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In organischen Solarzellen resultiert die photovoltaische Aktivität aus dem das Sonnenlicht absorbierenden Donor-Akzeptor-Heteroübergang. Die Grenzfläche zwischen den beiden organischen Materialien dient der effizienten Ladungsträgertrennung. Die vorliegende Arbeit leistet einen Beitrag im Verständnis zum Wirkungsmechanismus und der zu optimierenden Parameter in diesen Solarzellen. In Bezug auf die Anpassung des Donor-Akzeptor-Heteroübergangs wird neben dem Mechanismus der Ladungsträgergeneration an der Grenzfläche die erzielbare Leerlaufspannung in den Solarzellen diskutiert. Ein wesentliches Kriterium zur Erhöhung der Leerlaufspannung ist die Anpassung der Energieniveaus am Heteroübergang. Eine effiziente Ladungsträgertrennung wird durch eine hinreichende Stufe im Ionisationspotenzial sowie in der Elektronenaffinität am Heteroübergang erreicht. Zur Maximierung der Leerlaufspannung muss diese Überschussenergie, d.h. die Energiedifferenz zwischen photogeneriertem Exziton und freiem Ladungsträgerpaar, auf das notwendige Minimum reduziert werden. Eine Reihe von Dicyanovinyl-Oligothiophenen (DCVnT, n=3-6) wurden als Donor im Heteroübergang zu Fulleren C60 verwendet. Das Ionisationspotenzial der DCVnT nimmt mit zunehmender Kettenlänge ab, während die Elektronenaffinität, die weitestgehend durch die Dicyanovinyl-Endgruppen bestimmt wird, von der Kettenlänge nahezu unabhängig ist. Mittels photoinduzierter Absorptionsspektroskopie und zeitaufgelöster Fluoreszenzmessung wurde der Energie- und Elektronentransfer zwischen DCVnT und C60 entlang der homologen Reihe der DCVnT untersucht. Eine wesentliche Feststellung ist die Korrelation zwischen Rekombination in den Triplettzustand und der Leerlaufspannung. So konnte unter anderem gezeigt werden, dass durch die Verwendung angepasster Heteroübergänge unter bestimmten energetischen Voraussetzungen die indirekte Triplettbesetzung einen bislang nicht beachteten Verlustmechanismus für organische Solarzellen darstellt. Für organische Solarzellen ist demnach ein Kompromiss zwischen möglichst hoher Leerlaufspannung und effizienter Ladungsträgerdissoziation unter Vermeidung dieser Triplettrekombination zu erzielen. Weiterhin wird ein Konzept zur Nutzung dieser indirekten Triplettrekombination diskutiert. Dieses basiert auf der Tatsache, dass die Lebensdauer der Exzitonen im Triplettzustand gegenüber denen im Singulettzustand um 3-6 Größenordnungen höher ist. Damit wird eine höhere Diffusionslänge erwartet, was in einer dickeren und damit stärker absorbierenden aktiven Schicht genutzt werden könnte.

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Bottom-up nanofabrication, although still in its early stages with formidable challenges, is considered a potential alternative method to address the limitations of traditional top-down techniques by offering benefits including process simplification, cost reduction, and environmental friendliness. DNA-templated nanofabrication, one of the most powerful bottom-up methods, presents an innovative way to create advanced nanoelectronics. In this approach, nanomaterials with specific electronic, photonic, or other functions are precisely and programmably positioned on DNA nanostructures from a disordered collection of smaller parts. These self-assembled structures offer significant potential for improving many fields such as biosensing, drug delivery and electronic device manufacturing. This dissertation reports the successful fabrication of semiconductor-metal Schottky contacts using a DNA origami scaffold. The scaffold, consisting of DNA strands organized into a specific bar-shaped architecture, facilitates the competitive arrangement of gold and cadmium sulfide nanorods, forming heterojunctions, and addressing previous limitations in semiconductor nanomaterial availability. Electrical characterization reveals nonlinear Schottky barrier properties, with electrical conductivity ranging from 1.1 to 3.7 — 104 S/m, marking a several million-fold increase over prior work. This research establishes the feasibility of using cadmium sulfide prepared as a n-type semiconductor material and an innovative self-assembly approach for making nanoscale Schottky contacts, paving the way for the future development of DNA-based nanoscale logic gate circuits.

[pt] Heteroestruturas sensíveis à luz solar possuem grande potencial em diferentes aplicações direcionadas a um futuro limpo e sustentável, como a fotoprodução de hidrogênio (H2) e a remediação ambiental. No contexto da fotocatálise, o dióxido de titânio (TiO2) desempenha um papel crucial devido à sua ampla gama de aplicações, excelente estabilidade química, baixa toxicidade e custo relativamente baixo. No entanto, o TiO2 puro possui algumas desvantagens, como uma alta taxa de recombinação e baixa sensibilidade à luz solar, o que limita sua eficiência em aplicações fotocatalíticas. Portanto, o desenvolvimento contínuo de novos materiais com o objetivo de superar essas desvantagens é obrigatório. Entre as abordagens reportadas para superar as deficiências do TiO2 puro está a formação de heterojunções com outros semicondutores, melhorando a separação de cargas e, portanto, a eficiência fotocatalítica. Óxidos de níquel e óxidos de cobre são relatados como alternativas promissoras para a formação de heterojunções com TiO2, melhorando a transferência de carga e aumentando a absorção de luz no espectro visível do TiO2 puro. Esta tese apresenta diferentes estudos voltados para a síntese e caracterização de novos nanomateriais heteroestruturados eficientes para geração fotocatalítica de hidrogênio e degradação de poluentes perigosos. No primeiro estudo, foi relatada uma heterojunção p-n de NiO/TiO2 obtida via mecanoquímica, que apresentou uma taxa elevada de fotoprodução pelo sol de H2 em comparação com o TiO2 puro (8.85 mmol h-1 g-1 vs. 0.73 mmol h-1 g-1). Em todos os casos, a adição de NiO suportado em TiO2 reduziu a taxa de recombinação e aumentou a absorção de luz visível. Estudos de TEM, XPS e XAS demonstraram que uma dispersão homogênea e uma configuração de spin favorável dos pequenos aglomerados de NiO suportados em TiO2 foram responsáveis pela eficiência superior exibida pela amostra preparada via mecanoquímica, denominada NiO/P90- BM. Notavelmente, testes de ciclagem, de longo prazo e de envelhecimento mostraram que o fotocatalisador relatado é eficiente após vários ciclos, para uso prolongado e após longos períodos de armazenamento. Além disso, foram realizados estudos combinando EPR e a técnica de captura de spin para aprofundar na produção de superóxido e hidroxila pelas heterojunções de NiO/TiO2. Esses estudos forneceram insights sobre a aplicação potencial das heterojunções de NiO/TiO2 para a degradação fotocatalítica de poluentes gasosos e aquosos. Os resultados de EPR lançaram luz sobre a amostra de NiO/P90-BM como a mais eficiente na fotogeração de ROS, revelando que a síntese mecanoquímica resultou em uma arquitetura mais eficiente para a geração de radicais superóxido e hidroxila. Finalmente, foi relatada uma rota simples de química branda para preparar uma heteroestrutura de nanocubos de óxido cúprico (Cu2O NCs) e TiO2, denominada Cu2O NCs/TiO2, como um adsorvente eficiente para a tetraciclina (TC), que é um antibiótico de amplo espectro. FTIR e TGA foram realizados antes e após o processo de adsorção para demonstrar a adsorção de TC pela heteroestrutura Cu2O NCs/TiO2. Além disso, foram realizados testes com irradiação de luz visível para distinguir entre os processos de remoção por adsorção e fotocatalítica. Além disso, foram realizadas medições de EPR usando captura de spin para investigar a fotoprodução de ROS. Curiosamente, não houve fotoprodução de ROS detectável pela heteroestrutura Cu2O NCs/TiO2, demonstrando que a remoção de TC é exclusivamente devido à adsorção. Estes resultados contribuem para esclarecer uma discrepância na literatura quanto à atividade fotocatalítica dos Cu2O NCs sob luz visível. Coletivamente, esta pesquisa avançou o entendimento dos mecanismos fotocatalíticos e relatou novos nanomateriais heteroestruturados, destacando seu potencial para aplicações sustentáveis em diversos contextos relacionados ao meio ambiente e transição energética. / [en] Solar light-responsive heterostructures hold great potential in different applications toward a clean and sustainable future, such as hydrogen (H2) photoproduction and environmental remediation. In the context of photocatalysis, titanium dioxide (TiO2) plays a crucial role due to its wide range of applications, excellent chemical stability, low toxicity, and relatively low cost. However, neat TiO2 has some shortfalls, such as a high recombination rate and low sensitivity to solar light, which limits its efficiency in photocatalytic applications in general. Therefore, the continuous development of new materials aimed at improving these limitations is mandatory. Among the approaches to overcome the neat TiO2 shortfalls is the formation of heterojunctions with suitable semiconductors, improving charge separation and, therefore, photocatalytic efficiency. Nickel oxides and copper oxides are reported as promising alternatives for forming heterojunctions with TiO2, enhancing the charge transfer and broadening the light absorption in the visible spectrum. This thesis presents different studies aimed at the synthesis and characterization of new efficient heterostructured nanomaterials for photocatalytic hydrogen generation and hazardous pollutants abatement. In the first study, a NiO/TiO2 p-n heterojunction obtained via mechanochemistry was reported, which exhibited an improved solar-driven H2 photoproduction rate compared to neat TiO2 (8.85 mmol h-1g-1vs. 0.73 mmol h-1g-1). In all cases, the addition of NiO supported on TiO2 reduced the recombination rate and enhanced the visible light absorption. TEM, XPS, and XAS studies demonstrated that a homogenous dispersion and a favorable spin configuration of NiO clusters supported on TiO2 were responsible for the superior efficiency exhibited by the sample prepared via mechanochemistry, labeled as NiO/P90-BM. Noticeably, cycling, long-term, and aging tests have shown that the reported photocatalyst is efficient after several cycles, prolonged use, and after long periods of storage. Furthermore, studies combining EPR and the spin trapping technique were carried out to delve into the production of superoxide and hydroxyl by NiO/TiO2 heterojunctions. These studies provided insights into the potential application of the NiO/TiO2 heterojunctions for the photocatalytic degradation of gaseous and aqueous pollutants. The EPR results shed light on the NiO/P90-BM sample as the most efficient in ROS photogeneration, revealing that mechanochemical synthesis resulted in a more efficient architecture for generating superoxide and hydroxyl radicals. Besides, a simple soft chemistry route was reported to prepare a heterostructure of cuprous oxide nanocubes (Cu2O NCs) and TiO2, labeled as Cu2O NCs/TiO2, as an efficient adsorbent for tetracycline (TC), which is a broad-spectrum antibiotic. FTIR and TGA were carried out before and after the adsorption process to demonstrate the adsorption of TC by the Cu2O NCs/TiO2 heterostructure. Additionally, tests with visible light irradiation were performed to distinguish between adsorption and photocatalytic removal processes. In addition, EPR measurements were also carried out using spin trapping to investigate the ROS photoproduction. Interestingly, there was no detectable ROS photoproduction by the Cu2O NCs/TiO2 heterostructure, demonstrating that TC removal is solely due to adsorption. These results contribute to clarifying a discrepancy in the literature regarding the photocatalytic activity of Cu2O NCs under visible light. Collectively, this research has advanced the understanding of photocatalytic mechanisms and reported new heterostructured nanomaterials, while highlighting their potential for sustainable applications in diverse environmental and energy transition related contexts.

Grâce à leurs remarquables qualités de transport de charges et d’auto-organisation, les cristaux liquides colonnaires formés de molécules discotiques dérivées de colorants aromatiques sont des candidats prometteurs pour la réalisation de dispositifs photovoltaïques. Pour profiter à bien de ces propriétés, il est indispensable de maîtriser leur organisation en films minces. Un ancrage homéotrope avec les colonnes perpendiculaires au substrat est ainsi nécessaire pour conduire efficacement les charges aux électrodes. Cet alignement a été obtenu par transition d’ancrage entre un substrat solide et une cathode d’argent permettant d’obtenir des films ultra-minces (environ 25 nm d’épaisseur) homogènes orientés. Par ailleurs, une bicouche de composés discotiques intégralement alignée en ancrage homéotrope a été élaborée. A notre connaissance, ce travail constitue la première preuve de faisabilité d’une hétérojonction donneur – accepteur orientée constituée de cristaux liquides colonnaires. / Columnar liquid crystals made of discotic molecules derived from aromatic dyes are promising materials for the realization of photovoltaic devices thanks to their high charge mobility and their capacity to self-organize. In order to benefit from their anisotropic properties, it is necessary to control their organization in thin films. For example, a homeotropic anchoring where the columns are perpendicular to the substrate is required to carry the charges efficiently to the electrodes. Homogeneous homeotropically oriented ultra-thin films (approximately 25 nm) have been obtained by an anchoring transition between a solid substrate and a silver cathode. Moreover, a homeotropically oriented bilayer formed by discotic compounds has been achieved. This represents the first proof of principle of an organic heterojunction based on two oriented columnar liquid crystal layers.

Les processus photocatalytiques à la surface d’oxydes métalliques semi-conducteurs font l’objet d’intensesrecherches au niveau mondial car ils constituent des alternatives efficaces, respectueuses de l’environnement etpeu coûteuses aux méthodes conventionnelles dans les domaines de la purification de l’eau et de l’air, et de laproduction « verte » d’hydrogène. Cependant, certaines limitations pour atteindre des efficacitésphotocatalytiques élevées ont été mises en évidence avec les matériaux semiconducteurs classiques du fait de larecombinaison rapide des porteurs de charge générés par illumination. Le développement de photocatalyseurs àbase d’héterostuctures obtenues par dépôt de métaux à la surface de matériaux semiconducteurs ou parassociation de deux semiconducteurs possédant des bandes d’énergie bien positionnées devrait permettre delimiter ces phénomènes de recombinaison via un transfert de charge vectoriel. Dans ce contexte, trois typesd’hétérostructures telles que des nanomatériaux à base d’hétérojonction semiconducteur n/semiconducteur n(SnO2/ZnO), metal/semiconducteur n (RuO2/TiO2 and RuO2/ZnO) et semiconducteur p/semiconducteur n(NiO/TiO2) ont été synthétisées avec succès par différentes voies liquides. Leur composition, leur texture, leurstructure et leur morphologie ont été caractérisées par spectroscopies FTIR et Raman, par diffraction des rayonsX, microscopie électronique en transmission (MET) et porosimétrie de sorption d’azote. Par ailleurs, unecombinaison judicieuse des données issues de mesures effectuées par spectroscopie UV-visible en réflexiondiffuse (DRS) et par spectroscopies de photoélectrons X (XPS) et UV (UPS) a permis de déterminer lediagramme d’énergie des bandes pour chaque système étudié. Les catalyseurs ainsi obtenus ont conduit à desefficacités photocatalytiques plus élevées qu’avec le dioxyde de titane P25 pour la dégradation de colorantsorganiques (bleu de méthylène, l’orangé de méthyle) et la production d’hydrogène. En particulier, lesnanocomposites RuO2/TiO2 et NiO/TiO2 contenant une quantité optimale de RuO2 (5 % en masse) et de NiO(1% en masse), respectivement, ont conduit aux efficacités photocatalytiques les plus importantes pour laproduction d’hydrogène. Ces excellentes performances photocatalytiques ont été interprétées en termesd’alignement adéquat des bandes d’énergies des matériaux associé à des propriétés texturales et structuralesfavorables. Ce concept de photocatalyseurs à base d’hétérojonctions semiconductrices d’activité élevée devrait àl’avenir trouver des débouchés industriels dans les domaines de l’élimination de l’environnement de composésorganiques indésirables et de la production « verte » d’hydrogène. / Photocatalytic processes over semiconducting oxide surfaces have attracted worldwide attention aspotentially efficient, environmentally friendly and low cost methods for water/air purification as well as forrenewable hydrogen production. However, some limitations to achieve high photocatalytic efficiencies havebeen found due to the fast recombination of the charge carriers. Development of heterostucture photocatalystsby depositing metals on the surface of semiconductors or by coupling two semiconductors with suitable bandedge position can reduce recombination phenomena by vectorial transfer of charge carriers. To draw newprospects in this domain, three different kinds of heterostructures such as n-type/n-type semiconductor(SnO2/ZnO), metal/n-type semiconductor (RuO2/TiO2 and RuO2/ZnO) and p-type/n-type semiconductor(NiO/TiO2) heterojunction nanomaterials were successfully prepared by solution process. Their composition,texture, structure and morphology were thoroughly characterized by FTIR, X-ray diffraction (XRD), Ramanspectroscopy, transmission electron microscopy (TEM) and N2 sorption measurements. On the other hand, asuitable combination of UV–visible diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy(XPS) and ultraviolet photoemission spectroscopy (UPS) data provided the energy band diagram for eachsystem. The as-prepared heterojunction photocatalysts showed higher photocatalytic efficiency than P25 TiO2for the degradation of organic dyes (i.e. methylene blue and methyl orange) and the production of hydrogen.Particularly, heterostructure RuO2/TiO2 and NiO/TiO2 nanocomposites with optimum loading of RuO2 (5 wt %)and NiO (1 wt %), respectively, yielded the highest photocatalytic activities for the production of hydrogen.These enhanced performances were rationalized in terms of suitable band alignment as evidenced by XPS/UPSmeasurements along with their good textural and structural properties. This concept of semiconductingheterojunction nanocatalysts with high photocatlytic activity should find industrial application in the future toremove undesirable organics from the environment and to produce renewable hydrogen.

La production durable d’énergie et la recherche d’alternatives aux sources non renouvelables font l’objet d’un grand intérêt à l’heure actuelle. Le principal objectif de cette thèse était de synthétiser et étudier de nouveaux complexes organométalliques à base de Ru-acétylure, puis évaluer leurs propriétés photovoltaïques dans des cellules solaires hybrides à colorant et organique à hétérojonction volumique. Des complexes bimétalliques dissymétriques ont été développés afin d’obtenir des chromophores à absorption panchromatique, en bénéficiant d’une structure « push-pull » et du motif [Ru(dppe)2] comme excellent relai d’électron. En parallèle des complexes symétriques à un ou deux centres métalliques ont été développés, ceux-ci ont ensuite été intégrés à des cellules solaires organiques à hétérojonction volumique. Lors de cette étude, chaque dispositif a fait l’objet de différentes étapes d’optimisations dans le but d’améliorer les transferts de charges en améliorant la morphologie de la couche active. Les principales méthodes d’optimisations appliquées ont consisté à réaliser des traitements par « solvent vapor annealing », ajouter des additifs structurants et utiliser le colorant dans une matrice polymère dans un dispositif à mélange ternaire. / Today the sustainable energy production and research for alternatives to non-renewable sources attract a lot of interest. The aim of this PhD research was to synthetize and study new organometallic complexes Ru-diacetylide based, then to characterize their photovoltaic properties in hybrid dye-sensitized and organic bulk-heterojunction solar cells. To obtain panchromatic chromophores, asymmetric bimetallic complexes have been designed using [Ru(dppe)2] unit as excellent electron relay in a “push-pull” structure. In parallel, symmetric complexes have been developed with one or two metallic centres, and then they have been integrated to organic bulk-heterojunction solar cells. For this study, each device has been optimized through different steps, in order to improve charges transfers by improving morphology of the active layer. The main methods of optimization applied consisted of application of “solvent vapor annealing” treatment, addition of structure additives and addition of the dye in polymer matrix, in ternary molecules blend device.