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

Dans le cadre de la transition énergique, le déploiement de sources d’énergies ne produisant pas de gaz à effet de serre devient primordial. Bénéficiant de la surabondante énergie fournie par le Soleil, le photovoltaïque est un des éléments-clés du bouquet énergétique du futur. Le marché du photovoltaïque est actuellement dominé par les technologies à base de silicium et les meilleurs rendements de conversion dépassent les 26% avec la technologie de cellules à hétérojonction de silicium amorphe hydrogéné (a-Si:H) sur silicium monocristallin (c-Si).Le silicium amorphe hydrogéné, déposé par PECVD, permet d’obtenir une excellente passivation de la surface du substrat de silicium cristallin, et ainsi d’obtenir des tensions de circuit ouvert au-delà de 730 mV. Cependant l’a-Si:H montre une absorption parasite des photons ultraviolets, et sa faible conductivité limite la longueur de diffusion des porteurs de charge générés en son sein, limitant la performance électrique et aussi leur contribution au courant de la cellule.Pour augmenter le rendement de cette technologie, nous proposons de fabriquer et de caractériser une nouvelle structure de cellules photovoltaïques à base d'hétérojonction de phosphure de gallium (GaP) sur c-Si, déposé par dépôt en phase vapeur aux organométalliques (MOCVD). Matériau III-V, cristallin, et à énergie de bande interdite élevée (2.26 eV contre 1.6-1.9 eV pour l’a-Si:H et 1.12 eV pour le c-Si), le GaP permettrait une croissance par épitaxie sur le c-Si, une meilleure transparence face à l’a-Si:H, ainsi qu’une passivation par effet de champ repoussant les trous, porteurs de charge positive, loin de l’interface GaP/Si. Les améliorations des caractéristiques courant-tension de telles cellules avec seulement 10 nm de GaP ont précédemment montré, par simulation, une amélioration des rendements de 2% en absolu.Dans le cadre de cette thèse, nous avons étudié expérimentalement l’effet du dépôt de GaP sur le c-Si. Nous avons mis en évidence une dégradation de la durée de vie des porteurs dans le c-Si lors d’une étape de préparation de surface pour améliorer l’épitaxie du GaP, qui favoriserait la diffusion de contaminants issus de la chambre de dépôts III-V dans le substrat. Cette étape pourrait être retirée, mais elle est nécessaire pour limiter l’émergence de domaines d’antiphase, défauts cristallins liés à la nature polaire des liaisons Ga-P qui limitent aussi la durée de vie des porteurs. De plus, la durée de vie à l’interface GaP/Si est demeure inférieure à 150 µs, malgré l’hypothétique passivation par effet de champ et sans défauts cristallins.Se basant sur ces découvertes, nous avons cherché à comprendre et améliorer la passivation de l’interface GaP/Si. Des techniques d’analyses avancées ont montré la présence de traces de carbone et d’arsenic dans le GaP, accompagné de fluor à l’interface, ainsi qu’une oxydation du GaP post-épitaxie. Différentes couches de mouillage ont été testées, permettant de corréler la rugosité, la défectuosité du GaP à la durée de vie des porteurs.D’autre part, l’intégration d’étapes de décontamination du substrat (gettering) a permis avec succès de restaurer la durée de vie volumique des charges tout en maintenant le recuit de reconstruction de surface dans le procédé de fabrication. Ces étapes ont été optimisées pour minimiser leur impact sur la couche de GaP. Un cellule avec GaP déposé sans pré-recuit atteint 11.2% tandis qu’en reléguant le GaP à une couche fenêtre, une cellule GaP/(n+)c-Si/(p)c-Si a montré un rendement amélioré à 13.8% avec le recuit et les étapes de gettering.Ce travail s'appuie sur l'expertise du CEA-INES en cellules solaires à hétérojonctions et du CNRS-LTM en épitaxie et caractérisation des matériaux III/V. / In the frame of energy transition, the development of energy sources that do not generate greenhouse gases is paramount. Benefiting from the overabundant energy provided by the Sun, photovoltaics is a key element of the future energy mix. Photovoltaics market is currently led by the silicon-based technologies, and best conversion efficiencies exceed 26% with the heterojunction solar cells technology with hydrogenated amorphous silicon (a-Si:H) on monocrystalline silicon (c-Si).Hydrogenated amorphous silicon, deposited by PECVD, enables high surface passivation of crystalline silicon, and to reach over 730 mV of open-circuit voltage. However, the parasitic absorption in the Ultra Violet region limits photon collection, and its low conductivity limits the diffusion length of charge carriers it generates, limiting the electrical performance and their contributions to the cell current.To enhance the efficiency of this technology, we propose to fabricate and characterise a new structure of photovoltaic solar cells based on heterojunction of gallium phosphide on crystalline silicon, made by metalorganic chemical vapour deposition (MOCVD). This crystalline III-V material, with high bandgap energy (2.26 eV vs 1.6-1.9 for a-Si:H and 1.12 eV for c-Si), allows its pseudomorphic epitaxy on silicon, with higher transparency vs a-Si:H along with field effect passivation that repels the holes, positive charge carriers, away from the GaP/Si interface. The improvement of current-voltage characteristics, with only 10-nm-thick GaP, have previously shown by simulation an absolute improvement of the efficiency by 2%.In the frame of this thesis, we have experimentally studied the effect of GaP deposition on c-Si. We have outlined a carrier lifetime degradation in c-Si during a surface preparation annealing that favours the diffusion of contaminants from the III-V MOCVD chamber into the substrate. This step could be removed, but it is required to limit the formation of antiphase domains, which are crystalline defects linked to the polarity of Ga-P bonds that also limit the carrier lifetime. Moreover, GaP/Si interface lifetime remains below 150 µs, despite the hypothetic field effect passivation and without crystalline defects.From these conclusions, we sought to understand and improve the GaP/Si interface passivation. Advanced analysis techniques have shown carbon and arsenic traces in the GaP, with fluorine at the interface, as well as post-epitaxy GaP oxidation. Different wetting layers were tested, correlating the roughness and defectivity of Gap to the carrier lifetime.Furthermore, integration of substrate decontamination steps (gettering) enables successful bulk carrier lifetime recovery while maintaining the surface reconstruction annealing in the process flow. These steps were optimised to minimise their impact the GaP layer. A solar cell with GaP deposited on unannealed silicon reached 11.2% while, making GaP a window layer in a GaP/(n+)c-Si/(p)c-Si stack produced a solar cell with 13.8% with annealing and gettering steps.This work relies on the expertise of CEA-INES on heterojunction solar cells and CNRS-LTM on the epitaxy of III-V materials and their characterisation.

This thesis presents a work which has been devoted to the growth of silicon thin films on crystalline silicon for photovoltaic applications by means of RF PECVD. The primary goal of this work was to obtain an amorphous growth on any c-Si surface in order to provide an efficient passivation, as required in heterojunction solar cells. Indeed, we demonstrated that epitaxial or mixed phase growths, easy to obtain on (100) Si, would lead to poor surface passivation. We proved that growing a few nm thin a-Si1-xCx:H alloy film was an efficient, stable and reproducible way to hinder epitaxy while keeping an excellent surface passivation by the subsequent deposition of a-Si:H films. Process optimization mainly based on Spectroscopic Ellipsometry, Effective lifetime measurements (Sinton lifetime tester) and current-voltage characterization led us to demonstrate that it was possible to obtain a-Si:H/c-Si heterojunction solar cells with stable VOC of 710 mV and FF of 76 % on flat (n) c-Si wafers, with solar cells of 25 cm2 whose metallization was realized by screen-printing technology. This work has also demonstrated the viability of a completely dry process where the native oxide is removed by SiF4 plasma etching instead of the wet HF removal. Last but not least, the epitaxial growth of silicon thin films, undoped and n or p-type doped, on (100)-oriented surfaces has been studied by Spectroscopic Ellipsometry and Hall effect measurements. We have been able to fabricate homojunction solar cells with a p-type emitter as well as p-i-n structures with an undoped epitaxial absorber on a heavily-doped (p) c-Si wafers.

<p>Over the last few decades, bulk-heterojunction organic photovoltaic devices comprising an intimately mixed donor-acceptor blend have gained serious attention due to their potential for being cheap, light weight, flexible and environmentally friendly. In this thesis, APFO-3/PCBM bulk-heterojunction based organic photovoltaic devices with an inverted layer sequence were investigated systematically. Doctor blade coating is a technique that is roll-to-roll compatible and cost efficient and has been used to fabricate the solar cells.</p><p>Initial studies focused on optimization of the electrodes. A thin film of the conductive polymer PEDOT:PSS was chosen to be the transparent anode. Different PEDOT:PSS films with respect to the film thickness and deposition temperature were characterized in terms of conductivity and transmission. Decent conductance and transmittance were obtained in the films deposited with wet film thickness setting of 35 μm, The cathode was fabricated from a metal bilayer comprising Al and Ti with an area about 1 cm², and the best-working cathodes contained a 70 nm thick Al layer covered by a thin Ti layer of about 10 -15 nm.</p><p>Optimized coating temperature and wet film thickness settings for the active layer and PEDOT:PSS layer were experimentally determined. The highest efficiency of the APFO-3/PCBM based inverted solar cells fabricated by doctor blading was 0.69%, which exceeded the efficiency of spin-coated inverted cells.</p><p>A higher efficiency (0.8 %) was achieved by adding a small amount of high molecular weight polystyrene to the active layer. Morphological changes after adding of the polystyrene were observed by optical microscopy and AFM. A coating temperature dependent phase separation of the APFO-3/PCBM/polystyrene blend was found.</p><p> </p>

<p>In this thesis, the microstructure of organic photovoltaic APFO-3:PC₆₁BM bulk-heterojunction blends was examined. Earlier studies have focused on the microstructure after spin coating. This thesis aims to give a better insight into microstructural degradation as the films are annealed above the glass transition temperature, T_g, and the mixture approaches thermodynamic equilibrium. Electro- and photoluminescence studies indicate that the polymer and PC₆₁BM are intermixed on a scale shorter than the exciton diffusion length of 10 nm, even when annealed above T_g. The temperature stability of APFO-3:PC₆₁BM was also investigated with respect to the molecular weight of the polymer. The photovoltaic performance of these blends was found to be stable up to temperatures approaching the glass transition temperature, especially if a high molecular-weight APFO-3 grade was used.</p><p> </p><p>The crystallization of PC₆₁BM was also investigated. Above T_g, PC₆₁BM crystallization was found to commence, albeit slowly at temperatures close to T_g. At elevated temperatures instead, micrometer sized crystals were observed to form. It was also noted that illumination while annealing APFO-3:PC₆₁BM thin films above T_g affected PC₆₁BM crystallization, the origin of which is so far unclear although chemical degradation could be largely excluded.</p>

In this thesis, the microstructure of organic photovoltaic APFO-3:PC61BM bulk-heterojunction blends was examined. Earlier studies have focused on the microstructure after spin coating. This thesis aims to give a better insight into microstructural degradation as the films are annealed above the glass transition temperature, Tg, and the mixture approaches thermodynamic equilibrium. Electro- and photoluminescence studies indicate that the polymer and PC61BM are intermixed on a scale shorter than the exciton diffusion length of 10 nm, even when annealed above Tg. The temperature stability of APFO-3:PC61BM was also investigated with respect to the molecular weight of the polymer. The photovoltaic performance of these blends was found to be stable up to temperatures approaching the glass transition temperature, especially if a high molecular-weight APFO-3 grade was used.   The crystallization of PC61BM was also investigated. Above Tg, PC61BM crystallization was found to commence, albeit slowly at temperatures close to Tg. At elevated temperatures instead, micrometer sized crystals were observed to form. It was also noted that illumination while annealing APFO-3:PC61BM thin films above Tg affected PC61BM crystallization, the origin of which is so far unclear although chemical degradation could be largely excluded.

Passivation of the crystalline silicon (c-Si) wafer surface and decreasing the number of interface defects are basic requirements for development of high efficiency a-Si:H/c-Si heterojunction solar cells. Surface passivation is generally achieved by development of detailed silicon wafer cleaning processes and the optimization of PECVD parameters for the deposition of intrinsic hydrogenated amorphous silicon layer. a-Si:H layers are grown in UHV-PECVD system. Solar cells were deposited on the p type Cz-silicon substrates in the structure of Al front contact/a-Si:H(n)/a-Si:H(i)/c-Si(p)/Al back contact. Solar cell parameters were determined under standard test conditions namely, using 1000 W/m2, AM 1.5G illumination at 25 oC. Growth of (i) a-Si:H, films on the clean wafer surface was investigated as a function of substrate temperature, RF power density, gas flow rate, hydrogen dilution ratio and deposition time and was characterized using SEM, HRTEM, AFM, SE, ATR-FTIR and I/V measurements. Structural properties of the films deposited on silicon wafer surface are directly effective on the solar cell efficiency. Morphological characterization of the grown films on the crystalline surface was found to be very complex depending on the deposition parameters and may even change during the deposition time. At 225 oC substrate temperature, at the beginning of the deposition, (i) a-Si:H films was found grown in epitaxial structure, followed by a simultaneous growth of crystalline and amorphous structure, and finally transforming to complete amorphous structure. Despite this complex structure, an efficiency of 9.2% for solar cells with total area of 72 cm2 was achieved. In this cell structure, TCO and back surface passivation do not exist. In the

Over the last few decades, bulk-heterojunction organic photovoltaic devices comprising an intimately mixed donor-acceptor blend have gained serious attention due to their potential for being cheap, light weight, flexible and environmentally friendly. In this thesis, APFO-3/PCBM bulk-heterojunction based organic photovoltaic devices with an inverted layer sequence were investigated systematically. Doctor blade coating is a technique that is roll-to-roll compatible and cost efficient and has been used to fabricate the solar cells. Initial studies focused on optimization of the electrodes. A thin film of the conductive polymer PEDOT:PSS was chosen to be the transparent anode. Different PEDOT:PSS films with respect to the film thickness and deposition temperature were characterized in terms of conductivity and transmission. Decent conductance and transmittance were obtained in the films deposited with wet film thickness setting of 35 μm, The cathode was fabricated from a metal bilayer comprising Al and Ti with an area about 1 cm2, and the best-working cathodes contained a 70 nm thick Al layer covered by a thin Ti layer of about 10 -15 nm. Optimized coating temperature and wet film thickness settings for the active layer and PEDOT:PSS layer were experimentally determined. The highest efficiency of the APFO-3/PCBM based inverted solar cells fabricated by doctor blading was 0.69%, which exceeded the efficiency of spin-coated inverted cells. A higher efficiency (0.8 %) was achieved by adding a small amount of high molecular weight polystyrene to the active layer. Morphological changes after adding of the polystyrene were observed by optical microscopy and AFM. A coating temperature dependent phase separation of the APFO-3/PCBM/polystyrene blend was found.

Since the discovery of the photovoltaic effect in bulk heterojunction devices¡Mthe considerable publications in PSCs have been reported¡OPSCs based on the concept of bulk heterojunction (BHJ) configuration where active layer comprises of a p-type donor (conjugated polymer) and a n-type acceptor (fullerene derivative) materials¡Mrepresents the most useful strategy to maximize the internal donor-acceptor interface area allowing for efficient charge separation¡OTo further enhance the power conversion efficiency from solar cells made of poly(3-hexylthiophene)/[6,6]-phenyl C61 butyric acid methyl ester (P3HT/PCBM) ¡M a new conducting polymer with optimized band energy levels are demonstrated to be one of the key properties¡OIn this study¡MI synthesized a soluble and strongly visible-light absorbing alternating conducting polymer using Suzuki coupling polymerization method¡OThe UV-Vis absorption spectra of copolymer contains an intramolecular charge transfer (ICT) transition band¡Mwhich leads to absorption extending to near-infrared region and optical band gaps is 1.55 eV¡OThe photo-electron spectroscopy in air(PESA) measurements show that the HOMO level of the polymer is ~5.0eV which is lower than P3HT¡O

In this study, zinc oxide (ZnO) nanotip and nanorod were grown on glass substrate by aqueous solution deposition (ASD). Both characteristics of the two nanostructures were investigated. For fabrication of ZnO nanostructure UV photodetector, In-Zn inter-digitated metal electrode was evaporated on the top of the grown ZnO nanostructure to form the contact via. Compared with the common value (375 nm), both the peaks from the PL spectra of ZnO nanotip and nanorod are red-shifted (409 nm) due to the massive defects in nanotip and nanorod. In order to improve the photosensiblity, heterojunction of ZnO nanostructure/TiO2 film was prepared and were made into UV photodetector. Photoresponses of both nanotip and nanorod were improved after N2O annealing at 300oC. With the heterojunction of ZnO 1D nanostructure on TiO2 film, the photoresponses of both ZnO nanotip/TiO2 film can reach to 22.85, and the rise time and decay time are 40 and 82 seconds, respectively. On the other side, the photoresponses of both ZnO nanorod/TiO2 film can reach to 27.44, and the rise time and decay time are 22 and 133 seconds, respectively.