Electrically detected magnetic resonance (EDMR) is a sensitive spectroscopic technique, which can be used to readout few to single electron spins in semiconductor and carbon nanodevices for applications in solid state quantum information processing (QIP). Since only electrically active defects contribute to the EDMR signal, this technique can be used further to investigate defects and impurities in photovoltaic devices, in which they limit the sunlight-to-energy conversion efficiency significantly. Here, I employ X-band EDMR for semiconductor defect analysis and identify the most important recombination centres in Czochralski silicon with oxide precipitates, which can be intentionally grown to confine detrimental metallic impurities to inactive regions of the wafer in order to serve as a defect-free substrate for modern silicon photovoltaic devices. Those experiments show that oxide precipitation is accompanied by the formation of silicon dangling bonds. Furthermore, I describe a very promising route towards the fabrication and readout of few to single electron spins in carbon nanotube devices, which can be characterised structurally via transmission electron microscopy in order to relate their electrical and spin properties with their structure. Finally, I employ EDMR to read out electron spin states in donor-doped silicon field-effect transistors as a prerequisite for their application in QIP. I report on a novel cryogenic probe head for EDMR experiments in resonant microwave cavities operating at 0.35 T (9.7 GHz, X-band) and 3.34 T (94 GHz, W-band). This approach overcomes the inherent limitations of conventional X-band EDMR and permits the investigation of paramagnetic states with a higher spectroscopic resolution and signal intensity. Both advantages are demonstrated and discussed. I further report on a novel mechanism giving rise to the EDMR effect in donor-doped silicon field-effect transistors, which is capable of explaining why the EDMR signal intensities of the conduction electrons are enhanced by a factor of ∼100, while the donor resonance signals increase by a factor of ∼20 from X- to W-band only. The spin-relaxation and dephasing times are extracted from a series of pulsed-EDMR measurements and confirm this model. The author gratefully acknowledges funding from Trinity College Oxford, Department of Materials, EPSRC DTA, and Konrad-Adenauer-Stiftung e.V. (Begabtenförderung).

Le but de ce travail a été de développer des cellules à base d’oxyde nanoporeux photosensibilisé sur support plastique. Dans ce contexte, une nouvelle voie d’élaboration de couches de nanoparticules d’oxyde à basse température a été développée par irradiation ultraviolet sous air. Tout d’abord, des couches de dioxyde de titane ont été préparées par cette méthode, les films obtenus étant constitués d’un réseau mésoporeux de nanoparticules interconnectées de dioxyde de titane de structure anatase d’après les caractérisations effectuées par microscopie électronique à balayage, diffraction des rayons X, porosimétrie d’adsorption d’azote et d’intrusion de mercure et analyse thermogravimétrique. Après sensibilisation des couches par un complexe polypyridyle de ruthénium, les cellules photovoltaïques élaborées avec des films en contact avec un électrolyte liquide présentent des rendements de conversion énergétique compris entre 1,6 et 2,5 % suivant la nature des particules utilisées. Cette voie a ensuite été élargie à d’autres oxydes tels que l’oxyde de zinc et le dioxyde d’étain ainsi qu’à des oxydes en configuration « cœur-écorce ». Les rendements obtenus avec le dioxyde d’étain, 1,5 à 1,8%, sont tout à fait remarquables par rapport à ceux décrits dans la bibliographie pour des couches traitées à haute température. Les rendements plus élevés avec les couches traitées aux UV étant liés à une amélioration des tensions de circuit ouvert et des facteurs de forme, les phénomènes physiques régissant les performances de ces dispositifs ont été étudiés par différentes techniques, notamment la spectroscopie d’impédance électrochimique et le déclin de tension de circuit ouvert. Enfin, les performances électrochromes des films de dioxyde de titane traités aux UV ont été caractérisées sur support verre et plastique en présence d’un électrolyte liquide ionique, les efficacités de coloration étant comparables aux systèmes élaborés à haute température. / This work aimed to develop dye-sensitized solar cells on plastic substrates. In this context, a new low-temperature method to make nanoporous oxide layers based on ultraviolet irradiation under air was studied. First of all, titanium dioxide layers were prepared with this method; the films obtained were composed of a mesoporous network of interconnected anatase titanium dioxide nanoparticles as evidenced by scanning electron microscopy, X-ray diffraction, nitrogen sorption and mercury porosimetries, and thermogravimetric analysis. After sensitizing the films with a ruthenium polypyridyl complex, the photovoltaic cells based on the films in contact with a liquid electrolyte gave conversion efficiencies between 1.6 and 2.5% depending on the nature of the particles used. This low-temperature method based on ultraviolet irradiation was then expanded to other oxides, such as zinc oxide and tin dioxide, as well as to core-shell structures. The conversion efficiencies obtained with tin dioxide were very high, i.e. 1.5 to 1.8%, compared to those usually reported in the literature for films sintered at high temperatures. The higher efficiencies obtained for the UV-treated films were related to higher open circuit potentials and higher fill factors. Therefore, the physical phenomena involved were investigated with various techniques; in particular, electrochemical impedance spectroscopy and open circuit voltage decay. Finally, the electrochromic performances of the low-temperature UV-processed nanoparticulate titanium dioxide films were studied on glass and plastic substrates with an ionic liquid. The coloration efficiencies were found to be comparable to those of high-temperature processed layers.

Människans energianvändning måste förändras. Mer än 80 % av den primära energianvändningen är i dagsläget baserad på fossila bränslen. För att uppnå en mer hållbar klimatutveckling måste en större del av energianvändningen framställas av förnybara energikällor, exempelvis solenergi. Syftet med denna studie är att exemplifiera praktiska, tekniska, ekonomiska samt arkitektoniska faktorer och aspekter som bör tas i beaktande vid solcellsinstallationer i en bebyggelse. Genom en fallstudie undersöktes Sankt Sigfridområdet i Växjö. Fallstuiden avgränsades till fyra fastigheter med möjlig solcellsinstallation samt en möjlig solcellspark. Genom teoretiska utgångspunkter, studiebesök, observationer, solstudie samt tekniska- och ekonomiska beräkningar bedömdes solcellers möjliga elproduktion och potentiella besparing. Integreringsförslagen tog fram utifrån anskaffad teori och en surveyundersökning med utgångspunkt i hur byggnaders gestaltning påverkas vid en solcellsinstallation. Med dagens generösa statliga subventionsmedel finns möjlighet till en ekonomisk lönsamhet vid en solcellsinvestering, vilket återspeglas i resultatets besparingsberäkning. Fallstudien påvisar även komplexiteten vid solcellsinstallationer samt hur olika praktiska, tekniska, ekonomiska och arkitektoniska faktorer och aspekter komplicerar integreringen i en bebyggelse. / The global energy use must change, more than 80 % of the primary energy use is currently based on fossil fuels. To achieve a more sustainable development, a larger part of the energy consumption must be produced from renewable energy sources, such as solar energy. The purpose of this study is to exemplify practical, technical, economical and architectural factors and aspects that should be taken into consideration regarding solar cell integration in buildings. Through a case study, the Sankt Sigfrid area in Växjö was examined and bounded to four properties with possible solar cell installation as well as a possible solar cell park. Through theory, study visits, observations, solar study as well as technical and economical calculations, the solar cells' possible electricity production and potential savings were demonstrated. The integration proposals were compiled through the obtained theory and a survey based on how the design of building objects is affected by a solar cell installation. With today's generous government subsidies, there is a possibility of economic profitability regarding solar cell investments, which is reflected in the profit calculation of the result. The case study also demonstrates the complexity of solar cell installations as well as how various practical, technical, economical, architectural factors and aspects complicate the integrations onto buildings.

Dye-sensitized Solar Cells (DSSC), also known as Grätzel cells, have been identified as a cost-effective, easy-to-manufacture alternative to conventional solar cells. While mimicking natural photosynthesis, they are currently the most efficient third-generation solar technology available. Among others, their cost is dominated by the synthetic dye which consists of efficient Ruthenium based complexes due to their high and wide spectral absorbance. However, the severe toxicity, sophisticated preparation techniques as well as the elevated total cost of the sensitizing dye is of concern. Consequently, the current global trend in the field focuses on the exploitation of alternative organic dyes such as natural dyes which have been studied intensively. The main attractive features of natural dyes are their availability, environmental friendly, less toxicity, less polluting and low in cost. This contribution reports on the possibility of using sepia melanin dye for such DSSC application in replacement of standard costly ruthenium dyes. The sepia melanin polymer has interesting properties such as a considerable spectral absorbance width due to the high degree of conjugation of the molecule. This polymer is capable of absorbing light quantum, both at low and high energies ranging from the infrared to the UV region. The comprehensive literature survey on Grätzel solar cells, its operating principle, as well as its sensitization by natural dyes focusing on sepia melanin has been provided in this master’s dissertation. The obtained results in investigating the morphology, chemical composition, crystalline structure as well as optical properties of sepia melanin samples using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy x-ray diffraction, X-ray Diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), Raman spectroscopy, UV-VIS absorption spectroscopy as well as Photoluminescence (PL) for Grätzel solar cell application have been reported. These results represent an important step forward in defining the structure of melanin. The results clearly show that sepia melanin can be used as natural dye to DSSC sensitization. It is promising for the realization of high cell performance, low-cost production, and non-toxicity. It should be emphasized here that natural dyes from food are better for human health than synthetic dyes. / Physics / 1 online resource (xii, 101 leaves) : illustrations / M. Sc. (Physics)

Afin d’obtenir une approche où l’aspect industriel du projet est soutenu par les connaissances académiques et les capacités analytiques du monde de la recherche, ce travail portant sur les cellules photovoltaïques organiques souples grande surface commence par décrire l’énergie photovoltaïque dans son ensemble. Les tenants et aboutissants de son développement sont détaillés, ainsi que ses filières technologiques. Les semi-conducteurs organiques, les mécanismes physiques mis en jeu dans la production d’électricité d’origine photovoltaïque et les grandeurs électriques associées aux cellules photovoltaïques organiques ainsi que les différentes structures de celles-ci sont ensuite présentés. Les dispositifs réalisés dans le cadre de ce travail sur les cellules photovoltaïques organiques sont présentés. Les différentes techniques de dépôt de couches minces, aussi bien celles permettant la production en masse que celles permettant la production à plus petite échelle sont présentées. Cette présentation s’accompagne d’une recherche qui se veut exhaustive des publications relatant l’utilisation des ces techniques d’impression afin de créer des dispositifs photovoltaïques organiques. Une comparaison de ces différentes techniques est menée afin de déterminer les modes de production pertinents. Une étude bibliographique complète menée sur les cellules « grande surface » est présentée. Les cellules et modules réalisés grâce au procédé pilote d’enduction par héliogravure sont ensuite présentés. Le travail réalisé sur un autre procédé, le « doctor blade », est ensuite exposé. Enfin, la problématique du séchage et du recuit des couches minces déposées en continu est posée, et le traitement micro-onde proposé comme solution. / To obtain an approach where the industrial aspect of the project is supported by academic knowledge and the analytical capacities of research, this work concerning the large area flexible organic solar cells begins by describing the photovoltaic energy in general. The ins and outs of its development are detailed, as well as the different technologies involved. The organic semiconductors, the physical mechanisms involved in the photovoltaic electricity production and the physical values attached to the organic solar cells as well as the various structures of these cells are then presented. Devices realized within the framework of this work are then presented. The various techniques of depositing thin layers allowing the mass production as well as those allowing the smaller-scale production are presented. This presentation comes along with an exhaustive research of the publications telling the use of these techniques of printing to create organic photovoltaic devices. A comparison of those various techniques is led to determine the relevant means of production. A complete bibliographical study led on large area organic solar cells is presented. Cells and modules realized thanks to the experimental process of heliogravure coating are then presented. The work realized with another process called doctor blade is then exposed. Finally, the problem of the drying and annealing of the thin layers deposited continuously is raised, and the microwave treatment proposed as a possible solution.

Parmi les nitrures III-V, le matériau InGaN a été intensément étudié depuis les années 2000 pour des applications photovoltaïques, en particulier pour des cellules multi-jonctions, grâce à son large gap modulable pouvant couvrir quasiment tout le spectre solaire. On pourrait alors atteindre de hauts rendements tout en assurant de bas coûts. Cependant, l’un des problèmes de l’InGaN est l’absence de substrat accordé en maille provoquant une grande densité de défauts et limitant ainsi les performances des composants. Nous avons donc étudié la faisabilité de cellules solaires simples jonctions à base d’InGaN sur des substrats alternatifs comme le silicium et le verre afin de baisser les coûts et d’avoir de larges applications. Afin d’adapter l’InGaN sur ces substrats alternatifs, nous avons utilisé une couche tampon en ZnO. Ce travail a été réalisé dans le cadre du projet ANR NewPVonGlass. Plus particulièrement, dans ce projet, mon travail avait pour objectifs de réaliser des caractérisations électriques et optiques des matériaux et des composants. Les deux premières parties de cette thèse introduisent le matériau InGaN et l’effet photovoltaïque. Les techniques de caractérisation utilisées sont expliquées dans le troisième chapitre. Ensuite, les résultats obtenus lors de la caractérisation cristalline du matériau InGaN sont présentés en fonction du substrat, de la concentration d’indium et de l’épaisseur de la couche. Puis, la cinquième partie développe les caractérisations des premières cellules à base d’InGaN sur saphir. Enfin, dans le dernier chapitre, des simulations de cellules solaires à base d’InGaN ont été réalisées. Le modèle développé nous a permis d’optimiser la structure et le dopage du composant et de déterminer les paramètres critiques. Nous montrons donc, dans ce travail, le développement d’une cellule solaire à base d’InGaN : des caractérisations des matériaux de base à celles des cellules solaires, en passant par la modélisation. / Among III-V nitrides, the InGaN material has intensively been studied since the year 2000 for photovoltaic applications, in particular for multi-junction solar cells, thanks to its large tunable band gap covering almost the entire solar spectrum. Then, it will be possible to reach high efficiency and low cost. However, one of the problems of InGaN material is the absence of lattice-matched substrate leading to high defect density which limits device performances. We have thus studied the feasibility of single junction InGaN based solar cells on alternative substrate such as silicon and glass in order to lower the price and to benefit from their wide application fields. To adapt InGaN material on these new substrates, we have utilized ZnO buffer layer. This work has been carried out within the framework of the ANR project NewPVonGlass. More particularly, in this project, I was in charge of the electrical and optical characterizations of the materials and devices. In the two first parts of this manuscript, the InGaN material and the photovoltaic effect are introduced. Then, the characterization techniques are explained in the third chapter. In the fourth part, the results obtained during crystalline characterization of the InGaN materials are presented depending on the substrate, the indium percentage and the InGaN layer thickness. Then, the fifth chapter presents the first InGaN-based solar cell characteristics on sapphire substrate. Finally, in the last part, simulations of InGaN-based solar cell have been performed. The developed model was able to optimize the structure and to determine the critical parameters. Thus, we have shown in this work the development of an InGaN-based solar cell from the base material characterizations to the device tests, through modeling.

Parmi les filières de cellules photovoltaïques, les cellules solaires organiques suscitent un intérêt industriel par leur faible coût financier et de production énergétique et leur application possible sur des substrats flexibles de type plastique. L'ITO (Indium Tin Oxide) est l'électrode transparente conductrice (ETC) la plus utilisée pour ces cellules ainsi que pour d'autres dispositifs optoélectroniques. Cependant, ce matériau n'est pas sans présenter certains inconvénients (rareté de l'indium, structure non adaptée à des substrats flexibles,…), et la recherche d'alternatives à l'ITO est une préoccupation actuelle de la communauté scientifique internationale. Une possibilité est alors offerte par des structures multicouches de type Oxyde|Métal|Oxyde. Le rôle des deux couches d’oxydes est d’accorder, en ajustant les épaisseurs, la position, l’intensité et la largeur de la fenêtre spectrale de transmission. Des travaux numériques et expérimentaux couplés ont été effectués en particulier sur les structures SnOx|Ag|SnOx, TiOx|Ag|TiOx et ZnS|Ag|ZnS. Par microstructuration de telles électrodes ou bien par incorporation d’un bicouche Cu|Ag comme feuillet métallique au coeur de la structure, il est possible d’améliorer leurs performances optiques en amplifiant et en élargissant la fenêtre spectrale de transmission, sans dégrader leur haute conductivité. L’intégration d’électrodes SnOx|Ag|SnOx et TiOx|Ag|TiOx au sein de cellules solaires organiques inverses a été entrepris. Des résultats photoélectriques très prometteurs ont été obtenus avec la structure TiOx|Ag|TiOx qui permet d’atteindre des performances de niveau quasi-équivalent aux cellules de référence à base d’ITO. / Among all variants of photovoltaic thins films, organic solar cells generate a major industrial interest due to low manufacturing costs, reasonable levels of energy production and suitability to flexible substrates like plastic. ITO (Indium Tin Oxide) is the most used Transparent Conductive Electrode (TCE) for organic solar cells as well as other optoelectronic devices. However, this material is not without drawbacks (scarcity of indium, non-suitability to flexible substrates...), and the search for alternatives to ITO is actively pursued by the international scientific community. One possibility is offered by Oxide|Metal|Oxide multilayer structures. By reaching the thin metal layer percolation threshold and by varying its thickness, it is possible to obtain very high conductivity and transparency of this multilayer in the visible spectral range. The role of both oxide layers is to tune the position, intensity and width of the spectral transmission window by adjusting the oxides’ thicknesses. Coupled experimental and numerical works were lead in particularly on SnOx|Ag|SnOx, TiOx|Ag|TiOx and ZnS|Ag|ZnS structures. By microstructuring such electrodes, or by incorporating a Cu|Ag bilayer as metal sheet at the core of the structure, it is possible to increase the optical performances by amplifying and expanding the spectral transmission window without degrading the high conductivity. The integration of SnOx|Ag|SnOx and TiOx|Ag|TiOx electrodes in inversed organic solar cells was undertaken. Very promising photoelectric results were obtained with the TiOx|Ag|TiOx structure which allows to reach performances close to that obtained with ITO-based reference cells.

O presente trabalho tem como objetivo contribuir para o conhecimento, entendimento e desenvolvimento das células solares sensibilizadas por corantes. Assim foram abordadas rotas sintéticas com o fim de obter novas espécies supramoleculares constituídos por fragmentos que apresentam separadamente ótimas propriedades eletrônicas e eletroquímicas. A abordagem sintética feita é muito importante dado que dá as bases para sistemas supramoleculares como o apresentado nas perspectivas, nos quais estase visando diminuir os processos de recombinação e melhor aproveitamento do espectro solar através da estabilização do corante foto-oxidado e da transferência vetorial de elétron/energia. Na série de complexos apresentada e aplicada no presente trabalho realizou-se um estudo comparativo buscando determinar qual é o melhor sistema de injeção de elétrons na banda de condução do TiO2, obtendo uma diferença considerável entre os sistemas estudados, sendo assim o sistema com o ligante acido 2,2 -bipiridine-4,4 -dicarboxilico o complexo que melhor injeta elétrons na BC. / The present work aims to contribute to the knowledge, understanding and development of solar cells sensitized by dyes. Thus, synthetic routes were approached in order to obtain new supramolecular species constituted by fragments that separately present excellent electronic and electrochemical properties. The synthetic approach is very important since it provides the basis for supramolecular systems such as that presented in the perspectives, in which stasis is aimed at decreasing the processes of recombination and better utilization of the solar spectrum through the stabilization of the photo-oxidized dye and the vectorial transfer of electron /energy. In the series of complexes presented and applied in the present work, a comparative study was carried out to determine which is the best electron injection system in the conduction band of TiO2, obtaining a considerable difference between the studied systems, being thus the complex with the ligand 2,2 -Bipyridine-4,4 -dicarboxylic acid the best system that injects electrons into BC.

Esta tese tem como objetivo contribuir para o conhecimento e desenvolvimento das células solares sensibilizadas por corantes, através da elaboração de novas espécies supramoleculares e de estudos fundamentais de caracterização do filme de TiO2-P25 e da interface TiO2-Corante pela técnica de microscopia Raman confocal. Os estudos de microcopia Raman confocal da distribuição das fases cristalinas rutilo e anatase em filmes de TiO2-P25 (Degussa) mostraram que a fase rutilo está presente em agregados de diferentes tamanhos (de 250 nm a 3 µm) distribuídos na fase anatase e que estes agregados permaneceram mesmo após os processos de preparação da suspensão coloidal. Na presença do corante N3, verificou-se que a irradiação com laser em 532 nm, usando potência acima de 25 mW cm-2, provoca a absorção e posterior combustão do filme interfacial, com drásticas mudanças na morfologia visualizadas por microscopia Raman confocal, revelando a ocorrência da transformação de anatase em rutilo na região de incidência do feixe de laser. Outro ponto investigado nesta tese, foi a síntese e aplicação de novos sensibilizadores supramoleculares em células solares sensibilizadas por corante (DSC), visando diminuir os processos de recombinação e melhor aproveitamento do espectro solar através da estabilização do corante foto-oxidado e da transferência vetorial de elétron/energia. Além dos trabalhos com novas porfirinas supramoleculares, reproduzidas no apêndice, esta tese apresenta um estudo detalhado de uma série, formada por três espécies diméricas, constituídas pelas unidades [Ru(dcbH2)Cl]+ e [Ru(dmb)2Cl]+, unidas por ligantes ponte com dimensões lineares crescentes, isto é: bpy, bpe e bpeb (dcbH2= ácido-2,2\'-bipiridina-4,4\'-dicarboxílico, dmb= 4,4\'-dimetil-2,2\'- bipiridina, bpy= 4,4\'-bipiridina, bpe= trans-1,2-bis(4-piridil)-etileno e bpeb= trans-1,4- bis[2-(piridil)etenil]-benzeno). O rendimento global das DSCs correspondentes cresceram com o aumento do tamanho da ponte, passando de 2,78 % para o corante dim-Ru-bpy, para 2,89 e 3,25 % nos corantes dim-Ru-bpe e dim-Rbpeb, respectivamente. Foi observado que os valores de Jsc e η têm correlação linear com a distância de separação do buraco e da superfície do eletrodo de TiO2, ratificando que o processo de retardação da recombinação de carga, causado pelo aumento da ponte, é um fator muito importante para esta classe de compostos. Os resultados de IPCE mostraram que a unidade [Ru(dmb)2Cl(P)]+ também é responsável pela fotoinjeção de elétrons no TiO2. Assim, a excitação de qualquer uma das unidades, sempre acaba formando a espécie TiO2(e-)-Ru-Ru(h+) no filme interfacial. Os resultados confirmam as expectativas esperadas no planejamento energético vetorial, no qual o HOMO foi centrado na unidade distante da superfície e o LUMO ficou sobre a dcbH2 diretamente ancorada no superfície do TiO2. / This thesis encompasses our efforts to improve the knowledge and contribute to the development of dye-sensitized solar cells, by focusing on supramolecular design of new dyes and on critical aspects of the morphology of the TiO2-P25 and TiO2-Dye interfaces, as probed by confocal Raman microscopy. According to Raman imaging of the crystalline phase distribution of TiO2-P25 (Degussa) rutile was present as aggregates of different sizes (from 250 nm to 3 µm) dispersed in the 25 nm anatase powder, persisting even after applying criterious procedures for generating uniform colloidal suspensions. In addition, the irradiation of TiO2-P25 films containing adsorbed N3 dye, using a 532 nm laser (power over to 25 mW cm-2) led to the absorption and instantaneous combustion of the dye, promoting drastic local changes associated with the anatase to rutile conversion. The design and application of new supramolecular sensitizers in DSC has also been pursued, aiming an improvement of efficiency by slowing down the electron-hole recombination process, while enhancing the light harvesting effects in the visible range by means of vectorial electron/energy transfer. Studies concerning another efficient supramolecular porphyrin dye, have also been performed and published (Appendix). As the main subject, a series of dimeric species have been reported. They were based on the [Ru(dcbH2)Cl]+ and [Ru(dmb)2Cl]+ units connected by linear bridging ligands of increasing lengths, such as: bpy, bpe and bpeb (dcbH2= 2,2\'-bipyridine-4,4\'-dicarboxylic acid, dmb= 4,4\'-dimethyl-2,2\'-bipyridine, bpy= 4,4\'-bipyridine, bpe= trans-1,2-bis(4- pyridyl)-ethylene e bpeb= trans-1,4-bis[2-(4-pyridyl)ethenyl]-benzene). The overall yield of the corresponding DSCs increased with the bridging ligand length, from 2.78 % for dim-Ru-bpy, to 2.89 % and 3.25 % for dim-Ru-bpe and dim-Ru-bpeb, respectively. The electrochemical parameters associated with the short circuit current exhibited a linear correlation with the hole separation distance between the TiO2 electrode and the binuclear dye terminal, confirming that the retardation of charge recombination through the increasing distance is indeed a relevant factor for this series of compounds. The IPCE results indicated that the [Ru(dmb)2Cl(P)]+ unit is also involved in electron transfer, such that the dye excitation always leads the TiO2(e-)-Ru-Ru(h+) species. This conclusion confirmed the success of the supramolecular design and vectorial transfer strategy, in which the HOMO center was placed far away from the surface, but in communication with the LUMO center located at the dcbH2 group anchored on TiO2.

Esta tese tem como objetivo contribuir para o conhecimento e desenvolvimento das células solares sensibilizadas por corantes, através da elaboração de novas espécies supramoleculares e de estudos fundamentais de caracterização do filme de TiO2-P25 e da interface TiO2-Corante pela técnica de microscopia Raman confocal. Os estudos de microcopia Raman confocal da distribuição das fases cristalinas rutilo e anatase em filmes de TiO2-P25 (Degussa) mostraram que a fase rutilo está presente em agregados de diferentes tamanhos (de 250 nm a 3 µm) distribuídos na fase anatase e que estes agregados permaneceram mesmo após os processos de preparação da suspensão coloidal. Na presença do corante N3, verificou-se que a irradiação com laser em 532 nm, usando potência acima de 25 mW cm-2, provoca a absorção e posterior combustão do filme interfacial, com drásticas mudanças na morfologia visualizadas por microscopia Raman confocal, revelando a ocorrência da transformação de anatase em rutilo na região de incidência do feixe de laser. Outro ponto investigado nesta tese, foi a síntese e aplicação de novos sensibilizadores supramoleculares em células solares sensibilizadas por corante (DSC), visando diminuir os processos de recombinação e melhor aproveitamento do espectro solar através da estabilização do corante foto-oxidado e da transferência vetorial de elétron/energia. Além dos trabalhos com novas porfirinas supramoleculares, reproduzidas no apêndice, esta tese apresenta um estudo detalhado de uma série, formada por três espécies diméricas, constituídas pelas unidades [Ru(dcbH2)Cl]+ e [Ru(dmb)2Cl]+, unidas por ligantes ponte com dimensões lineares crescentes, isto é: bpy, bpe e bpeb (dcbH2= ácido-2,2\'-bipiridina-4,4\'-dicarboxílico, dmb= 4,4\'-dimetil-2,2\'- bipiridina, bpy= 4,4\'-bipiridina, bpe= trans-1,2-bis(4-piridil)-etileno e bpeb= trans-1,4- bis[2-(piridil)etenil]-benzeno). O rendimento global das DSCs correspondentes cresceram com o aumento do tamanho da ponte, passando de 2,78 % para o corante dim-Ru-bpy, para 2,89 e 3,25 % nos corantes dim-Ru-bpe e dim-Rbpeb, respectivamente. Foi observado que os valores de Jsc e η têm correlação linear com a distância de separação do buraco e da superfície do eletrodo de TiO2, ratificando que o processo de retardação da recombinação de carga, causado pelo aumento da ponte, é um fator muito importante para esta classe de compostos. Os resultados de IPCE mostraram que a unidade [Ru(dmb)2Cl(P)]+ também é responsável pela fotoinjeção de elétrons no TiO2. Assim, a excitação de qualquer uma das unidades, sempre acaba formando a espécie TiO2(e-)-Ru-Ru(h+) no filme interfacial. Os resultados confirmam as expectativas esperadas no planejamento energético vetorial, no qual o HOMO foi centrado na unidade distante da superfície e o LUMO ficou sobre a dcbH2 diretamente ancorada no superfície do TiO2. / This thesis encompasses our efforts to improve the knowledge and contribute to the development of dye-sensitized solar cells, by focusing on supramolecular design of new dyes and on critical aspects of the morphology of the TiO2-P25 and TiO2-Dye interfaces, as probed by confocal Raman microscopy. According to Raman imaging of the crystalline phase distribution of TiO2-P25 (Degussa) rutile was present as aggregates of different sizes (from 250 nm to 3 µm) dispersed in the 25 nm anatase powder, persisting even after applying criterious procedures for generating uniform colloidal suspensions. In addition, the irradiation of TiO2-P25 films containing adsorbed N3 dye, using a 532 nm laser (power over to 25 mW cm-2) led to the absorption and instantaneous combustion of the dye, promoting drastic local changes associated with the anatase to rutile conversion. The design and application of new supramolecular sensitizers in DSC has also been pursued, aiming an improvement of efficiency by slowing down the electron-hole recombination process, while enhancing the light harvesting effects in the visible range by means of vectorial electron/energy transfer. Studies concerning another efficient supramolecular porphyrin dye, have also been performed and published (Appendix). As the main subject, a series of dimeric species have been reported. They were based on the [Ru(dcbH2)Cl]+ and [Ru(dmb)2Cl]+ units connected by linear bridging ligands of increasing lengths, such as: bpy, bpe and bpeb (dcbH2= 2,2\'-bipyridine-4,4\'-dicarboxylic acid, dmb= 4,4\'-dimethyl-2,2\'-bipyridine, bpy= 4,4\'-bipyridine, bpe= trans-1,2-bis(4- pyridyl)-ethylene e bpeb= trans-1,4-bis[2-(4-pyridyl)ethenyl]-benzene). The overall yield of the corresponding DSCs increased with the bridging ligand length, from 2.78 % for dim-Ru-bpy, to 2.89 % and 3.25 % for dim-Ru-bpe and dim-Ru-bpeb, respectively. The electrochemical parameters associated with the short circuit current exhibited a linear correlation with the hole separation distance between the TiO2 electrode and the binuclear dye terminal, confirming that the retardation of charge recombination through the increasing distance is indeed a relevant factor for this series of compounds. The IPCE results indicated that the [Ru(dmb)2Cl(P)]+ unit is also involved in electron transfer, such that the dye excitation always leads the TiO2(e-)-Ru-Ru(h+) species. This conclusion confirmed the success of the supramolecular design and vectorial transfer strategy, in which the HOMO center was placed far away from the surface, but in communication with the LUMO center located at the dcbH2 group anchored on TiO2.