One of the main limitations of training deep learning-based object detection models is the availability of large amounts of data annotations. When annotations are scarce, semi-supervised learning provides frameworks to improve object detection performance by utilising unlabelled data. This is particularly useful in plant leaf detection and possible leaf stress recognition, where data annotations are expensive to obtain due to the need for specialised domain knowledge. This project aims to investigate the feasibility of the Unbiased Teacher, a semi-supervised object detection algorithm, for detecting plant leaves and recognising possible leaf stress in experimental settings where few annotations are available during training. We build an annotated data set for this task and implement the Unbiased Teacher algorithm. We optimise the Unbiased Teacher algorithm and compare its performance to that of a baseline model. Finally, we investigate which hyperparameters of the Unbiased Teacher algorithm most significantly affect its performance and its ability to utilise unlabelled images. We find that the Unbiased Teacher algorithm outperforms the baseline model in the experimental settings when limited annotated data are available during training. Amongst the hyperparameters we consider, we identify the confidence threshold as having the most effect on the algorithm’s performance and ability to leverage unlabelled data. Ultimately, we demonstrate the feasibility of improving object detection performance with the Unbiased Teacher algorithm in plant leaf detection and possible stress recognition when few annotations are available. The improved performance reduces the amount of annotated data required for this task, reducing annotation costs and thereby increasing usage for real-world tasks. / En av huvudbegränsningarna med att träna djupinlärningsbaserade objektdetekteringsmodeller är tillgången på stora mängder annoterad data. Vid små mängder av tillgänglig data kan semi-övervakad inlärning erbjuda ett ramverk för att förbättra objektdetekteringsprestanda genom att använda icke-annoterad data. Detta är särskilt användbart vid detektering av växtblad och möjlig igenkänning av stressymptom hos bladen, där kostnaden för annotering av data är hög på grund av behovet av specialiserad kunskap inom området. Detta projekt syftar till att undersöka genomförbarheten av Opartiska Läraren (eng. ”Unbiased Teacher”), en semi-övervakad objektdetekteringsalgoritm, för att upptäcka växtblad och känna igen möjliga stressymptom hos blad i experimentella miljöer när endast en liten mängd annoterad data finns tillgänglig under träning. För att åstadkomma detta bygger vi ett annoterat dataset och implementerar Opartiska Läraren. Vi optimerar Opartiska Läraren och jämför dess prestanda med en baslinjemodell. Slutligen undersöker vi de hyperparametrar som mest påverkar Opartiska Lärarens prestanda och dess förmåga att använda icke-annoterade bilder. Vi finner att Opartiska Läraren överträffar baslinjemodellen i de experimentella inställningarna när det finns en begränsad mängd annoterad data under träningen. Bland hyperparametrarna vi överväger identifierar vi konfidensgränsen som har störst effekt på algoritmens prestanda och dess förmåga att utnyttja icke-annoterad data. Vi demonstrerar möjligheten att förbättra objektdetekteringsprestandan med Opartiska Läraren i växtbladsdetektering och möjlig stressigenkänning när få anteckningar finns tillgängliga. Den förbättrade prestandan minskar mängden annoterad data som krävs, vilket minskar anteckningskostnaderna och ökar därmed användbarheten för användning inom mer praktiska områden.

Movement is a core mechanism through which animals interact with their environment. A popular approach for investigating animal movement involves the use of GPS telemetry, which provides insights into both the spatial and temporal patterns exhibited by an individual or population. While many approaches for evaluating movement data have often analyzed intensity of use, most studies focused on a single property of use: the total duration an animal spent in a location. While this can provide insight into which landscape and habitat characteristics an individual may be selecting for, it does not fully account for how that space is being used. Therefore, it could be beneficial to combine more than one aspect of intensity of use to evaluate the behavioral mechanisms leading to patterns in space use, and by extension the drivers of home range structuring. As a territorial, central-place forager, the North American beaver (Castor canadensis) presents an ideal system for investigating drivers of home range structuring. However, while some species are easily tracked through traditional GPS attachment methods (such as GPS collars or backpacks), other species such as beavers present unique challenges given their fusiform shape and tapered neck. The overall objective of my thesis was to better understand fine-scale movement of beavers and the drivers of home range structuring. To do so, in chapter 1, I first developed and tested three different GPS transmitter attachment methods to determine which was most effective in terms of retention time (RT, total number of days a transmitter remains attached) and GPS fix success rate (FSR, % of successful fixes vs. attempted) and investigated to what degree various factors (season, sex, and age class) affected these results. In chapter 2, I analyzed space use in relation to four intensity of use metrics with machine learning to define homogenous types of space use. These metrics included the total number of visits, total and mean duration of visits, and mean interval between visits. GPS transmitters glued to the lower back of beavers provided up to two months of fine-scale data, as well as producing the highest FSR. In addition, longer retention times were found for transmitters attached to males versus females, and for transmitters deployed in the fall versus the spring. Using these data, I was able to capture five distinct population level intensity of use types including, low use – irregular, low use – regular, medium use – short duration, medium use – long duration, and lodge use. These types of use were all generally observed towards the core of the home range. In addition, all types of use were characterized by low intervals between visits except for the low use – irregular cluster. These results suggest highly structured, regular movements occurring in the core of beaver home ranges related primarily to shelter, foraging patches, and the movement paths used to link these locations. Overall, this approach allowed me to delineate between two distinct low use and medium use types and provided insight into the different behavioral mechanisms that may be driving these similar types of use. Capturing these different types of use was only possible by specifically combining multiple movement metrics at once to evaluate space use, as opposed to strictly using the number of GPS fixes to evaluate a location.

The purpose of this research is to establish the effectiveness of tuned-mass-dampers (TMD) using semi-active magneto-rheological (MR) dampers to mitigate annoying floor vibrations. Annoying floor vibration is becoming more common in today's building structures since building materials have become stronger and lighter; the advent of computers has resulted in "paperless" offices; and the use of floors for rhythmic activities, such as aerobics and concerts, is more common. Analytical and experimental studies were conducted to provide an understanding of the effects of incorporating the semi-active-TMD as a remedy to annoying floor vibration. A pendulum tuned mass damper (PTMD) in which the tuning parameters could independently be varied was used. Closed form solutions for the response of the floor using passive dampers were developed. In addition, a numerical integration technique was used to solve the equations of motion where semi-active dampers are utilized. The optimum design parameters of PTMDs using passive and semi-active dampers were found using an optimization routine. Performances of the PTMD in reducing the floor vibration level at the optimum and when subjected to off-tuning of design parameters using passive and semi-active dampers were compared. To validate the results obtained in the analytical investigation, an experimental study was conducted using an 8 ft x 30 ft laboratory floor and a commercial PTMD. Comparative studies of the effectiveness of the PTMD in reducing floor vibrations using semi-active and passive dampers were conducted. / Master of Science

In this thesis, we propose a statistical framework for estimating correlation between sensor systems measuring diverse physical phenomenon. We consider systems that measure at different temporal frequencies and measure responses with different dimensionalities. Our goal is to provide estimates of correlation between all pairs of sensors and use this information to flag potentially anomalous readings. Our anomaly detection method consists of two primary components: dimensionality reduction through projection and Gaussian process (GP) regression. We use non-metric multidimensional scaling to project a partially observed and potentially non-definite covariance matrix into a low dimensional manifold. The projection is estimated in such a way that positively correlated sensors are close to each other and negatively correlated sensors are distant. We then fit a Gaussian process given these positions and use it to make predictions at our observed locations. Because of the large amount of data we wish to consider, we develop methods to scale GP estimation by taking advantage of the replication structure in the data. Finally, we introduce a semi-supervised method to incorporate expert input into a GP model. We are able to learn a probability surface defined over locations and responses based on sets of points labeled by an analyst as either anomalous or nominal. This allows us to discount the influence of points resembling anomalies without removing them based on a threshold. / Ph. D.

Vehicle suspension systems play an integral role in influencing the overall performance of a vehicle. The suspension system of a vehicle performs multiple tasks, such as maintaining contact between the tires and the road and isolating the frame of the vehicle from road-induced vibration and shocks. A significant amount of research has been directed to improving the performance of the suspension system by varying the damping coefficient so as to alter the frequency response of the system. This study describes the development of such a damper. The goal of this research has been to design, model, fabricate and test a novel semi-active damper. The damper consists of two independent electronically controlled units placed in series with one another. The system was initially simulated using a 2 DOF quarter-car model and the performance characteristics of the damper were outlined. Following that, multiple design iterations of the damper were created and a MATLAB/Simulink model was used to simulate physical and flow characteristics of the damper. After the design and analysis was complete, the damper was fabricated and tested using a shock dyno at CenTiRe. The test results were then compared to the simulation results so as to confirm performance of the damper. Additionally, the results obtained on the dyno were then compared against that of a relative single semi-active and passive damper. / Master of Science

The incorporation of substituted stilbenes in copolymers affects the resulting solution properties and their controlled radical polymerizations. Substituted stilbene monomers readily polymerize in an alternating fashion with acceptor comonomers such as maleic anhydride and maleimide. These sterically crowded polymer backbones are classified as semi-rigid. As this is an uncommon category of polymer backbone rigidity, examples of semi-rigid and rigid polyzwitterions in the literature were reviewed as well as stilbene-containing semi-rigid polymers. Using a deprotection strategy, anionic polyelectrolytes and polyampholytes of stilbene-maleic anhydride copolymers were synthesized and characterized by first synthesizing organic-soluble polymer precursors. Solution shear rheology and statistical segment length measurements reveal that carboxylated polyanions containing stilbene and maleic acid remain semi-rigid in aqueous solutions. It was found that these semi-rigid polyanions exhibited excellent anti-HIV activity possibly due to their more extended polymer chains. This was the first time that intrinsic polymer rigidity was introduced as a possible design parameter for microbicidal applications. Reversible addition fragmentation chain transfer (RAFT) polymerization techniques were used to copolymerize 4-diethylaminostilbene with maleic anhydride. These new semi-rigid copolymers were incorporated into double hydrophilic block copolymers (DHBCS) containing semi-rigid and flexible segments. The subsequent solutions properties of these DHBCs were evaluated with respect to pH and salt responsiveness. Notably, the DHBCs exhibited a "like-charge" attraction as ionic strength increased which was attributed to the semi-rigid character of the polyampholyte block copolymer. / Ph. D.

No / The reversible in situ formation of a self-assembly building block (naphthalenediimide (NDI)–dipeptide conjugate) by enzymatic condensation of NDI-functionalized tyrosine (NDI-Y) and phenylalanine-amide (F-NH2) to form NDI-YF-NH2 is described. This coupled biocatalytic condensation/assembly approach is thermodynamically driven and gives rise to nanostructures with optimized supramolecular interactions as evidenced by substantial aggregation induced emission upon assembly. Furthermore, in the presence of di-hydroxy/alkoxy naphthalene donors, efficient charge-transfer complexes are produced. The dynamic formation of NDI-YF-NH2 and electronic and H-bonding interactions are analyzed and characterized by different methods. Microscopy (TEM and AFM) and rheology are used to characterize the formed nanostructures. Dynamic nanostructures, whose formation and function are driven by free-energy minimization, are inherently self-healing and provide opportunities for the development of aqueous adaptive nanotechnology.

Thèse ou mémoire avec insertion d'articles / Les molécules organiques semi-conductrices (MOS) ont suscité un intérêt considérable ces dernières années en raison de leurs propriétés électroniques uniques et de leurs applications potentielles dans divers domaines, tels que les diodes électroluminescentes (DEL), les transistors à effet de champ (FET) et les cellules solaires. Leurs propriétés intrigantes découlent des systèmes d'électrons π conjugués, qui permettent la délocalisation des électrons sur des structures moléculaires étendues. La synthèse des MOS implique la conception et la construction de molécules organiques présentant des propriétés électroniques spécifiques. Diverses stratégies de synthèse, notamment l'ingénierie moléculaire, la polymérisation, les complexes donneur-accepteur et les techniques d'auto-assemblage, ont été utilisées pour adapter les structures moléculaires et optimiser leurs propriétés. La possibilité de moduler la largeur de bande interdite et la structure électronique des MOS a facilité le développement de dispositifs électroniques avancés. Dans ce travail, les MOS sont préparées en utilisant des approches synthétiques modernes et de nouvelles connaissances sur le comportement des systèmes π découvertes au cours des dernières décennies pour former des hydrocarbures aromatiques polycycliques (HAPs) de grande taille et à faible bande interdite. Tout d'abord, une série de composés diradicalaires a été synthétisée en fusionnant des motifs fluorène dans un axe longitudinal sur un noyau conjugué plutôt qu'en les fusionnant latéralement, comme effectué précédemment dans la littérature. Les diradicaux neutres et les dication tetrathiafulvalène ont été étudiés et présentent un caractère diradicalaire très marqué, constituant l'un des rares exemples rapportés. De plus, une méthode efficace a été développée pour produire un isomère de l'azulénoazulène, dont la synthèse n'avait été rapportée que dans les années 1970. Les composés d'intérêt sont obtenus en moins d'étapes de synthèse et peuvent être facilement fusionnés avec d'autres unités aromatiques. Les molécules non-benzénoïdes peuvent être comparées à leur forme annulène. Cette classe de composés n'avait jamais été rapportée auparavant et présente une forte absorption dans la région UV-visible, ainsi qu'un comportement de couche ouverte, un processus de dimérisation/photodissociation et une bonne mobilité de charge dans les dispositifs FET. De plus, le vat orange 3, un colorant, est utilisé comme précurseur de polymères conjugués. En reliant son noyau à ses unités voisines par des positions spécifiques avec des atomes de carbone $sp^\textit{3}$, l'encombrement stérique est minimisé. Il s'agit des premiers dérivés d'anthantrone entièrement planarisés et conjugué. L'aplanissement des motifs conjugués avec le noyau d'anthantrone améliore les propriétés optoélectroniques, résultant en un meilleur chevauchement des orbitales π, bien que certains défis de connectivité entre le noyau et les comonomères soient identifiés dans les polymères synthétisés. Enfin, de nouveaux dérivés d'anthantrone entièrement conjugués ont été synthétisés en utilisant une stratégie similaire à celle précédente, cette fois en reliant les unités avec des atomes de carbone $sp^\textit{2}$. Ces dérivés montrent des déplacements exceptionnels d'absorption UV-visible en fonction des unités de solubilisation et un comportement d'agrégation en solution. Deux de ces analogues sont incorporés avec succès dans des dispositifs FET. / Semiconducting organic molecules (SOMs) have gained significant attention in recent years due to their unique electronic properties and potential applications in various fields, such as in light-emitting diodes (LEDs), field-effect transistors (FETs) and solar cells. Their intriguing properties arise from the conjugated π-electron systems, which enable the delocalization of electrons over extended molecular frameworks. The synthesis of SOMs involves the design and construction of organic molecules with specific electronic properties. Various synthetic strategies, including molecular engineering, polymerization, donor-acceptor complexes, and self-assembly techniques, have been employed to tailor the molecular structures and optimize their properties. The ability to tune the energy bandgap and the electronic structure of SOMs has facilitated the development of advanced electronic devices. In this work, SOMs are synthesized by taking advantage of modern synthetic approaches and novel knowledge about π-system behavior discover in the last decades to form low bandgap large polycyclic aromatic hydrocarbons (PAHs). Firstly, a series of diradical compounds is synthesized by fusing fluorene moieties in a longitudinal axis on a conjugated core rather than laterally fused, as previously shown in the literature. The neutral and tetrathiafulvalene dication diradicals are studied and both classes exhibit high diradical character, which is one of the few reported examples. Additionally, an efficient synthetic method is developed to produce an azulenoazulene isomer, whose synthesis was only reported in the 1970s. The compounds of interest are obtained in fewer synthetic steps and could be easily fused with other aromatic units. The resulting non-benzenoid molecules can be compared to their annulene form. That class of compounds has never been made before and it exhibits strong absorption in the UV-visible region and shows open-shell behavior, dimerization/ photodissociation process and good charge mobility in FET devices. Furthermore, vat orange 3, a common dye, is utilized as a precursor for conjugated polymers. By bridging its core to its linking units at specific positions with $sp^\textit{3}$ carbons, the steric hindrance is minimized. It is the first report of a fully planarized π-extended anthanthrone derivative. Flattening the conjugated moieties with the anthanthrone core improves optoelectronic properties, resulting of a better π-orbitals overlap, although some challenges in connectivity between the aromatic core and the comonomers are identified in the synthesized polymers. Finally, new fully conjugated anthanthrone derivatives are synthesized by using a similar strategy than before, this time by bridging the units on specific positions with $sp^\textit{2}$ carbon atoms. These are demonstrating exceptional solubilizing units-dependant UV-visible absorption shifts and in-solution aggregation behavior. Two of these analogs are successfully incorporated into FET devices.

L'énergie solaire est la source d'énergie la plus abondante au monde et elle peut être convertie en énergie chimique via des processus photocatalytiques. Au cours des dernières décennies, la photocatalyse sous la lumière du soleil est apparue comme une alternative innovante aux combustibles fossiles afin de résoudre et prévenir des problèmes graves liés à la crise environnementale et énergétique. Actuellement, les matériaux à base de semi-conducteurs (tels que TiO₂, C₃N₄, In₂O₃, WO₃) sont intensivement étudiés pour diverses applications photocatalytiques, y compris la réaction d’évolution d'hydrogène (HER) et la réduction de l'azote en ammoniac (NRR). Par conséquent, diverses approches telles que l'ingénierie structurelle, les hétérojonctions nanocomposites ont été étudiées afin de surmonter les problèmes de ces matériaux et ainsi augmenter l'activité catalytique. Dans le cadre de cette thèse, nous avons développé des nouvelles stratégies pour la synthèse des quatre types de photocatalyseurs efficaces pour la production d'hydrogène et la fixation de l'azote sous la lumière du soleil. Nos matériaux présentent une structure unique, qui favorise l'absorption de la lumière visible, la séparation des charges électrons-trous et l’augmentation du nombre de sites actifs.Pour l'application de la génération d'hydrogène photocatalytique, nous avons d'abord synthétisé les sphères de type éponge CdI₂nS₄ monophasées via une méthode solvothermique suivie d'un traitement au gaz contenant H₂S. La formation du complexe Cd/In avec une distribution uniforme de Cd²⁺ et In³⁺ a joué un rôle crucial dans la formation du spinelle monophasé CdIn₂S₄. L'énergie de la bande interdite s'est avérée être significativement réduite, ce qui permet une absorption étendue de la lumière visible jusqu'à 700 nm, ceci est principalement attribué à la dispersion d'espèce sulfure sur la bande de valence du CdIn₂S₄ monophasé. Avec le dépôt de Ni métallique comme cocatalyseur de réduction, le photocatalyseur hybride Ni-CdIn₂S₄ a montré une efficacité améliorée pour la production d'hydrogène sous la lumière solaire, ce qui représente une augmentation de l’activité d’environ, respectivement, 5,5 et 3,6 fois que celle des échantillons Pt-CdIn₂S₄ et Pd-CdIn₂S₄. Le deuxième système photocatalytique développé implique la préparation de nitrure de carbone graphitique dopé au S (Ni-SCN). Ce dernier est chimiquement ancré au nickel par une technique connue sous le nom de processus de photo-dépôt assisté par sulfuration. L'origine de la structure distinctive du Ni-SCN est dû à l'existence de liaisons chimiques NiS-C-N dans le système, ce qui favorisait la séparation des charges photogénérées et améliorait la capacité d’absorption lumineuse du photocatalyseur. Par conséquent, l’échantillon NiSCN synthétisé présente une excellente activité photocatalytique pour la production d'hydrogène sous la lumière du soleil. En effet, ce système présente une activité beaucoup plus élevée que celle des systèmes g-C₃N₄ dopés au S, Ni supporté g-C₃N₄ et Pt supporté g-C₃N₄ dopés au S. Pour une application photo (électro) catalytique de fixation de l'azote, nos travaux sont les premiers à rapporter la synthèse de nanoparticules d'Au chargées de nanoparticules W₁₈O₄₉ dopées au Fe (notées WOF-Au) par une synthèse solvothermique suivie d'un dépôt in situ des nanoparticules d'Au. L'incorporation de dopants Fe peut non seulement guérir les états de défaut de masse dans les réseaux non stœchiométriques W₁₈O₄₉, mais également favoriser la séparation et la migration interfaciale des électrons du photocatalyseur vers les molécules N₂ chimisorbées; tandis que les nanoparticules Au décorées sur la surface dopée au Fe W₁₈O₄₉ ont fourni les électrons à haute énergie pour la réduction de N₂ via l'effet de résonance plasmonique de surface localisé (LSPR). Le système WOF-Au plasmonique résultant montre un rendement amélioré pour la production de NH₃, beaucoup plus élevé que celui du W₁₈O₄₉ pur ainsi qu'une très grande stabilité. L'amélioration des performances photoélectrocatalytiques est principalement due à l'effet synergique des dopants Fe et des nanoparticules Au dans l'hôte W₁₈O₄₉. Enfin, les cacahuètes creuses de In₂O₃ dopées au Ru (dénotées Ru-In₂O₃ HPN) ont été fabriquées par la nouvelle stratégie d'auto-matrice suivie de la calcination des précurseurs synthétisés. Les nanoparticules uniformes In₂O₃ sont étroitement agglomérées ensemble pour former une structure de cacahuète creuse, ce qui facilite la séparation et le transport des l'électrons-trous photoexcités, améliorant l’absorption de la lumière par multi-réflexion. De plus, l'introduction des dopants Ru induit de nombreuses lacunes en oxygène à la surface et réduit l'énergie de la bande interdite du système photocatalytique. Ces lacunes d'oxygène agissent comme des centres de piégeage, facilitant la séparation des électrons trous photoexcités. Par conséquent, le taux de production d'ammoniac des Ru-In₂O₃ HPNs est 5,6 fois plus élevé que celui des In₂O₃ HPNs purs et largement supérieur au matériau en vrac d'In₂O₃, lorsqu’il est soumis à l’irradiation solaire. / Solar energy is the most abundant energy source in the world, and it can be converted into chemical energy via photocatalytic processes. Over the last decades, sunlight-driven photocatalysis has emerged as an innovative alternative to fossil fuels for solving the severe problems related to environmental diseases and the energy crisis. Currently, semiconductorbased materials (such as TiO₂, C₃N₄, In₂O₃, WO₃, BiVO₄) have been intensively studied for diverse photocatalytic applications, including the hydrogen evolution reaction (HER) and the nitrogen reduction reaction (NRR) to produce ammonia. However, the drawbacks of weak visible light absorption, low electron-hole separation with high recombination rate, and lack of surface active-sites have limited the photocatalytic performance of these semiconductorbased photocatalysts. Therefore, various approaches such as structural engineering, nanocomposite heterojunctions have been applied to overcome the limitations of these materials and boosting the catalytic activity. In this thesis, we employed novel strategies to develop four efficient photocatalytic systems for hydrogen production and nitrogen fixation. Our materials possessed a unique structure, which is advantageous to promote the visiblelight absorption, facilitate the separation of charge carrier, and increase the number of surface-active sites. For the photocatalytic hydrogen evolution application, we firstly synthesized the singlephase CdIn₂S₄ sponge-like spheres via solvothermal method followed by H₂S gas treatment. The formation of CdIn-complex with uniform distribution of Cd²⁺ and In³⁺ played a crucial role in achieving the spinel structured-single phase CdIn₂S₄. The bandgap energy was found to be significantly reduced, resulting in the extended visible light absorption up to 700 nm, which was primarily attributed to the sulfide species-mediated modification of the valence band in CdIn₂S₄ single-phase. With the deposition of Ni metal as a reduction cocatalyst, the hybrid Ni-CdIn₂S₄ photocatalyst showed enhanced solar light-driven photocatalytic hydrogen evolution efficiency, which is around 5.5 and 3.6 folds higher than that of Pt-CdIn₂S₄ and Pd-CdIn₂S₄ samples, respectively. The second developed photocatalytic system involved the preparation of chemically bonded nickel anchored S-doped graphitic-carbon nitride (Ni-SCN) through a technique known as sulfidation assisted photo-deposition process. The origin of the distinctive structure of Ni-SCN was due to the existence of Ni-S-C-N chemical bonds in the system, which fundamentally favored the separation of photogenerated electron-hole and improved the light-harvesting capabilities of the photocatalyst. Consequently, the synthesized Ni-SCN exhibited an excellent sunlight-driven photocatalytic activity toward hydrogen evolution, which was several times higher than Sdoped g-C₃N₄, Ni supported g-C₃N₄ and Pt loaded S-doped C₃N₄ systems. For photo(electro)catalytic nitrogen fixation application, our work is the first to report the synthesis of Au nanoparticles loaded Fe doped W₁₈O₄₉ (denoted as WOF-Au) nanorods through a solvothermal synthesis following by in situ deposition of Au nanoparticles. The incorporation of Fe dopants can not only heal the bulk-defect-states in nonstoichiometric W₁₈O₄₉ lattices but also promote the separation and interfacial migration of electrons from photocatalyst to chemisorbed N₂ molecules; while Au nanoparticles decorated on the Fe doped W₁₈O₄₉ surface provided the high energetic electrons for N₂ reduction via the localized surface plasmon resonance effect (LSPR). The obtained plasmonic WOF-Au system shows an enhanced NH₃ yield, which is much higher than that of the bare W₁₈O₄₉, as well as very high stability. The enhancement in photoelectrocatalytic performance is mainly contributed by the synergetic effect of Fe dopants and plasmonic Au nanoparticles on the W₁₈O₄₉ host. Lastly, Ru doped In₂O₃ hollow peanuts (demoted as Ru-In₂O₃ HPNs) were fabricated by the novel self-template strategy followed by the calcination of the as-synthesis precursors. The uniform In₂O₃ nanoparticles were closely packed together to form a hollow peanut structure, which facilitated the separation and transportation of photoinduced electron-hole and favored the light-harvesting ability by the internal multi-reflection process. Furthermore, the introduction of Ru dopants induced numerous surface oxygen vacancies and narrow down the bandgap energy of the photocatalytic system. These oxygen vacancies act as trapping centers, facilitating the separation of photoexcited electrons and holes. Consequently, the ammonia production rate of Ru-In₂O₃ HPNs was 5.6 times and much higher as compared to pure In₂O₃ HPNs and bulk material of In₂O₃ under solar light irradiation.

A une époque où les technologies nouvelles fleurissent chaque jour, un domaine particulier se détache : l’électronique organique. Par son utilité et sa facilité de mise en œuvre, l’électronique organique affiche de grandes promesses pour l’avenir. Dans le but d’améliorer le procédé de fabrication et la durée de vie de ces dispositifs, le travail de cette thèse s'est focalisé sur la synthèse de copolymères à architectures variées à base de poly(3-hexylthiophène) (P3HT). Après avoir exposé les problématiques et objectifs de la thèse dans une première partie, la synthèse de différents précurseurs P3HT est décrite. Ces matériaux représentent la base des travaux présentés dans cet ouvrage. Dans un premier temps, l'optimisation de la synthèse des copolymères à blocs rigide-flexible a été réalisée en suivant une stratégie adaptée pour une application en électronique organique. La conception de nouveaux matériaux semi-conducteurs à architectures ramifiées est traitée par la suite. Enfin, le dernier chapitre porte sur l'intégration d’un copolymère, le P3HT-b-Poly(4vinylpyridine), en cellule photovoltaïque organique en tant qu'additif de la couche active. Cette approche s’avère être particulièrement puissante, permettant notamment de diminuer le temps et le coût énergétique de la mise en œuvre de ces cellules en s’affranchissant d’une étape clé de la fabrication, le recuit. / At a time when new technologies emerge every day, a specific domain stands out: the organic electronic. Through its low cost processing or even its utility, the organic electronic constitutes a very promising future.In order to improve the fabrication process and the lifetime of the devices, the work of this thesis was focused on the synthesis of copolymers with various architectures based on poly(3-hexylthiophene) (P3HT). After a first part where main issues and objectives are presented, the synthesis of different P3HT-based precursors is described in a part which could be considered as the heart of these works. Starting with appropriated precursors, the optimization of rod-coil diblock copolymer synthesis was performed following a strategy designed specifically for organic electronic application. Moreover, the precursors were used for the conception of new semi-conducting materials with a variety of architectures, such as graft and star copolymers. Finally, the last part deals with the integration of the P3HT-b-Poly(4-vinylpyridine) copolymer into organic solar cell as an additive of the active layer. This approach turns out to be powerful, especially allowing decreasing the time and the energy cost by avoiding the key step of the fabrication process of those devices, the annealing step.