was tested using laser ablation of CsI. The CsI signals were detected by the charge detector, amplified and sent to the oscilloscope. Fourier transformation was used to convert the data to the frequency domain spectrum. The resolution of Cs+ is around 1000 (m/Δm) from initial flexible EIBT test. The mass accuracy of the Cs+ peak is better than 0.1%.

No description available.