To accelerate environmentally friendly thin film photovoltaic (PV) technologies, copper-based chalcogenides are attractive as absorber materials. Chalcopyrite copper indium gallium selenide (CIGS ≡ CuIn1–xGaxSe2) is today a commercially important PV material, and it is also in many aspects a very interesting material from a scientific point of view. Copper zinc tin sulfide selenide (CZTSSe ≡ Cu2ZnSn(S1–xSex)4) is considered as an emerging alternative thin film absorber material. Ternary Cu2SnS3 (CTS) is a potential absorber material, thus its related alloys Cu2Sn1–xGexS3 (CTGS) and Cu2Sn1–xSixS3 (CTSS) are attractive due to the tunable band gap energies. CuSb(Se1–xTex)2 and CuBi(S1–xSex)2 can be potential as ultra-thin (≤ 100 nm) film absorber materials in the future. In the thesis, analyses of these Cu-based chalcogenides are based on first-principles calculations performed by means of the projector augmented wave method and the full-potential linearized augmented plane wave formalisms within the density functional theory as implemented in the VASP and WIEN2k program packages, respectively. The electronic and optical properties of CIGS (x = 0, 0.5, and 1) are studied, where the lowest conduction band (CB) and the three uppermost valence bands (VBs) are parameterized and analyzed in detail. The parameterization demonstrates that the corresponding energy dispersions of the topmost VBs are strongly anisotropic and non-parabolic even very close to the Γ-point. Moreover, the density-of-states and constant energy surfaces are calculated utilizing the parameterization, and the Fermi energy level and the carrier concentration are modeled for p-type CIGS. We conclude that the parameterization is more accurate than the commonly used parabolic approximation. The calculated dielectric function of CuIn0.5Ga0.5Se2 is also compared with measured dielectric function of CuIn0.7Ga0.3Se2 collaborating with experimentalists. We found that the overall shapes of the calculated and measured dielectric function spectra are in good agreement. The transitions in the Brillouin zone edge from the topmost and the second topmost VBs to the lowest CB are responsible for the main absorption peaks. However, also the energetically lower VBs contribute significantly to the high absorption coefficient. CTS and its related alloys are explored and investigated. For a perfectly crystalline CTS, reported experimental double absorption onset in dielectric function is for the first time confirmed by our calculations. We also found that the band gap energies of CTGS and CTSS vary almost linearly with composition over the entire range of x. Moreover, those alloys have comparable absorption coefficients with CZTSSe. Cu2XSnS4 (X = Be, Mg, Ca, Mn, Fe, Ni, and Zn) are also studied, revealing rather similar crystalline, electronic, and optical properties. Despite difficulties to avoid high concentration of anti-site pairs disordering in all compounds, the concentration is reduced in Cu2BeSnS4 partly due to larger relaxation effects. CuSb(Se1–xTex)2 and CuBi(S1–xSex)2 are suggested as alternative ultra-thin film absorber materials. Their maximum efficiencies considering the Auger effect are ~25% even when the thicknesses of the materials are between 50 and 300 nm. / <p>QC 20170523</p>

Given the promise of the Inductive Power Transfer (IPT) technology for eRoad applications, the potential challenges for a successful integration of dynamic IPT technology into the physical road structure are explored extensively in this research work. The Finite Element Method (FEM) is selected for studying the structural performance of an eRoad under operational conditions. In this, an energy-based finite strain constitutive model for asphalt materials is developed and calibrated, to enable the detailed investigation of the structural response and optimization of the considered eRoad. In the context of enabling both dynamic charging and autonomous driving for future electric vehicles, the influences to the pavement (rutting) performance by the changed vehicle behaviour are investigated as well. Moreover, to study the effect on the IPT system by the integration, the potential power loss caused within eRoad pavement materials is further examined by a combined analytic and experimental analysis. The direct research goal of this Thesis is therefore to enhance the possibility of a sustainable implementation of the eRoad solutions into the real society. At the same time, it aims to demonstrate that the road structure itself is an important part of smart infrastructure systems that can either become a bottleneck or a vessel of opportunities, supporting the successful integration of these complex systems. / Givet de förutsättningar som induktiv energiöverföring (IPT Inductive Power Transfer) har för eRoad applikationerna, utforskas möjligheterna för en framgångsrik integration av dynamisk IPT i den fysiska vägkonstruktionen på en djupgående nivå i detta forskningsarbete. Speciellt har finita elementmetoden använts för att studera det strukturella beteendet hos en e-väg under driftsmässiga förhållanden. Inom detta har en energibaserad konstitutiv model för stora töjningar utvecklats och kalibrerats för att möjliggöra detaljerade undersökningar av strukturell respons och optimering av de föreslagna e-vägarna. I samband med att möjliggöra både dynamisk laddning och autonom körning för framtida elektriska fordon, har beläggningars (spårbildnings)egenskaper studerats utifrån de laddande fordonen beteende. Dessutom för att studera effekten av IPT-systemet har den potentiella energiförlusten inom e-vägars beläggningsmaterial undersökts genom en kombinerad analytisk och experimentell undersökning. Som sådant är det direkta forskningsmålet med denna avhandling att utöka möjligheterna för en hållbar implementering av eRoad systemet inom det verkliga samhället. Samtidigt är målet att visa att vägkonstruktionen i sig själv är en viktig del av det smarta infrastruktursystemet som antingen kan bli en flaskhals eller en bärare av möjligheter, stödjande en framgångsrik implementering av dessa komplexa system. / <p>QC 20161108</p>

Electroporation affects the dielectric properties of cells. Dielectric measurement techniques can provide a label-free and non-invasive modality to study this phenomenon. In this thesis we introduce a dielectrophoresis (DEP) based technique to study changes in the cytoplasm conductivity of single Chinese hamster ovary (CHO) cells immediately after electroporation. Using a microfluidic chip, we study changes in the DEP response of single CHO cells a few seconds after electroporation. First, in order to quantify our DEP measurement results and relate them to the cells internal conductivity, we introduce a dielectric model for CHO cells. This is achieved by measuring the DEP response of many individual cells in the β-dispersion frequency region and curve fitting to the measured data. Second, we present quantitative results for changes in the cytoplasm conductivity of single cells subjected to pulsed electric fields with various intensities. We observe that when electroporation is performed in media with lower ionic concentration than cells cytoplasm, their internal conductivity decreases after electroporation depending on the intensity of applied pulses. We also observe that with reversible electroporation there is a limit on the decrease in the cells’ internal conductivity. We hypothesize the reason is the presence of large and relatively immobile negative ions inside the cell which attract mobile positive ions (mainly sodium and potassium) to maintain cell electrical neutrality. We monitor the temporal response of cells after electroporation to measure the time constant of changes due to ion transport and observe this ranges from seconds to tens of seconds depending on the applied pulse intensity. This result can be used to infer information about the density and resealing time of very small pores (not measurable with conventional marker molecules). Lastly, we measure the electroporation of cells in media with different conductivities. Our results show that electroporation in very low conductivity media requires stronger pulses to achieve a similar poration extent as in high conductivity media. The outcome of this thesis can be used to improve our understanding of the dynamics of electroporation as well as its modelling in order to make more accurate predictions or optimize the process for specific applications. / February 2017

This study is an investigation of the chemical vapor deposition (CVD) of aluminum and copper on fluoropolymer surfaces and the subsequent interfacial interactions.

Ce travail concerne l’étude de l’effet des impuretés sur les phénomènes physico-chimiques apparaissant durant le frittage des kaolins entre 900 et 1600 °C et les propriétés physiques qui en découlent. Le kaolin est utilisé dans le domaine des céramiques : céramique traditionnelle, porcelaine, céramiques réfractaires (mullite, chamotte), porcelaines électrotechniques, etc… Il est d’usage de contrôler la teneur et la nature des impuretés car leur présence peut limiter leurs applications.Sept kaolins ont été choisis pour les impuretés qu’ils contiennent à savoir ;• Feldspaths, quartz et oxydes de fer pour les kaolins de Tamazert (Algérie)• Matières organiques et oxyde de manganèse pour les kaolins de Djebel Debbagh (Algérie).• Matières organiques, oxydes de fer, gibbsite et anatase pour les kaolins des Charentes (France). La kaolinite ou l'halloysite, de même composition, est le minéral majeur dans chaque cas. L'ensemble des matériaux a été réduit par broyage à la taille de 63 μm. Le premier volet de l’étude consiste en une caractérisation physico-chimique des différents kaolins pour identifier et quantifier les principaux minéraux qui les composent. Le second volet concerne la compréhension des transformations thermiques qui se produisent lors du processus de deshydroxylation de la kaolinite (metakaolin) et lors de la formation de la mullite et de la cristobalite à de hautes températures (1600 °C). La microstructure, le retrait, la densification, la porosité sont les principaux paramètres étudiés dans ce volet.Le troisième volet porte sur les propriétés des kaolins lors du frittage à savoir : Les propriétés colorimétriques, mécaniques et diélectriques. L’effet des impuretés ainsi que la microstructure lors du frittage sur ces propriétés (colorimétrique, mécaniques et diélectriques) sont largement développés. Lors du frittage des différents kaolins la taille des cristallites de mullite augmente avec la température. Ces cristallites incorporent les impuretés colorantes tels que Fe2+/Fe3+, Ti4+/Ti2+ et Mn4+/Mn2+ (selon la température), ce qui résulte dans l’augmentation de la chromaticité et la diminution de la clarté à partir de 1100 °C. La transformation de la phase anatase à la phase rutile diminue le paramètre de clarté des kaolins des charentes. La présence de cristobalite dans le cas du kaolin de Djebel Debbagh riche en manganèse participe à l’augmentation de sa clarté au delà de 1400 °C. La présence de feldspath dans les kaolins de Tamazert améliore leurs propriétés diélectriques grâce à la formation de la phase vitreuse. Lors de l’augmentation de la température à1300 °C, ces propriétés augmentent, elles diminuent avec l’augmentation des fréquences (107-109Hz). Les pertes diélectriques sont plus importantes par rapport à celles rencontrées dans les matériaux céramiques (Porcelaines) utilisés dans les diélectriques qui sont en générale <10-3. Une dernière partie est consacrée à l’application d'un kaolin naturellement riche en anatase dans le domaine des porcelaines diélectriques. L’identification et la quantification des phases formées durant le frittage à 1300 °C , la porosité, la microstructure (observée par MEB) et les propriétés mécaniques et diélectriques sont déterminés. La permittivité relative théorique des porcelaines obtenues, calculée en utilisant la règle des mélanges des phases minéralogiques formées est en bon accord avec les valeurs expérimentales trouvées. / This work concerns the study of the effect of impurities on the physico-chemical phenomena occurring duringthe sintering of kaolin between 900 and 1600 °C and the resulting physical properties. Kaolin is used in the field ofceramics: traditional ceramics, porcelain, refractory ceramic (mullite, chamotte), electrotechnical porcelain, etc. ... It iscustomary to control the content and nature of impurities that may limit their applications.Seven kaolin were selected for the impurities they contain namely; Feldspar, quartz and iron oxides in kaolin of Tamazert (Algeria). Organic matters and manganese oxide for kaolin of Djebel debbagh (Algeria). Organic matter, iron oxides, gibbsite and anatase in kaolin of Charentes basin (France).Kaolinite and halloysite, with the same composition, is the major mineral in each case. All the materials werereduced by grinding to the size of 63 μm.The first part of the study consists of physico-chemical characterizations of different kaolin to identify andquantify the major minerals that compose them.The second part concerns the understanding of thermal transformations that occur during the process ofdehydroxylation of kaolinite (metakaolin) and during the formation of mullite and cristobalite at high temperatures(1600 ° C). The microstructure, shrinkage, densification, the porosity are the main parameters studied in this part.The third part deals with the properties of kaolin during sintering where colorimetric, mechanical and dielectricproperties were studied.The effect of impurities and the microstructure during sintering of these properties (color, mechanical anddielectric) are widely developed. During sintering, crystallite size of mullite of different kaolins increases withtemperature. These crystallites incorporate impurities coloring such as Fe2 +/ Fe3 +, Ti4 +/ Ti2 + and Mn4 +/ Mn 2 +(depending on temperature), resulting in the increase of the chromaticity and the decrease in brightness from 1100 ° C.The transformation of anatase to rutile phase decreases the parameter of clarity of the charente kaolin. Presence ofcristobalite in the case of kaolin of Djebel Debbagh (which is rich in manganese) participates to the increase in claritybeyond 1400 ° C. The presence of feldspar in kaolin of Tamazert improves their dielectric properties through theformation of the glassy phase. When increasing the temperature at 1300 ° C, these properties increase. Relativepermittivity of the calcined kaolin decrease with increasing frequency (107-109Hz). The dielectric losses are largercompared to those found in materials used in the dielectric which are in general <10-3.The last part is devoted to the application of kaolin naturally rich in anatase in the field of dielectric porcelain.The identification and quantification of phases formed during sintering at 1300 °C, porosity, microstructure (observedby SEM) and mechanical and dielectric properties are determined. The theoretical relative permittivity obtained bycalculation using a mixing rule of the mineralogical phases formed agrees with the experimental values.

Ce travail de thèse porte sur l'intégration de matériaux de haute constante diélectrique (High-k) en tant que diélectrique interpoly dans les mémoires non volatiles de type Flash. L'objectif est de déterminer quel matériaux High-k seraient des candidats probables au remplacement de l'empilement ONO utilisé en tant que diélectrique interpoly. Une gamme de matériaux high-k ont été étudiés via des caractérisations électriques (I-V, C-V, statistique de claquage…) et physiques (TEM, EDX, XPS…) afin d'éliminer les matériaux ne répondant pas au cahier des charges d'un diélectrique interpoly. Les difficultés et les obstacles liés a l'intégration de matériaux High-k dans une chaine de procédés de fabrication de mémoires Flash ont été pris en compte, et des solutions ont été proposées. / The work of this thesis is on integration of high dielectric constant materials (High-k) as dielectric interpoly in Flash non volatile memories. The objective is to determine which High-k materials are suitable as interpoly dielectric in place of the ONO stack currently used. A range of High-k materials have been studied by electrical characterizations (I-V, C-V, breakdown statistics…) and physical characterizations (TEM, EDX, XPS…) in order to select those with the best properties for an interpoly dielectric. The difficulties in integration of High-k materials in a Flash memory process flow have been taken in account and solutions have been proposed.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / The integration of high-κ dielectrics with silicon and III-V semiconductors is important due to the need for high speed and high power electronic devices. The purpose of this research was to find the best conditions for fabricating high-κ dielectrics (oxides) on GaN or Si. In particular high-κ oxides can sustain the high breakdown electric field of GaN and utilize the excellent properties of GaN. This research developed an understanding of how process conditions impact the properties of high-κ dielectric on Si and GaN. Thermal and plasma-assisted atomic layer deposition (ALD) was employed to deposit TiO₂ on Si and Al₂O₃ on polar (c-plane) GaN at optimized temperatures of 200°C and 280°C respectively. The semiconductor surface treatment before ALD and the deposition temperature have a strong impact on the dielectric’s electrical properties, surface morphology, stoichiometry, and impurity concentration. Of several etches considered, cleaning the GaN with a piranha etch produced Al₂O₃/GaN MOS capacitors with the best electrical characteristics. The benefits of growing a native oxide of GaN by dry thermal oxidation before depositing the high-κ dielectric was also investigated; oxidizing at 850°C for 30 minutes resulted in the best dielectric-semiconductor interface quality. Interest in nonpolar (m-plane) GaN (due to its lack of strong polarization field) motivated an investigation into the temperature behavior of Al₂O₃/m-plane GaN MOS capacitors. Nonpolar GaN MOS capacitors exhibited a stable flatband voltage across the measured temperature range and demonstrated temperature-stable operation.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / Gallium nitride is a promising semiconductor for fabricating field effect transistors for power electronics because of its unique physical properties of wide energy band gap, high electron saturation velocity, high breakdown field and high thermal conductivity. However, these devices are extremely sensitive to the gate leakage current which reduces the breakdown voltage and the power-added efficiency and increases the noise figures. To solve this problem, employing a gate dielectric is crucial to the fabrication of metal insulator semiconductor high electron mobility transistors (MISHEMTs), to reduce the leakage current and increase the magnitude of voltage swings possible. For this device to be successful, imperfections at the oxide-semiconductor interface must be suppressed to maintain the high electron mobility of the device. This research explored multiple high dielectric constant gate oxides (Al[subscript]2O[subscript]3, TiO[subscript]2, and Ga[subscript]2O[subscript]3), deposited on different crystalline orientations and polarities of GaN by atomic layer deposition (ALD) to form metal oxide semiconductor capacitors, including effects of pretreatment on N-polar GaN, ALD TiO[subscript]2/Al[subscript]2O[subscript]3 nano-laminate on thermal oxidized Ga-polar GaN and ALD Al[subscript]2O[subscript]3 on [Italic]c- and [Italic]m-plane GaN Surface pretreatments were shown to greatly alter the morphology of reactive N-polar GaN which is detrimental to the electrical properties. 14 nm thick ALD Al[subscript]2O[subscript]3 films were directly deposited on N-polar GaN without thermal or chemical pretreatments which yield a smooth surface (RMS=0.23 nm), low leakage current (2.09 x 10[superscript]-[superscript]8 A/cm[superscript]2) and good Al[subscript]2O[subscript]3/GaN interface quality, as indicated by the low electron trap density (2.47 x 10[superscript]10 cm[superscript]-[superscript]2eV[superscript]-[superscript]1). In the nano-laminate study, a high dielectric constant of 12.5 was achieved by integrating a TiO[subscript]2/Al[subscript]2O[subscript]3/Ga[subscript]2O[subscript]3 oxide stack layer, while maintaining a low interface trap density and low leakage current. There was a strong correlation between the surface morphology and electrical properties of the device discovered from comparing the ALD Al[subscript]2O[subscript]3 on [Italic]c- and [Italic]m-plane GaN, namely smooth surface lead to small hysteresis. These results indicate the promising potential of incorporation gate dielectric for future GaN devices.

La complexité des mécanismes de transport en nanofiltration (NF) nécessite ledéveloppement d’outils de modélisation fiables permettant de comprendre et d’optimiser lesopérations de séparation en NF.La présente étude comprend deux volets. Le premier porte sur la rétention d’un soluténeutre – le poly(éthylène glycol) à 600 g mol-1 (PEG) – seul et en présence d’ions, par unemembrane organique de NF (polyamide). Les résultats obtenus montrent que la rétention dusoluté neutre chute en présence d’ions et ce, d’autant plus que la concentration du sel estélevée. Ce phénomène ne peut être expliqué par le seul phénomène de déshydratation dusoluté neutre par les ions environnants. Un phénomène supplémentaire de gonflement de porea été mis en évidence et corrélé à la densité de charge membranaire. La contribution des deuxphénomènes à la chute du taux de rejet du PEG a été évaluée pour différents sels à plusieursconcentrations.Le deuxième volet du travail est consacré à (i) l’évaluation de la constante diélectrique desolutions à l’intérieur de nanopores (ep) d’une membrane organique de NF (polyamide) àpartir de mesures de potentiel de membrane et (ii) la validation de cette méthode. Les valeursobtenues s’avèrent être inférieures à celle de la solution externe (effet du confinement) etdiminuer avec l’augmentation de la proportion en ions calcium du mélange (effet structurantdes ions). L’accord entre les constantes diélectriques ep déterminées à partir de mesures depotentiel de membrane et de taux de rejet ionique (mélanges ternaires) valide la cohérence dumodèle de transport utilisé (exclusion stérique, électrique et diélectrique aux interfaces) etmontre que les mesures de potentiel de membrane peuvent être envisagées pour l’évaluationcorrecte de la constante diélectrique à l’intérieur de nanopores / The complexity of transport mechanisms in nanofiltration (NF) requires the developmentof reliable modelling tools for understanding and optimizing the separation process.This study is composed of two parts. The first one focuses on the retention of a neutralsolute – poly(ethylene glycol) 600 g mol-1 (PEG) – in single solute solutions and in thepresence of mineral salts by an organic NF membrane (polyamide). Results show that PEGrejection is significantly lower in mixed-solute solutions and that rejection rate drop increaseswith salt concentration. This phenomenon cannot be imputed to only the partial dehydrationof PEG molecules by surrounding ions (salting-out effect). The additional hypothesis whichwas considered in the present work is an increase in the effective pore size (pore swelling).This hypothesis was supported by electrokinetics charge density data. The contribution ofpore swelling and salting-out to the overall decrease in the rejection rate of PEG wasevaluated for different salts at various concentrations.The second part of this study deals with (i) the determination of the dielectric constantinside pores (ep) of an NF organic membrane from membrane potential measurements and (ii)the validation of this technique. Membrane potential data were analyzed by means of theSEDE (steric, electric and dielectric exclusion) transport model. ep values were found to besmaller than the bulk value and to decrease when sodium ions were replaced by calcium ions.The agreement between ep values obtained from membrane potential measurements and thosecalculated from ion rejection rate data (ternary mixtures) highlights the global coherence ofthe transport model used and shows that membrane potential measured with electrolytemixtures can be used to determine the dielectric constant inside pores with no requirement ofadditional rejection rate measurements.

Dans ces travaux de recherche nous avons cherché à développer et optimiser un procédé d'oxydation avancée dédié au traitement de l'eau. Pour cela, nous avons développé un procédé combinant la génération de radicaux hydroxyles par décharge plasma à pression atmosphérique et un catalyseur fixe. L'originalité de ce travail a été d'utiliser un système d'écoulement permettant l'obtention d'un film liquide (épaisseur<1mm) afin de permettre une interaction entre le plasma, le liquide et la surface catalytique. Les résultats ont montré que l'utilisation d'une décharge de type DBD était préférable au Glidarc, thermique, énergétique et produisant trop de NOx. Les valeurs d'efficacité respectives étaient de 0,67g.kWh-1 pour la DBD et 0,23g.kWh-1 pour le Glidarc. Les résultats ont également montré que le matériau de la contre-électrode/plaque d'écoulement pouvait influencer l'efficacité du procédé. Ainsi dans le cas du laiton, la présence de réactions de corrosion produisant des NO2- réduit l'efficacité de moitié comparée à une plaque d'acier. Le développement d'un modèle CFD 1D à partir des données expérimentales du procédé a été effectué. Ce modèle a permis d'estimer que l'efficacité énergétique de production des HO est de 4,4.10-9 molHO.J-1 pour la décharge DBD. Il a également permis de montrer que le facteur majoritairement limitant était la diffusion moléculaire des espèces dans le liquide. En effet les réactions chimiques ne dure pas plus de 1µs après l'impact du streamer et n'ont lieu que dans les premiers 5% d'épaisseur de liquide. Enfin, un dépôt catalytique de DLC dopé à l'argent et réalisé par rf-PECVD a permis d'améliorer de près de 10% l'efficacité maximale du procédé. / The aim of this research lies in the development and optimization of an advanced oxidation process dedicated to wastewater treatment. This process combines an atmospheric plasma discharge with an immobilized catalyst (Ag-DLC) in order to generate hydroxyl radicals. The novelty of this work relies in the use of a falling thin film system (thickness < 1mm) to promote the interaction between plasma discharge, the solution and the catalytic surface. The results demonstrate the interest of employing a Dielectric Barrier Discharge configuration instead of a Glidarc system. Indeed, the Glidarc system leads to a too high production level of NOx. The efficiencies of these two processes were respectively 0,67 g.kWh-1 and 0,23 g.kWh-1 for the DBD and the Glidarc system. Moreover, the influence of the counter-electrode / flowing plate material on the process efficiency was pointed out. Compared to stainless steel, the presence of corrosion reactions on the brass surface produced NO2- and thus, reduced the process efficiency. The production of HO??radicals at the plasma / water interface was estimated to be 4,4.10-9 molHO.J-1 by the use of 1D CFD modeling. Side reactions such as HO? recombinaison appear as the major limiting factors. Futhermore the model demonstrates that the time needed to complete all the chemical reactions was less than 1 µs and these reactions occurred only in the first 5% of the top liquid film. Finally with an Ag-DLC based catalytic coating elaborated by RF-PECVD, the efficiency was increased to 10% compared to the best efficiency observed with the non-catalytic system.