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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
41

Development of novel organic optoelectronic technologies for biomedical applications / Développement des technologies optoélectroniques à base des matériaux organiques pour les applications dans le biomédical

Rezaei Mazinani, Shahab 16 October 2017 (has links)
Les dispositifs optoélectroniques organiques possèdent plusieurs avantages pour les applications dans le domaine du biomédical. Le photodétecteur organique (OPD) est un type de dispositif optoélectronique qui n’est pas encore utilisé pour la détection d’activité cérébrale. L’objectif de cette thèse a été d’explorer l’utilisation des OPD, constitués de différent matériaux donneur-accepteur d’électrons, dans le domaine des neurosciences. Nous avons présenté différent types d’OPD possédant une structure minimale, une excellente sensibilité et un grand potentiel d’intégration dans les méthodes de microfabrication existantes. Les détecteurs organiques ont été utilisés pour l’enregistrement de signaux optiques intrinsèques et de signaux fluorescents reflétant l’activité du calcium dans le cerveau. De plus, un autre aspect des OPD est présenté (en combinaison avec les transistors électrochimiques organiques (OECT)) : des systèmes électroniques biomimétiques basé sur une architecture électronique neuro-inspirée. Cette thèse démontre le potentiel des OPD pour enregistrer des activités cérébrales. Elle ouvre une nouvelle perspective, grâce à leur grande sensibilité, comme capteur optique en combinaison avec des dispositifs neuronaux implantables. Ceci élargira les frontières de l’électrophysiologie optique pour explorer les mécanismes complexes du cerveau et des maladies neurodégénératives. / Organic optoelectronic devices have many promising qualities for biomedical applications. Organic photodetectors (OPD), one type of such devices, have yet to be utilized for the detection of signals in the brain, to the best of our knowledge. The goal of this thesis was to explore the use of OPDs, based on different electron-donor and -acceptor materials in neuroscience applications. Different types of minimal-structure OPDs are presented, which have an excellent sensitivity and a high potential for incorporation into existing microfabrication methods. The organic sensors were utilized for monitoring the brain’s intrinsic optical signals and fluorescent calcium dynamics. Additionally, another aspect of these devices is presented (in combination with organic electrochemical transistors (OECT)): neuroinspired electronics, electronics that mimic biology. This thesis establishes the promise of OPDs for monitoring brain activities, which would lead to their integration, as high-sensitive micron-scale optical sensors in organic neural probes. Such device would result in exploring optical biological activities in the deep brain on the cellular level and would push the frontiers of optical-electrophysiology by giving a better understanding of complex mechanisms of the brain function and neurodegenerative diseases.
42

SiGe HBTs Operating at Deep Cryogenic temperatures

Yuan, Jiahui 09 April 2007 (has links)
As Si-manufacturing compatible SiGe HBTs are making rapid in-roads into RF through mm-wave circuit applications, with performance levels steadily marching upward, the use of these devices under extreme environment conditions are being studied extensively. In this work, test structures of SiGe HBTs were designed and put into extremely low temperatures, and a new negative differential resistance effect and a novel collector current kink effect are investigated in the cryogenically-operated SiGe HBTs. Theory based on an enhanced positive feedback mechanism associated with heterojunction barrier effect at deep cryogenic temperatures is proposed. The accumulated charge induced by the barrier effect acts at low temperatures to enhance the total collector current, indirectly producing both phenomena. This theory is confirmed using calibrated 2-D DESSIS simulations over temperature. These unique cryogenic effects also have significant impact on the ac performance of SiGe HBTs operating at high-injection. Technology evolution plays an important role in determining the magnitude of the observed phenomena, and the scaling implications are addressed. Circuit implication is discussed.
43

Synthèse d'oligomères et de polymères enrichis en porphyrines pour la conversion de l'énergie solaire

Bucher, Léo January 2017 (has links)
Le projet de cette thèse consistait à élaborer de nouveaux matériaux donneurs d’électrons pour les cellules solaires organiques. Cette technologie photovoltaïque émergente en plein essor a d’ores et déjà atteint la limite d’efficacité lui permettant d’être industrialisée et commercialisée à grande échelle. Le faible coût de production des dispositifs photovoltaïques organiques les rendent compétitives vis-à-vis des technologies inorganiques déjà bien implantées. Mais leur plus gros avantage est surement leur légèreté et leurs propriétés mécaniques qui les rendent très souples. Elles devraient donc certainement avoir un rôle majeur à jouer dans le futur en complément des cellules solaires classiques, avec une utilisation pour des applications spécifiques. Nous avons ainsi développé des polymères en utilisant des chromophores réputés pour leurs propriétés photophysiques : les porphyrines, les BODIPY et les dicétopyrrolopyrroles. Ces différentes unités absorbent intensément la lumière, ce qui les rend adéquates pour être utilisées pour la conversion de l’énergie solaire en électricité. En concevant un design original et adapté à cette application, nous avons ainsi obtenu plusieurs nouveaux polymères prometteurs. Nous avons ensuite pu étudier leurs propriétés électrochimiques et électroniques, ainsi que leurs caractéristiques photophysiques. Pour cela nous avons utilisé de nombreux outils (caméra streak, absorption transitoire femtoseconde, etc.) afin de comprendre en détails leur propriétés d’absorption et de luminescence. Ces informations nous ont permis de pouvoir ensuite comprendre leur comportement une fois intégrés dans la couche active des dispositifs photovoltaïques. En effet, le mécanisme de fonctionnement pour la création d’un courant électrique met en jeu des transferts d’électrons ultrarapides (∼50 fs) vers un accepteur d’électron. Il est alors crucial de pouvoir comprendre et contrôler les paramètres pouvant influencer l’efficacité de ces transferts et la stabilisation des charges qui en résultent, pour pouvoir finalement mener à des rendements de conversion de l’énergie lumineuse élevés.
44

Lighting and Sensing Applications of Nanostructured ZnO, CuO and Their Composites

Elsharif Zainelabdin, Ahmed ELtahir January 2012 (has links)
Low dimensional nanostructures of zinc oxide (ZnO), cupric oxide (CuO), and their composite nanostructures possess remarkable physical and chemical properties. Fundamental understanding and manipulation of these unique properties are crucial for all potential applications. Integration of nanostructured ZnO and CuO and their hybrid composites may play a significant role in the existing technology while paving the way for new exciting areas. Solution based low temperature synthesis of ZnO and CuO nanostructures have attracted extensive research efforts during the last decade. These efforts resulted in a plenteous number of nanostructures ranging from quantum dots into very complex three dimensional nanomaterials. Among the various low temperature synthesis methods the hydrothermal technique became one of the most popular approaches. The use of hydrothermal approach enabled the synthesis of diversity of nanomaterials on conventional and nonconventional substrates such as metals, glass, plastic and paper etc. The primary objectives of this thesis are to study and understand the characteristics of nanostructured ZnO, CuO, and their hybrid composites synthesized at low temperature. Likewise, the hybrid composites were successfully utilized to fabricate light emitting diodes and sensors. This thesis is organized into three major parts. In the beginning the synthesis and characterization of nanostructured ZnO, CuO, and their composite nanostructures are elaborated. Efforts have been made to understand the selective assembly of hierarchical CuO nanostructures on ZnO nanorods and to correlate it to the observed unique properties of the CuO/ZnO composite nanostructures. In the second part of the thesis fabrication, characterization, and device application of ZnO/p-polymer hybrid light emitting diode (HyLEDs) on flexible substrates are presented. In particular single and blended p-type light emissive polymers were controllably developed for potential greener and cheaper white light emitters. It was found that the HyLEDs exhibited rectifying diode characteristics together with white light emission covering the entire visible range. In the third part, pH and relative humidity sensing applications of CuO nanoflowers, and CuO/ZnO nanocorals, respectively, are described. A pH sensor based on CuO nanoflowers demonstrated good sensitivity and reproducibility over a wide range of pH. By taking the advantages of the selective growth of CuO nanostructures on ZnO nanorods and their naturally formed p-n heterojunction the realization of high sensitivity humidity sensor was achieved. The humidity sensor fabricated from the CuO/ZnO nanocorals displayed the highest sensitivity factor reported so far for its constituent materials; along with reasonably fast dynamic responses. A brief outlook into future challenges and opportunities are also presented in the last part of the thesis. / Nanophotonics
45

DC, MICROWAVE, AND NOISE PROPERTIES OF GAN BASED HETEROJUNCTION FIELD EFFECT TRANSISTORS AND THEIR RELIABILITY ISSUES

Zhu, Congyong 13 September 2013 (has links)
AlGaN/GaN and InAlN/GaN-based heterojunction field effect transistors (HFETs) have demonstrated great high power and high frequency performance. Although AlGaN/GaN HFETs are commercially available, there still remain issues regarding long-term reliability, particularly degradation and ultimately device failure due to the gate-drain region where the electric field peaks. One of the proposed degradation mechanisms is the inverse-piezoelectric effect that results from the vertical electric field and increases the tensile strain. Other proposed mechanisms include hot-electron-induced trap generation, impurity diffusion, surface oxidation, and hot-electron/phonon effects. To investigate the degradation mechanism and its impact on DC, microwave, and noise performance, comprehensive stress experiments were conducted in both un-passivated and passivated AlGaN/GaN HFETs. It was found that degradation of AlGaN/GaN HFETs under reverse-gate-bias stress is dominated by inverse-piezoelectric effect and/or hot-electron injection due to gate leakage. Degradation under on-state-high-field stress is dominated by hot-electron/phonon effects, especially at high drain bias. Both effects are induced by the high electric field present during stress, where the inverse-piezoelectric effect only relates to the vertical electric field and the hot-electron effect relates to the total electric field. InAlN/GaN-based HFETs are expected to have even better performance as power amplifiers due to the large 2DEG density at the InAlN/GaN interface and better lattice-matching. Electrical stress experiments were therefore conducted on InAlN/GaN HFETs with indium compositions ranging from 15.7% to 20.0%. Devices with indium composition of 18.5% were found to give the best compromise between reliability and device performance. For indium compositions of 15.7% and 17.5%, the HFET devices degraded very fast (25 h) under on-state-high-field stress, while the HFET devices with 20.0% indium composition showed very small drain. It was also demonstrated that hot-electron/phonon effects are the major degradation mechanism for InAlN/GaN HFETs due to a large 2DEG density under on-state operations, whereas the inverse-piezoelectric effect is very small due to the small strain for the near lattice-matched InAlN barrier. Compared to lattice-matched InAlN/GaN HFETs, AlGaN/GaN HFETs have much larger strain in the barrier and about half of the drain current level; however, the hot electron/hot phonon effects are still important, especially at high drain bias.
46

Investigation of Surface States and Device Surface Charging in Nitride Materials Using Scanning Kelvin Probe Microscopy

Sabuktagin, Mohammed Shahriar 01 January 2005 (has links)
In this work Scanning Kelvin Probe Microscopy (SKPM) was used to characterize surface states and device surface charging in nitride materials. Samples grown by Molecular Beam Epitaxy (MBE), Metal Organic Chemical Vapor Deposition (MOCVD) and Hydride Vapor Phase Epitaxy (HVPE) typically show a high surface band bending of about 1 eV. In an n-type sample with 3X1017 cm-3 carrier concentration, 1 eV upward band bending corresponds to 1.7X1012 cm-2 trapped charge density in the surface states. Under continuous ultraviolet (UV) illumination up to 0.6 eV surface photo voltage effect could be observed in some samples, which further indicates that surface band bending is very likely larger than 0.6 eV, i.e. close to 1 eV. Reactive Ion Etching (RIE)damage was observed to increase surface band bending by about 0.4 eV where as surface treatments in organic solvents and inorganic acids did not affect surface band bending significantly. These results indicate presence of high density of surface states in devices fabricated in nitride materials. Surface potential measurements immediately after turning off a reverse bias to the Schottky contact of a GaN Schottky diode as well as an AlGaN/GaN Hetero-junction Field Effect Transistor (HFET) show an increase of band bending near the Schottky contact edge. For an applied reverse bias of 4 V, about 0.5 eV increase of band bending was observed. This increase of band bending was caused by tunneling of electrons from the Schottky contact and their subsequent capture by surface states near the contact edge. In case of the HFET, the increase of band bending for a bias that caused no current flow through the device was similar to a bias that did. This showed that hot electron injection from the channel did not play a significant role in increasing surface band bending. The accumulated charge near the gate edge of a HFET can deplete the channel, which would cause the drain current to decrease. The total times of accumulation and dissipation of excess surface charge near the gate edge of the HFET were comparable to the time scales of drain current transients of current collapse and recovery. From this observation we attributed current collapse phenomena to charge accumulation near the edge of the reverse biased gate contact of a HFET.
47

II-VI Core-Shell Nanowires: Synthesis, Characterizations and Photovoltaic Applications

Wang, Kai 02 August 2012 (has links)
The emergence of semiconducting nanowires as the new building blocks for photovoltaic (PV) devices has drawn considerable attention because of the great potential of achieving high efficiency and low cost. In special, nanowires with a coaxial structure, namely, core-shell structures have demonstrated significant advantages over other device configurations in terms of radial charge collection and cost reduction. In this dissertation, several core-shell nanowire structures, including ZnO/ZnSe, ZnO/ZnS, and CdSe/ZnTe, have been synthesized and the photovoltaic devices processed from a ZnO/ZnS core-shell nanowire array and a single CdSe/ZnTe core-shell nanowire have been demonstrated. By combining the chemical vapor deposition and pulsed laser deposition (PLD) techniques, type-II heterojunction ZnO/ZnSe and ZnO/ZnS core-shell nanowire array were synthesized on indium-tin-oxide substrates. Their structures and optical properties have been investigated in detail, which revealed that, despite highly mismatched interfaces between the core and shell, both systems exhibited an epitaxial growth relationship. The quenching in photoluminescence but enhancement in photocurrent with faster response upon coating the core with the shell provides the evidence that the charge separation and collection in the type II core-shell nanowire is greatly improved. This demonstration brings much greater flexibility in designing next generation PV devices in terms of material selection and device operation mechanisms for achieving their maximum energy conversion efficiencies at a low cost and in an environmentally friendly manner. In order to achieve a high quality interface in the core-shell nanowire, CdSe and ZnTe, which have close lattice parameters and thermal expansion coefficients, were chosen to fabricate nanowire solar cells. ZnTe and CdSe nanowires were first synthesized by thermal evaporation and the shells were subsequently deposited by PLD. ZnTe/CdSe nanowires represented an inhomogeneous coating while the CdSe/ZnTe core-shell exhibited a conformal coating with obvious ZnTe eptilayer. The final PV device based on an individual CdSe/ZnTe nanowire demonstrated an efficiency of ~1.7%. In addition, a controllable synthesis of CdSe nanowire array on muscovite mica substrate was presented, providing the possibility to harvest hybrid energies in an all-inorganic nanowire array.
48

Les propriétés photoélectroniques de vitrocéramique de chalcogénures / The photoelectronic properties of chalcogenide glass ceramic

Xu, Yang 05 September 2014 (has links)
Une nouvelle famille de vitrocéramiques, avec une microstructure inédite, a été fabriquée par une cristallisation contrôlée des verres dans le système GeSe2-Sb2Se3-CuI. L'influence de la composition et du processus de cristallisation des verres de base, sur la microstructure et sur l’intensité du photo-courant des vitrocéramiques a été étudiée. Une composition optimisée, le 40GeSe2-40Sb2Se3-20CuI, a été particulièrement étudiée avec des résultats suivants: (1) Après une étude systématique , il a été constaté que cette composition donne la plus forte intensité de photo-courant parmi tous les verres étudiés dans ce système pseudo-ternaire GeSe2-Sb2Se3-Cul. Il a été également démontré que le photo-courant généré par différentes vitrocéramiques est non seulement déterminé par la composition, mais aussi par la microstructure composite de la vitrocéramique, qui est déterminée par le processus de céramisation. Ce processus de céramisation a ensuite été optimisé. Par rapport au procédé de traitement thermique en deux étapes, le procédé en une seule étape à basse température est une stratégie plus appropriée pour obtenir une microstructure efficace, favorisant la séparation des charges, construisant des canaux conducteurs et donnant une intensité de photo-courant élevée dans la vitrocéramique. (2) La microstructure composite inédite, discutée ci-dessus est composée de micro-domaines conducteurs interconnectés, formées par des cristaux Sb2Se3 faiblement conducteur en forme de tiges, couverts par des nano-cristaux de Cu2GeSe3 beaucoup plus conducteurs. Le procédé le plus probable de la photo-génération efficace des charges est le suivant: les photons sont efficacement et essentiellement absorbés par Sb2Se3 ainsi que par Cu2GeSe3. Les hétérojonctions formées par les Sb2Se3 du type n et les Cu2GeSe3 du type p, favorisent la séparation de charges, tandis que les Cu2GeSe3 interconnectées et conductrices fournissent des canaux conducteurs et jouent ainsi le rôle de collecteur efficace de charges. Il en résulte ainsi une très longue durée de vie des porteurs de charge et un fort photo-courant. (3) La formation de nano-hétérojonctions entre les cristaux Sb2Se3 et Cu2GeSe3 dans un seul micro-domaine peut conduire à une séparation efficace des électrons et des trous photo-générés. Par conséquent, pour application photo-catalytique, il n’est pas nécessaire de former des canaux conducteurs (conducteurs interconnectés des micro-domaines) dans l'ensemble de la vitrocéramique. De plus, la formation de ces canaux conducteurs, nécessiterait une augmentation de la durée ou/et la température de recuit, pouvant conduire à une diminution de l'activité photo-catalytique à cause de la taille relativement grande des grains cristallins. Les vitrocéramiques optimisées montrent une bonne capacité de désamination oxydative et une forte activité photo-catalytique en général, démontrant ainsi son potentiel en tant que photo-catalyseur efficace. / A totally new family of glass ceramics with a unique microstructure was fabricated by controlling the crystallization of the GeSe2-Sb2Se3-CuI glass system. The influences of the material composition and the crystallizing process of the precursor glasses on the microstructure and photocurrent of the prepared glass ceramics were investigated. An optimized composition, 40GeSe2-40Sb2Se3-20CuI, was particularly studied with the following significant results: (1) After a systematic study, it was found that this particular composition shows the highest photocurrent density among all studied glasses in the pseudo-ternary GeSe2-Sb2Se3-CuI system. It is also demonstrated that the photocurrent generated by different glass ceramics is not only determined by the composition, but also by the composite microstructure of the glass ceramic, which is determined by the ceramisation process. This process was then carefully studied. Compared with the two-step heat treatment process, the single-step process at a low temperature is a more efficient strategy to build up an efficient composite microstructure, which promotes charge carrier separation and provides a conductive channel, leading to a high photocurrent intensity in the glass ceramic. (2) The above-mentioned unique composite microstructure is composed of interconnected conductive microdomains, formed by low conductive rod-like Sb2Se3 crystals, covered by relatively high conductive Cu2GeSe3 nanocrystals. The most likely process for efficient photogeneration of charges is proposed as follows: photons are efficiently and essentially absorbed by Sb2Se3 as well as by Cu2GeSe3, and then the heterojunction formed by n-type Sb2Se3 and p-type Cu2GeSe3 promotes the charge separation, whereas the oriented and relatively conductive Cu2GeSe3 aggregate provides a conductive channel and plays the role of efficient charge collector. This structure results in exceptionally long lifetime of charge carriers (around 16 µs) and high photocurrent (at least 100 times higher than any of Sb2Se3 and Cu2GeSe3 individually). (3) The formation of nano-heterojunctions between Sb2Se3 and Cu2GeSe3 crystals within a single conductive microdomain can fully lead to an efficient separation of photo-generated electrons and holes. Therefore, for the photocatalytic application, it is unnecessary to form conductive channels (interconnected conductive microdomains) in the whole glass ceramic. Moreover, in order to form conductive channels, the necessary increase of annealing time or/and temperature may decrease the photocatalytic activity due to its relatively large crystal grain size. The optimized glass ceramic exhibits a good oxidative deamination ability and high photocatalytic activity, demonstrating its potential as an efficient photocatalyst.
49

Estudo e caracterização de dispositivos fotovoltaicos orgânicos (OPV) baseados em heterojunção de volume / Study and characterization of organic photovoltaic devices (OPV) based on bulk heterojunction

Coutinho, Douglas José 26 July 2011 (has links)
Um dos grandes desafios do século XXI está na produção de energia limpa e renovável, já que a demanda mundial por energia continuará crescendo, assim como a necessidade de despoluir o planeta e de diminuir a emissão dos gases do efeito estufa. Nesse contexto, a conversão de energia solar em elétrica coloca-se como uma excelente alternativa, e com isso a dos dispositivos fotovoltaicos. A tecnologia fotovoltaica baseada no silício e em outros semicondutores orgânicos encontra-se em estágio relativamente avançado, porém o custo de produção e de manutenção a proíbe em uso de grande escala. Mais recentemente, iniciaram-se pesquisas com filmes de semicondutores orgânicos, e a rápida melhora na performance dessas células solares a coloca como promissora ao mercado fotovoltaico. Em nosso trabalho, realizamos estudos sobre a performance de dispositivos fotovoltaicos orgânicos baseados na estrutura de heterojunção, estudando a influência de vários parâmetros na performance dos dispositivos. Usamos como camada ativa para nossos dispositivos o poli(3-hexiltiofeno) (P3HT) regiorregular, que é um polímero condutor de gap eletrônico em torno de 1,8 eV misturado ao [6,6]-fenil-C61-ácido butírico-metil ester (PCBM). Essa mistura é apropriada à dissociação dos éxcitons gerados nas cadeias poliméricas pelos fótons absorvidos porque, sendo o PCBM muito eletronegativo, ele captura o elétron do éxciton antes do processo natural de recombinação. Como esse fenômeno ocorre em todo o volume da camada ativa, o dispositivo leva o nome de heterojunção de volume. A estrutura básica que usamos foi de ITO/P3HT-PCBM/Al, isto é, o ITO como eletrodo transparente e bom injetor de buracos e o alumínio como eletrodo injetor de elétrons. Outros dispositivos foram feitos adicionando uma camada transportadora de buracos entre o ITO e o polímero ativo, o Poli(3,4-etileno dióxido-tiofeno):poliestireno-sulfonado (PEDOT:PSS) e/ou cálcio (Ca) entre a camada de alumínio e o polímero. Verificamos que a performance do dispositivo fotovoltaico é bastante alterada quando mediante o contato utilizado, a espessura da camada ativa e a temperatura em que o tratamento térmico é realizado. Investigou-se também, os mecanismos de injeção, transporte e geração de portadores sob variação de temperatura, no intervalo de 90 à 330K. Foi mostrado que, mediante a variação da temperatura, a corrente de curto circuito (JSC), é governada principalmente pela mobilidade dos portadores. A eficiência dos dispositivos desenvolvidos neste trabalho é comparável aos principais valores obtidos na atualidade. Para obtenção destes resultados, foi necessária intensa pesquisa em processamento, principalmente mantendo todas as etapas de fabricação em atmosfera controlada. / One big challenge of the humanity along the 21st Century is to produce energy based on clean and renewable sources. The energy consumption certainly will increase, as well as the necessity in decreasing the emission of greenhouse gases. In this context, solar energy becomes an important alternative for the production of electric energy, in particular, that of photovoltaic devices. Photovoltaics made of silicon and of other inorganic semiconductors are already available, but due to the high cost is not an alternative to produce energy in a large scale. More recently, the organic photovoltaics, due to their quick progress, have becoming as promising technology for the solar energy market. In this work, we studied bulk heterojunction organic photovoltaics, varying several parameters and its influence on the device performance. We used regio-regular poli(3-hexylthiophene) (P3HT), that has an electronic gap close to 1.8 eV, mixed with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). PCBM acts in order to dissociate the photogenerated exciton because, being highly electronegative, it captures the electron form the exciton before the recombination process. We used as basic structure the ITO/P3HT-PCBM/Al. ITO as transparent electrode and injector of holes, and aluminum as the electrons injector electrode. In other devices we added a thin layer of Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), as hole transport layer and/or calcium (Ca) between the Al and the polymer. We verify that the device performance changes considerably with the insertion of such layers, and with the thickness of the active layer and the annealing treatment. We also investigated phenomena related to injection, generation and transport of charge carriers, in the 90-330 K temperature range. We showed that the temperature is the main factor that governs the short-circuit current (JSC). It is important to remark that our devices exhibited similar efficiency compared to that of the literature.
50

Microréacteurs photocatalytiques utilisant des oxydes métalliques semi-conducteurs sensibilisés par des Quantum Dots CuInS2/ZnS / Photocatalytic microchannel reactors using metal-oxide semiconductors sensitized with CuInS2/ZnS quantum dots

Donat, Florian 20 July 2017 (has links)
La pollution actuelle des effluents hospitaliers par des médicaments, nécessite le développement de nouvelles techniques de traitement, la photocatalyse étant l’une des plus efficaces pour remédier à ce type de pollution. Cependant, les oxydes métalliques utilisés pour la photocatalyse (TiO2, ZnO, …) ne sont activables que sous irradiation UV. L’association de ces oxydes à des Quantum Dots (QDs), crée une hétérojonction qui étend la zone d’activation du photocatalyseur vers les rayonnements visibles et diminue les recombinaisons des porteurs de charges. La première partie de ce travail décrit le développement d’un photocatalyseur activable sous irradiation solaire pour la dégradation du colorant Orange II. Nous avons d’abord caractérisé l’hétérojonction créée entre ZnO et les QDs CuInS2/ZnS (ZCIS) puis étudié leur efficacité photocatalytique, en regardant notamment leurs capacités à générer des espèces réactives de l’oxygène. Dans la seconde partie, nous avons évalué la photodégradation d’un agent anticancéreux, l’Ifosfamide, présent dans les effluents hospitaliers. Pour cela, des réacteurs fermés agités et des microréacteurs ont été utilisés. Dans les deux cas, l’Ifosfamide, ainsi que ses intermédiaires de dégradation, sont photodégradés efficacement par le catalyseur ZnO/ZCIS sous une irradiation solaire de faible intensité (5 mW/cm2). Dans le cas des microréacteurs, le dépôt du catalyseur dans le microcanal a été optimisé et sa stabilité évaluée. Les résultats montrent que le catalyseur ZnO/ZCIS est réutilisable cinq fois sans perte d’activité, témoignant d’une bonne recyclabilité, ce qui en fait un bon candidat pour des applications photocatalytiques / The pollution of hospital effluents by pharmaceutical drugs, requires the development of new treatment techniques. Among these processes, photocatalysis is one of the most efficient one and allows the remediation of this kind of pollution. However, metal oxides used for photocatalysis (TiO2, ZnO, …) can only be activated by UV light. The association of these oxides with quantum dots (QDs) creates an heterojunction, which not only allows to extend the activation spectrum of the photocatalyst to the visible region but also decreases the charge carriers recombinations. The first part of this work describes the development of a catalyst responding to solar light irradiation for the degradation of the Orange II dye. First, we characterized the heterojunction created between ZnO and the CuInS2/ZnS (ZCIS) QDs and evaluated their photocatalytic efficiency. This work was undertaken by evaluating the capacity of the ZnO/ZCIS catalyst to produce reactive oxygen species (ROS). In the second part, we studied the photodegradation of the antineoplastic agent Ifosfamide commonly found in hospital effluents. For this purpose, closed and agitated reactors but also microreactors were used. In both cases, Ifosfamide, and the compounds originating from its degradation, can be fully photodegraded under simulated light of weak intensity (5 mW/cm2) using the ZnO/ZCIS catalyst. In the case of microreactors, the deposition of the catalyst was optimized and its stability evaluated. Results obtained demonstrate that the ZnO/ZCIS catalyst can be reused, at least five times, without significant loss in activity, thus demonstrating its ability to be used in real photocatalytic applications

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