Cardiovascular complications associated with elevated levels of glucose in the blood (Hyperglycemia, HG) is a growing health concern. HG is known to be associated with a variety of cardiovascular morbidities including higher incidence of electrical disturbances. Although effects of chronic HG have been widely investigated, electrophysiological effects of acute hyperglycemia are relatively less known. Further, hyperglycemic effects on adrenergic response is not widely investigated. We used excised ventricular tissues from mice to record trans-membrane potentials during a variety of pacing protocols to investigate cellular/tissue level electrophysiological effects of acute hyperglycemia and adrenergic stimulation (1µM Isoproterenol, a β-adrenergic agonist). A custom program was used to compute action potential durations (APD), maximal rates of depolarization (dv/dtmax), and action potential amplitudes (APA) from the recorded trans-membrane potentials. From these computed measures, electrical restitution and alternans threshold were quantified. Restitution was quantified using the Standard Protocol (SP; basic cycle length BCL= 200ms), Dynamic Protocol (DP; 200-40ms or until blockade) and a novel diastolic interval (DI) control protocol with Sinusoidal Changes in DI. Results from 6 mice show that acute hyperglycemia causes prolongation of the APD. Effects of adrenergic stimulation during acute hyperglycemia were partially blunted compared with non-hyperglycemic state, i.e. hyperglycemia minimized the decrease in APD that was produced by adrenergic stimulation. Similar, but less consistent (across animals) effects were seen in other electrophysiological parameters such as alternans threshold. These results show that acute hyperglycemia may itself alter cellular level electrophysiology of myocytes and importantly, modify adrenergic response. These results suggest that in addition to long term re-modeling that occurs in diabetes, acute changes in glucose levels also affect electrical function and further may contribute to systemically observed changes in diabetes by blunting adrenergic response. Therefore, further investigation into the electrophysiological effects of acute changes in glucose levels are warranted.

Les techniques polarimétriques ont connu un récent essor, notamment dans le domaine de l'imagerie satellitaire ou du biomédical. Ces techniques se sont étendues au cas des milieux désordonnés. Dans ce contexte, des théories unifiées sont apparues, mêlant cohérence temporelle et spatiale, dépolarisation...L'équipe CONCEPT de l'Institut Fresnel, est aujourd'hui étroitement impliquée dans l'étude de la polarisation dans le speckle de la lumière diffusée. Des résultats nouveaux ont été mis en évidence, comme la dépolarisation spatiale multi-échelle, les phénomènes de repolarisation temporelle, la dépolarisation spectrale. La prédominance de ces effets est naturellement liée à l'origine du speckle (surface, volume), mais aussi aux niveaux d'absorption et aux propriétés structurelles (rugosités, hétérogénéités) des milieux désordonnés.La plupart de ces études sont de nature théorique. Ce constat est lié à l'extrême difficulté de mesurer avec précision la polarisation de la lumière à l'échelle du grain de speckle. Les travaux réalisés dans le cadre de cette thèse avaient ainsi pour but de remédier à cette lacune, et nous ont amenés à développer une procédure optique pour extraire les états de polarisation, et le degré de polarisation (DOP), à l'échelle du grain de speckle. En conséquence la polarisation est ici extraite pour chaque pixel d'une matrice CCD, ce qui amène tout d'abord à mettre en évidence des nuages de points plus ou moins étendus sur la sphère de Poincaré. Les histogrammes de DOP sont ensuite utilisés comme véritables signatures des milieux désordonnés. / Polarimetric techniques knew a recent rise, especially in the field of satellite imaging andbiomedical, optics. These techniques are extended to the case of the disordered media, for applications related to the imaging scattering medium. In this context the unified theories appeared, combiningtemporal and spatial coherence, and depolarization...The team CONCEPT at Fresnel Institute, established in 2012, is now closely involved in the study of the polarization state of the scattered light within the speckle size. New results have been highlighted, such as the multi-scale spatial depolarization, the temporal enpolarization phenomena, and the spectral depolarization. The predominance of these effects is naturally related to the speckle origin (surface, bulk), but also to the absorption levels and the structural properties (roughness, heterogeneities) of disordered media.However, most of these studies are theoretical, and few experiments were previously able to reinforce the predictions. This statement is related to the extreme difficulty of accurately measuring the polarization of light across the speckle grain. Our thesis had the aim to address this gap in, and we were able to develop a procedure to extract the optical polarization states, and the degree of polarization (DOP), inside of the speckle grain.Consequently, the polarization is here extracted for each pixel of a CCD matrix, which leads first to highlight a cloud of points more or less extended on the Poincaré sphere. DOP histograms are then used as genuine signatures of disordered media.

The influence of depolarization and its role in causing data retention failure in ferroelectric memories is investigated. Ferroelectric Hf₀.₅Zr₀.₅O₂ thin films 8 nm thick incorporated into a metal-ferroelectric-metal capacitor are fabricated and characterized with varying thicknesses of an Al₂O₃ interfacial layer. The magnitude of the depolarization field is adjusted by controlling the thickness of the Al₂O₃ layer. The initial polarization and the change in polarization with electric field cycling is strongly impacted by the insertion of Al₂O₃ within the device stack. Transient polarization loss is shown to get worse with larger depolarization fields and data retention is evaluated up to 85 °C.

While dental caries represents the major chronic disease of humans, visual and tactile inspection are the methods of choice in daily dental practice. Several optical technologies have been developed in recent years for the purpose of dental examination, including near-infrared light transillumination as a promising tool for the supplementation and partial replacement of radiography. In case of occlusal alterations, the incidence of surface discolorations impedes the visual assessment, whereas tactile inspection appears to yield little diagnostic information or might be detrimental. Optical coherence tomography (OCT) facilitates depth-resolved imaging with μm resolution, utilizing near-infrared light, and has already shown its potential for various dental applications. We have recently demonstrated that depolarization imaging utilizing the degree of polarization uniformity (DOPU) extends those abilities by the detection of early carious lesions, as it provides an unambiguous demineralization contrast. Here, we show that this approach also enables the assessment of occlusal enamel lesions in the presence of stains, and compare PS-OCT cross sections with polarized light microscopy (PLM) images of thin sections. For tooth samples with discoloration or demineralization, respectively, PS-OCT and PLM results are in good agreement.

Cette thèse examine une nouvelle méthode de diagnostic, appelée Polarimètrie de Mueller, pour l’étude des interactions plasma-surface. Cette technique d’imagerie permet la caractérisation optique résolue en temps des cibles exposées au plasma. Les matrices de Mueller mesurées sont analysées en utilisant la décomposition logarithmique donnant des informations polarimétriques sur la diattenuation, la dépolarisation et la biréfringence. Cette dernière est exploitée en examinant des matériaux optiquement actifs afin d’identifier des aspects spécifiques de l’interaction avec le plasma, tels que les champs électriques ou la température de surface.Ce travail se concentre sur les cibles électro-optiques, qui permettent principalement la détection de champs électriques induits par la charge de surface déposée lors de l’interaction. La biréfringence est couplée analytiquement au champ électrique, en rapportant le retard de phase du faisceau sonde de lumière polarisée, à l’ellipsoïde d’index perturbé suivant l’effet Pockels. Grâce à cette approche analytique, les matériaux ayant des propriétés électrooptiques spécifiques peuvent être choisis de telle manière que toutes les composantes individuelles de champ électrique (axiales et radiales) induites à l’intérieur de l’échantillon soient imagées séparément. Pour la première fois les composantes du champ électriques peuvent être découplées permettant de mieux comprendre la dynamique du plasma proche d’une surface diélectrique.Cette technique est utilisée pour étudier l’impact d’ondes d’ionisation sur des surfaces. Ces décharges, générées par un jet de plasma à pression atmosphérique dans la gamme kHz, sont des plasmas froids filamentaires généralement utilisés pour des applications diverses telles que la fonctionnalisation de surface de polymères ou des traitements biomédicaux, mais les méthodes de diagnostic disponibles pour étudier les effets induits sur les surfaces sont limités. L’imagerie de polarimètrie Mueller appliquée aux cibles électro-optiques permet d’examiner les champs axiaux et radiaux en termes d’amplitude (3-6 kV/cm), d’échelles spatiales (<1mm axiales and <1cm radiales) et d’échelles temporelles (< 1μs pulsée and < 10μs CA) pour divers paramètres de fonctionnement du jet, e.g. amplitude de tension et gaz environnant.Simultanément à la biréfringence transitoire induite par le champ électrique, un signal de fond constant est également observé. Il est induit par la contrainte résultante du gradient de température induit à l’intérieur du matériau ciblé. Une relation analytique est obtenue en utilisant l’effet photo-élastique, permettant de développer une procédure de fitting pour retrouver la distribution de température. Cette procédure est utilisée, après calibration, pour montrer que la température de l’échantillon peut varier jusqu’`a 25 degrés par rapport aux conditions ambiantes – tandis que les changements dans le champ électrique sont également mesurés – et dépend de la fréquence de la tension d’alimentation AC du jet de plasma. La détermination précise de la température induite dans les cibles est importante car la plupart des applications visent des échantillons thermosensibles.Enfin, ce travail montre comment des échantillons complexes (aussi bien en terme d’état de surface que de composition chimique) peuvent être examinés lors d’une interaction plasma-surface, en les combinant avec une cible électrooptique. En raison de l’ajout d’un échantillon complexe, une composante de dépolarisation est ajoutée due à la diffusion du faisceau lumineux polarisé. Les changements de dépolarisation sont liés à l’évolution de l’échantillon complexe au cours du traitement par plasma. Ceux-ci, couplés aux champs électriques mesurés simultanément, fournissent un outil de diagnostic unique pour examiner les interactions plasma-surface. Cela a été appliqué à un cas test où une seule couche de cellules d’oignon est exposée aux ondes d’ionisation générées par le jet de plasma froid. / In this thesis, a new diagnostic method called Mueller Polarimetry is examined for the investigation of plasma-surface interactions. This imaging technique allows the time-resolved optical characterization of targets under plasma exposure. The measured Mueller matrices are analyzed by using the logarithmic decomposition providing polarimetric data on diattenuation, depolarization, and birefringence. The latter is used by examining materials that possess optically active behavior to identify specific aspects of the plasma interaction, e.g. electric fields or temperature.This work focusses on electro-optic targets, which primarily enables the detection of electric fields induced by surface charge deposited during the interaction. The birefringence is coupled to the externally induced electric field by analytically relating the phase retardance for the probing polarized light beam to the perturbed index ellipsoid, according to the Pockels effect. Through this analytical approach, materials with specific electro-optic properties can be chosen in such a way – together with the orientation of the Mueller polarimeter itself – that all the individual electric field components (axial and radial) induced inside the sample are imaged separately. This has never been done before and allows to better understand the plasma dynamics in the vicinity of a dielectric surface.It is used to investigate the surface impact by guided ionization waves generated by a kHz-driven atmospheric pressure plasma jet. These non-thermal filamentary discharges are generally applied to various samples for e.g. surface functionalization of polymers or biomedical treatment of organic tissues. However, available diagnostic tools are limited to study these interactions. Imaging Mueller polarimetry applied to electro-optic targets examines the axial and radial field patterns in terms of amplitude (3-6 kV/cm), spatial scales (< 1mm axial and <1cm radial), and timescales (<1μs pulsed and <10μs AC) for various operating parameters of the jet, for example voltage amplitude and surrounding gas.Simultaneous with the transient birefringence induced by the electric field, a constant background pattern is also observed. This results from strain induced by temperature gradients inside the targeted material. An analytical relation is obtained following the photo-elastic effect, which allowed a fitting procedure to be designed to retrieve the temperature pattern. This procedure is used after calibration to show that the temperature of the sample can vary up to 25 degrees relative to room conditions – while changes in the electric field are seen as well – depending on the operating frequency of the AC driven plasma jet. The accurate determination of the temperature is important since most applications involve temperature sensitive samples.Lastly, this work shows how complex samples (in terms of surface geometry and/or chemical composition) can be examined during a plasma-surface interaction. This is done by combining them with the electro-optic targets. Due to the addition of a (thin) complex sample, depolarization is added to the system through scattering of the polarized light beam. In-situ observed changes of depolarization relate to the evolution of the complex sample during the plasma treatment. This, coupled with the simultaneously monitored electric field patterns, provides a unique diagnostic tool to examine the plasma-surface interactions. This has been applied for a test case where a single layer of onion cells is exposed to the ionization waves generated by the non-thermal plasma jet.

The discovery of the ferroelectric orthorhombic phase in doped hafnia films has sparked immense research efforts. Presently, a major obstacle for hafnia's use in high-endurance memory applications like nonvolatile random-access memories is its unstable ferroelectric response during field cycling. Different mechanisms are proposed to explain this instability including field-induced phase change, electron trapping, and oxygen vacancy diffusion. However, none of these is able to fully explain the complete behavior and interdependencies of these phenomena. Up to now, no complete root cause for fatigue, wake-up, and imprint effects is presented. In this study, the first evidence for the presence of singly and doubly positively charged oxygen vacancies in hafnia–zirconia films using thermally stimulated currents and impedance spectroscopy is presented. Moreover, it is shown that interaction of these defects with electrons at the interfaces to the electrodes may cause the observed instability of the ferroelectric performance.

Historically ceramic crystal laser material has had disadvantages compared to single crystal laser material. However, progress has been made in the last decade and a half to overcome the disadvantages associated with ceramic crystal. Today, because of the promise of ceramic crystal as a high power laser material, investigation into its properties, both physical and optical, is warranted and important. Thermal expansion was measured in this thesis for Nd:YAG (yttrium aluminum garnet) ceramic crystal using an interferometric method. The interferometer employed a spatially filtered HeNe at 633 nm wavelength. Thermal expansion coefficients measured for the ceramic crystal samples were near the reported values for single crystal Nd:YAG. With a similar experimental setup as that for the thermal expansion measurements, dn/dT for ceramic crystal Nd:YAG was measured and found to be slightly higher than the reported value for single crystal. Depolarization loss due to thermal gradient induced stresses can limit laser performance. As a result this phenomenon was modeled for ceramic crystal materials and compared to single crystals for slab and rod shaped gain media. This was accomplished using COMSOL Multiphysics, and MATLAB. Results indicate a dependence of the depolarization loss on the grain size where the loss decreases with decreased grain size even to the point where lower loss may be expected in ceramic crystals than in single crystal samples when the grain sizes in the ceramic crystal are sufficiently small. Deformation-induced thermal lensing was modeled for a single crystal slab and its relevance to ceramic crystal is discussed. Data indicates the most notable cause of deformation-induced thermal lensing is a consequence of the deformation of the top and bottom surfaces. Also, the strength of the lensing along the thickness is greater than the width and greater than that due to other causes of lensing along the thickness of the slab. Emission spectra, absorption spectra, and fluorescence lifetime were measured for Nd:YAG ceramic crystal and Yb:Lu2O3 ceramic crystal. No apparent inhomogeneous broadening appears to exist in the Nd:YAG ceramic at low concentrations. Concentration and temperature dependence effects on emission spectra were measured and are presented. Laser action in a thin disk of Yb:Y2O3 ceramic crystal was achieved. Pumping was accomplished with a fiber coupled diode laser stack at 938 nm. A slope efficiency of 34% was achieved with maximum output energy of 28.8 mJ/pulse.

The ensuring of reliability of piezoelectric thin films is crucial for a successful piezoelectric micro-electromechanical system (piezoMEMS) application. One of the most important limiting factors for reliability is resistance degradation, where the leakage current increases over time under electrical load. The understanding of resistance degradation in piezoelectric thin films requires knowledge about point defects inside the materials. In this dissertation, the resistance degradation mechanism in sputtered lead zirconate titanate (PZT) and lead-free alternative sodium potassium niobate (KNN) thin films is studied in both voltage polarities, and its relation to point defects is established. The conduction mechanism of both PZT and KNN thin films is found to be Schottky-limited. Furthermore, the resistance degradation is due to the reduction in Schottky barrier height, which results from the interfacial accumulation of additional charged defects. In order to study those defects, we use thermally stimulated depolarization current (TSDC) measurements and charge-based deep level transient spectroscopy (Q-DLTS) to characterize the defects in both PZT and KNN thin films. In PZT thin films, the resistance degradation take place in different waves of increasing leakage current. Both oxygen vacancies and lead vacancies contribute to the different waves of resistance degradation in both voltage polarities. A physical degradation model was developed based on hopping migration of oxygen vacancies at constant speed and exponent accumulation of lead vacancy trapping, where the natural logarithm of leakage current is proportional to the accumulated defect concentration to the power of 0.25. By using the oxygen vacancy concentration measured by TSDC and lead vacancy concentrations measured by Q-DLTS, the model successfully explained the resistance degradation behaviors of PZT films varying due to deposition non-uniformity and due to different process parameters. The accumulation of oxygen vacancies at cathode is supported by X-ray photoelectron spectroscopy (XPS), and the resistance degradation can be restored by proper heat and electrical treatment as predicted by the defect characterization results. In KNN thin films, oxygen vacancies contribute to the resistance degradation when a negative voltage is applied at the top electrode, whereas sodium and potassium vacancies contribute to the resistance degradation when a positive voltage is applied at the top electrode. The model developed for PZT can be applied also to KNN, where the model successfully explained the resistance degradation behaviors of KNN films varying due to the deposition non-uniformity by using the defect concentration measured by TSDC. The accumulation of oxygen vacancies at cathode and sodium plus potassium vacancies at anode are supported by transmission electron microscopy energy dispersive X-ray spectroscopy (TEM-EDX), and the resistance degradation can be restored also by proper heat and electrical treatment as predicted by the defect characterization results. This dissertation revealed the similarity of the resistance degradation between sputtered PZT and KNN thin films. The degradation is controlled by the crystallography point defects created during deposition process inside the material, indicating the significance of process control on material reliability. This dissertation also demonstrates the applicability of TSDC and Q-DLTS as alternative methods to assess the quality of the piezoelectric thin films. Both measurement techniques provide additional information regarding specific defects when comparing with conventional highly accelerated lifetime test (HALT) or other relevant tests. / Die Sicherstellung der Zuverlässigkeit piezoelektrischer Dünnschichten ist entscheidend für eine erfolgreiche Anwendung in piezoelektrischen mikro-elektromechanischen Systemen (piezoMEMS). Einer der wichtigsten limitierenden Faktoren für die Zuverlässigkeit ist die Widerstandsdegradation, bei der der Leckstrom mit der Zeit unter elektrischer Last zunimmt. Das Verständnis der Widerstandsdegradation in piezoelektrischen Dünnschichten erfordert laut Literatur Kenntnisse über Punkt-Defekte innerhalb der Materialien. In dieser Dissertation wird der Mechanismus der Widerstandsdegradation in gesputterten Blei-Zirkonat-Titanat (PZT) Dünnschichten und dessen bleifreier alternative Kalium-Natrium-Niobat (KNN) in beiden Spannungspolaritäten untersucht und deren Zusammenhang mit Punkt-Defekte hergestellt. Der Leitungsmechanismus von PZT- und KNN-Dünnschichten ist Schottky-begrenzt. Außerdem ist die Widerstandsdegradation auf die Reduzierung der Schottky-Barrierhöhe zurückzuführen, die von der Akkumulation zusätzlicher aufgeladener -Defekte an der Grenzfläche stammt. Um diese -Defekte zu untersuchen, verwenden wir thermisch stimulierte Depolarisationsstrommessungen (Thermally stimulated depolarization current, TSDC) und ladungsbasierte Deep-Level-Transientenspektroskopie (Charge-based deep level transient spectroscopy, Q-DLTS), um die Defekte sowohl in PZT- als auch in KNN-Dünnschichten zu charakterisieren.Die Wiederstandsdegradation in PZT-Dünnschichten findet in unterschiedlichen Wellen des erhöhenden Leckstroms statt. Sowohl Sauerstofffehlstellen als auch Bleifehlstellen tragen zu den unterschiedlichen Wellen der Widerstandsdegradation in beiden Spannungspolaritäten bei. Ein physikalisches Degradationsmodell wurde entwickelt, basierend auf der Hopping-Migration von Sauerstofffehlstellen bei konstanter Geschwindigkeit und exponentieller Akkumulation von Ladungseinfang durch Bleifehlstellen, wobei der natürliche Logarithmus des Leckstroms proportional zur akkumulierten Defektkonzentration hoch 0,25 ist. Durch die Verwendung der Sauerstofffehlstellen- und Bleifehlstellenkonzentrationen konnte das Modell das Widerstandsdegradationsverhalten von PZT-Dünnschichten erklären, das wegen der Ungleichmäßigkeit der Deposition und wegen der verschiedenen Prozessparameters variiert. Die Sauerstofffehlstellenkonzentration wird durch TSDC gemessen und die Bleifehlstellenkonzentrationen wird durch Q-DLTS gemessen. Die Akkumulation von Sauerstofffehlstellen an der Kathode wird durch die Röntgen-Photoelektronenspektroskopie (X-ray photoelectron spectroscopy, XPS) unterstützt und die Widerstandsdegradation kann durch eine ordnungsgemäße Wärme- und elektrische Behandlung wiederhergestellt werden, wie durch die Ergebnisse von Defektecharakterisierung vorhergesagt wurde. Bei KNN-Dünnschichten tragen Sauerstofffehlstellen zu der Widerstandsdegradation bei, wenn eine negative Spannung an der oberen Elektrode anliegt, und Natrium- und Kaliumfehlstellen tragen zu der Widerstandsdegradation bei, wenn eine positive Spannung an der oberen Elektrode anliegt. Das für PZT entwickelte Modell kann auch auf KNN angewendet werden. Das Modell erklärt erfolgreich das Widerstandsdegradationverhalten von KNN-Dünnschichten, das durch die Ungleichmäßigkeit der Deposition variiert werden, was mithilfe der mit TSDC gemessenen Defektkonzentrationen erklärt werden kann. Die Akkumulation von Sauerstofffehlstellen an Kathode und Natrium- und Kaliumfehlstellen an der Anode wird durch die transmissionselektronenmikroskopische energiedispersive Röntgenspektroskopie (transmission electron microscopy energy dispersive X-ray spectroscopy, TEM-EDX) unterstützt, und die Widerstandsdegradation kann auch durch eine ordnungsgemäße Wärme- und elektrische Behandlung wiederhergestellt werden, wie durch die Ergebnisse von Defektecharakterisierung vorhergesagt wurde. Diese Dissertation zeigt die Ähnlichkeit der Widerstandsdegradation zwischen gesputterten PZT- und KNN-Dünnschichten. Die Degradation wird durch die kristallographischen Punkt-Defekte gesteuert, die während des Abscheidungsprozesses im Material entstehen. Das weist auf die Bedeutung der Prozesskontrolle für die Zuverlässigkeit des Materials hin. Diese Dissertation zeigt auch die Anwendbarkeit von TSDC und Q-DLTS als alternative Methoden zur Beurteilung der Qualität der piezoelektrischen Dünnschichten. Beide Messtechniken liefern zusätzliche Informationen zu spezifischen Defekte im Vergleich zu traditionellen HALT-Prüfungen (highly accelerated lifetime test).

Cette thèse s'inscrit dans la thématique technologique des décharges électrostatiques sur les panneaux solaires des satellites de télécommunication en orbite géostationnaire. Son objectif est de déterminer les évolutions des propriétés électriques d'un adhésif silicone commercial en environnement spatial et de les corréler aux évolutions de sa structure chimique. Les principaux constituants du matériau ont été identifiés et des échantillons dépourvus de particules de renfort - assimilés à la matrice polymère isolée - ont été élaborés. Afin d'évaluer l'influence des particules, ils ont été systématiquement comparés aux échantillons nominaux dans l'ensemble de ces travaux. La structure physico-chimique du matériau à l'état initial a été caractérisée en étudiant ses relaxations enthalpiques, mécaniques et en pratiquant des analyses chimiques. Son comportement électrique (relaxations dipolaires et conductivité) a été sondé grâce à une approche expérimentale inédite croisant la technique de relaxation de potentiel électrostatique de surface, la spectroscopie diélectrique dynamique et l'analyse des courants thermo-stimulés. Le vieillissement du matériau en environnement spatial a été simulé expérimentalement par l'exposition des échantillons à des flux élevés d'électrons de haute énergie. Les analyses chimiques, notamment en RMN du solide, ont montré la prédominance d'un processus de réticulation du matériau sous irradiation, et des mécanismes de dégradation à l'échelle microscopique ont été proposés. Le comportement électrique du matériau est fortement impacté par l'évolution de sa structure chimique : sa résistivité augmente considérablement avec la dose ionisante. Il est suggéré que la résistivité de ce matériau soit directement liée à son degré de réticulation, influant sur la mobilité des porteurs dans le cadre du hopping et de la percolation électrique. Cette augmentation est beaucoup plus marquée en présence de particules, ce qui a été attribué à la formation de nœuds de réticulation matrice-particules qui constituent des pièges plus profonds pour les porteurs de charges. Ces travaux apportent une meilleure compréhension des phénomènes de vieillissement des élastomères silicones en environnement spatial. Ils permettront d'anticiper des évolutions structurales qui pourraient mettre en péril leur fonction d'adhésion, ainsi que des évolutions de résistivité électrique intrinsèque, facteur décisif dans le déclenchement de décharges électrostatiques. / This PhD thesis falls within the technical field of electrostatic discharges occurring on the solar arrays of communications satellites in the geostationary orbit. Its main objective consists in assessing the evolutions of a space-used commercial silicone adhesive's electrical properties, and to correlate them with the evolutions of its chemical structure. The main components of this material have been identified, and neat samples (deprived of fillers) were elaborated so as to study the isolated polymer matrix. In order to assess the influence of filler incorporation, neat samples were systematically compared with the commercial ones in this study. The material's physicochemical structure in the initial state was characterized by studying its enthalpy relaxations, mechanical response, and by performing chemical analysis. Its electrical behavior (dipole relaxations and conductivity) was investigated thanks to an original experimental approach combining surface potential decay measurements, broadband dielectric spectroscopy, and thermally stimulated depolarization currents. Aging in the space environment was experimentally simulated by exposing the samples to high fluxes of high energy electrons. Chemical analysis (solid state NMR in particular) revealed the predominant crosslinking tendency of this material under ionizing radiations, and allowed to suggest degradation mechanisms at the microscopic scale. These structural evolutions also strongly impact its electrical behavior: a great increase in electrical resistivity has been observed with increasing ionizing dose. It is believed that electrical resistivity directly depends on the degree of crosslinking, which affects charge carrier mobility, in the theoretical frame of hopping and percolation models. The increase in resistivity is considerably more pronounced in the filled material, which could be associated with crosslinking occurring at the matrix-particles interface. Such crosslinks are thought to represent deeper traps for charge carriers. This work brought better understanding of aging phenomena in silicone elastomers exposed to the ionizing space environment. This knowledge will help predicting structural evolutions that may compromise vital properties such as adhesion, and the evolutions of intrinsic conductivity, a critical factor involved in the triggering of electrostatic discharges.

Polymeric materials have provided pathways to products that could not be manufactured otherwise. A new technology which merges the benefits of ceramics into these polymer products has created materials ideally suited to many different industries, like food packaging. Nano Scale Surface Systems, Inc. (NS3), a company which coats polymers with ceramic oxides like SiO2 through a process known as plasma enhanced chemical vapor deposition (PECVD), was interested in the feasibility of an in line measurement system for monitoring the deposited films on various polymer products. This project examined two different coated polymer products, polyethylene terephthalate (PET) beverage containers and biaxially oriented PET food packaging, commonly known as plastic wrap in an effort to determine the feasibility of an ellipsometry based measurement system for NS3’s purpose. Due to its extensive use in the semiconductor industry for monitoring films deposited on silicon, a measurement systems known as ellipsometry, adept at monitoring the thickness and refractive index of thin films deposited on various substrates, appeared to be an ideal system for the measurement of ceramic oxides deposited on various polymer substrates. This project set out to determine the feasibility of using an ellipsometry based measurement system to monitor ceramic films, specifically silicon oxides (SiOX), deposited on polymer products. A preliminary experiment determined linearly polarized light could induce a discernible change in polarized light traversing a coated beverage container relative to an uncoated container. However, the experiment lacked repeatability due to the measurement apparatus’ cheap setup, prompting the construction of a null (conventional) ellipsometer for further research. The curved surface of the beverage containers under study unnecessarily complicated the feasibility study so further research examined PECVD SiOX on biaxially oriented PET instead. Characterization of the PECVD SiOX-PET material was divided into three experiments, with the first two analyzing the SiOX film and PET substrate separately while the third analyzed them together. To assist with the characterization experiments, NS3 provided samples, both SiOX coated and uncoated, of various deposition thicknesses on silicon and biaxially oriented PET substrates. Null ellipsometry was used in conjunction with spectroscopic reflectometry to characterize the refractive index and thickness of the deposited films. The combined measurement systems found the refractive index of the deposited SiOX films to be between 1.461 and 1.465. The measured thicknesses resulting from the two measurement systems coincided well and were usually 10-20 nm thicker than the predicted thicknesses by the deposition processing parameters. Abeles’ method and monochromatic goniometry were attempted; however, the results had to be discarded due to irrecoverable errors discovered in the reflectance measurement. X-ray photoelectron spectroscopy (XPS) data provided by NS3 showed the deposited SiOX films to be homogeneous with stoichiometries between 2.15 and 2.23. Characterization of the uncoated biaxially oriented PET required numerous measurement systems. From spectroscopic transmission, trirefringent anisotropy was discovered, intertwined with thickness variations in the PET foil. Goniometry measurements displayed distinct interference curves resulting from rear interface reflections interfering with front interface reflections from the PET sample. Subsequent goniometric models produced multiple solutions due to an unknown optical phenomenon, probably scattering, which degraded the reflection measurements. However, a combined measurement technique utilizing goniometry and differential scanning calorimetry (DSC) determined the refractive indices of the polymer to be NX = 1.677, NY = 1.632 and NZ = 1.495 with a thickness of 11.343 μm and a volume fraction crystallinity of 35-41%. Utilizing the measured refractive indices, ellipsometric models produced only an adequate fit of the measured data due to the presence of depolarization caused by non-uniform PET thickness and scattering resulting from embedded microscopic crystallites. The majority of the error in the ellipsometric data was observed in the Δ measurement. XPS measurements of SiOX deposited on polypropylene (PP) provided by NS3 showed a heterogeneous interphase layer between the deposited oxide and the polymer substrate where the composition of the layer was continually changing. A similar region, which violates the homogenous assumption the ellipsometric model relied on, was anticipated for the SiOX-PET samples under investigation. The use of an effective medium approximation (EMA) to represent the interphase region was attempted, but failed to provide a decent model fit of the measured data. Depolarization and high optical anisotropy caused by the polymer substrate in combination with a heterogeneous interphase region and the effects of the deposited SiOX layer all interacted to prevent ellipsometric modelling of the null ellipsometry measurements conducted. Goniometry measurements were conducted on the thickest deposited SiOX film (approximately 100 nm) which allowed for the refractive index of the film to be approximated through Abeles’ method (n = 1.46); however the validity of this approximation was questionable given the presence of interference fringes resulting from interference between reflections at both the front and rear interfaces of the material. From the experiments conducted, it was concluded that null ellipsometry with conventional ellipsometric models could not adequately measure a SiOX film’s refractive index or thickness when deposited on biaxially oriented PET. The reasons for the failure were interactions between multiple sources of error which led to both measurement errors and inaccurate model assumptions. Use of generalized ellipsometry, possibly with spectroscopic ellipsometry, may overcome the failures of conventional ellipsometry when studying this complex optical material.