Energy from the sun can be converted to low cost electricity using dye-sensitized solar cells (DSCs). Dye molecules adsorbed to the surface of mesoporous TiO2 absorb light and inject electrons into the semiconductor. They are then regenerated by the reduced redox species from an electrolyte, typically consisting of the iodide/tri-iodide redox couple in an organic solvent. In a solid state version of the DSC, the liquid electrolyte is replaced by an organic hole conductor. Solid state DSCs using 2,2'7,7'-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene (spiro-MeOTAD) have reached conversion efficiencies of up to 6 %, which is about half of the efficiency of the best iodide/tri-iodide cells.   Measurement techniques, such as spectroelectrochemistry and photo-induced absorption spectroscopy (PIA), were developed and applied to study the working mechanism of organic dyes in solid state DSCs under solar cell operating conditions. The energy alignment of the different solar cell components was studied by spectroelectrochemistry and the results were compared to photoelectron spectroscopy. PIA was used to study the injection and regeneration processes. For the first time, it was shown here that the results of PIA are influenced by an electric field due to the electrons injected into the TiO2. This electric field causes a shift in the absorption spectrum of dye molecules adsorbed to the TiO2 surface due to the Stark effect.   Taking the Stark effect into consideration during the data analysis, mechanistic differences between solid state and conventional DSCs were found. A perylene dye, ID176, was only able to efficiently inject electrons into the TiO2 in presence of lithium ions and in absence of a solvent. As a result, the sensitiser worked surprisingly well in solid state DSCs but not in liquid electrolyte ones. Regeneration of oxidised dye molecules by spiro-MeOTAD was found to be fast and efficient and spiro-MeOTAD could even reduce excited dye molecules.

Le but de cette thèse était d’auto-assembler des entités triarylamines donneurs d’électrons et capables de s’empiler en fibres conductrices sous l’action de la lumière, avec des entités accepteurs d’électrons de manière à obtenir des hétérojunctions supramoléculaires. Ces objectifs ont été atteints dans des versions dites statiques (distances constantes entre canauxdonneur et accepteur d’électrons) mais aussi dans une version dynamique ou la distance entre unités électroactives change grâce à l’action contrôlée d’un muscle moléculaire intégré. Ces systèmes auto-assemblés fonctionnels ont montré des changements très importants de leurs propriétés optoélectroniques en réponse à des stimuli orthogonaux comme la lumière et le pH. / The aim of this thesis was to self-assemble electron-donating triarylamine units, capable of aggregation into conducting fibers triggered by light, with electron-accepting entities to obtain supramolecular heterojunctions. These objectives were attained, that is in static versions (with constant distances between electron-donating and -accepting channels) and in a dynamicversion wherein the distance between the electroactive units changes owing to the controlled action of an integrated molecular muscle. These functional self-assembled systems showed very important changes in their optoelectronic properties in response to orthogonal stimuli such as light and pH.

Le contrôle de la morphologie de la couche active en optoélectronique organique représente un objectif majeur du fait de son impact sur la stabilité et les performances des dispositifs. En particulier, le degré d'autoorganisation d'un mélange de deux composés à caractère donneur (D) et accepteur (A) d’électrons, ainsi que leurs orientations sont déterminants pour obtenir à la fois un de transfert de charges efficace et des chemins de percolation continus jusqu'aux électrodes. Durant ce travail de thèse, nous avons synthétisé plusieurs séries de co-oligomères à blocs donneur-accepteur capables de s’auto-organiser pour former des lamelles alternées D/A à longue distance. Les co-oligomères présentent une architecture moléculaire de type diade (DA) ou triade (DAD ou ADA), et sont constitués d’une longueur de bloc D variable. Les molécules sont toutes composées d'un bloc A à base de perylène diimide et d'un bloc D contenant les motifs thiophène, fluorène et benzothiadiazole. Une attention particulière a été portée sur l'étude des propriétés optiques, électrochimiques, photophysiques, structurales ou encore opto-électroniques de nos matériaux. En particulier, nous nous avons montré que l’organisation lamellaire était très fortement dépendante de l’architecture moléculaire, puisque seuls les systèmes AD et ADA conduisent à une structuration à longue distance. Par ailleurs, en ajustant la densité électronique au sein du bloc D, nous avons montré qu’il était possible de contrôler à la fois le temps de formation et la durée de vie des états à transfert de charges. Enfin,les premiers résultats de caractérisation du transport de charges et des propriétés photovoltaïques démontrent l’intérêt de ces matériaux dans la réalisation de dispositifs photovoltaïques organiques mono-composants. / In the field of organic opto-electronics, the good control of the active layer morphology in devices represents a major objective to improve the stability and the photovoltaic performances. Especially when blends of selforganizing electron donor (D) and acceptor (A) moieties are combined, their mutual orientation and the degree of supramolecular ordering are determinant in controlling the fundamental energy, the electron transfer processes and the existence of continuous percolation pathways for charge carriers. In this work, we have designed and synthesized different series of donor-acceptor block co-oligomers able toself-assemble in a lamellar structure at very long range. The co-oligomers are made of a dyad (AD) or triad (DAD, or ADA) molecular architecture, and have a variable length of the D block. The A block is constituted of a perylene diimide unit, and the D block of benzothiadiazole, thiophene and fluorene segments. A particular attention was paid on the studies of optical, electrochemical, photophysical, structural and opto-electronical properties. In particular, we showed that the lamellar organization was strongly dependent on the molecular architecture, since only the AD and ADA systems lead to long-range organization. Moreover, by tuning the electronic density along the D block, it has been possible to control both the formation and lifetime of the charge transfer states. Finally, the first results on charge transport and photovoltaic properties demonstrate the high interest of these materials for the elaboration of single component organic photovoltaic devices.

L'électronique plastique est devenue en une dizaine d'années un domaine actif, tant en recherche fondamentale qu'en application. La compréhension et le contrôle des forces motrices du transport ambipolaire est un objectif clé de la recherche dans le domaine de l'électronique organique, et plus particulièrement des transistors. Après une introduction rappelant les principes des transistors organiques ambipolaires et un état de l'art du domaine, les outils et méthodes utilisés au cours de ce travail ont été présentés. Le premier chapitre présente les résultats obtenus des transistors réalisés par évaporation sous vide de phtalocyanines de cuivre. Dans un premier temps la stabilité et les performances des deux semi-conducteurs isolés ont été caractérisés, puis une étude morphologique, électrique et structurelle a été menée sur des dispositifs en structure bicouche ou interpénétrée. Le deuxième chapitre présente une nouvelle méthode d'élaboration de transistors : le LIFT (LAser Induced Forward Transfer). Les premiers transistors à canal p et n'ont ainsi été réalisés à base de phtalocyanines de cuivre, avant de tenter d'obtenir des dispositifs ambipolaires. Cette méthode récente peut permettre de déposer des films à une très grande cadence menant à des dispositifs microstructurés de grande précision. Le dernier chapitre présente une approche par voie liquide. Des solutions de DH-DS2T et PDIF-CN2 ont été élaborées afin de réaliser des encres par le mélange de ces deux solutions pour être déposées par tournette ou dépôt par goutte. en conclusion, les différentes méthodes sont évaluées et comparées afin de déterminer leur utilité et applicabilité respectives. / During the past decade, plactic electronics has become an active research domain, both fundamental and application side. Undestanding and controling the phenomenom which rule the ambipolar transport is one of the main aims of research in organic electronics and transistors. After an introduction giving the principles and a state of the art of organic ambipolar transistors, materials and methods used are described. The first chapter deals with the results obtains whith transistors based on copper phtalocyanines elaborated by a vacuum evaporation process. Stability is isolated moieties was first investigated. Then, morphology, performance and structure of bilayer and blend systems. The second chapter presents the results obtained for transistors elabored by LIFT (Laser Induced Forward Transfer). The first n-channel and p-channel transistors elabored by laser deposition were obtained from copper phtalocynanines. Then the possibility to obtain ambipolar decives was investigated. This brand new technology can permit to create microstructures with a great deposition velocity. The last chapter presents the liquid way approach. DH-DS2T and PDIF-CN2 solutions were used to realise link by mixing the two solutions. those ink where deposited by drop-cast or spin-coating. Finally, the different methods used in this work were evaluated and compared in order to define their usefulness and applicability

L’amélioration des performances des dispositifs photovoltaïques organiques passe par le contrôle de la morphologie de leurs couches actives. Nous cherchons à préparer une hétérojonction volumique donneur-accepteur nanostructurée en utilisant la nucléation hétérogène des poly(3-alkylthiophène)s (P3AT) donneurs sur des fibres d'organogélateurs accepteurs à base de pérylène bisimide (PBI).La première partie de ce travail présente la synthèse de trois dérivés PBI symétriquement N-substitués par des dendrons portant des groupes amides avec des chaînes latérales linéaires (PBI-C8) et ramifiées (PBI-C10) ou par une chaîne alkyle linéaire (PBI-L18). Leur étude physicochimique comparée met en évidence le rôle des liaisons H et de la substitution des chaînes latérales dans l’auto-assemblage.La seconde partie détaille les conditions d’obtention, la structure et les propriétés de deux polymorphes du PBI-C10 générés par la réorganisation des liaisons H.Finalement nous donnons une preuve de concept de l’obtention d’une hétérojonction donneur-accepteur par la nucléation des fibrilles de P3BT sur des rubans de PBI-C8 auto-assemblés. / Improving the performances of organic photovoltaic devices requires morphology control of the active layers. We seek to prepare highly nanostructured donor-acceptor bulk heterojunctions using the nucleation of semi-conducting donor polymers e.g. poly(3-alkylthiophene)s (P3AT) on self-assembled ribbons of perylene bisimide organogelators.The first part of this work concerns the synthesis of three PBI compounds symmetrically N-substituted by dendrons bearing amide groups and having linear (PBI-C8) and branched (PBI-C10) side-chains or a linear alkyl chain (PBI-L18). Their compared physicochemical study points to the role of H bonds and of side-chains substitution in the self-assembly process.The second part develops to a large extent the structure and the properties of two polymorphs of PBI-C10 generated by H bond reorganization.Finally, a proof of concept is given for the elaboration of donor-acceptor heterojunctions in solution by nucleating P3BT fibrils on self-assembled ribbons of PBI-C8.

Master of Science / Department of Chemistry / Daniel A. Higgins / Three water-soluble perylene diimides (PDIs) were investigated to examine differences in their thin film forming properties. The PDI thin films investigated in this thesis are formed in an electrostatic-self-assembled (ESA) layer-by-layer (LBL) process by the use of a dip coater. The three PDIs employed are sodium bis (sulfonatopropyl) perylene diimide (PDISO[subscript]3[superscript]2-), bis (trimethylammonioethyl) perylene diimide diiodide (PDIDI[superscript]2+), and N-(butoxypropyl)-N'-(2-(N,N,N-trimethylammonio)-ethyl) perylene-3,4,9,10-tetracarboxylic diimide iodide (C[subscript]7OPDI[superscript]+). Thin films were made by alternately depositing the PDIs with counter polyelectrolyte (PEs). The PEs employed were poly(diallyldimethylammonium chloride) (PDDA[superscript]+) and poly(acrylic acid) (PA[superscript]-), depending on the charge of the PDI. PDIs were determined to be aggregated in all three PDI precursor solutions. The fraction of PDI aggregated in each was found to be 0.972, 0.903, and 0.993, for the PDISO[subscript]3[superscript]2-, PDIDI[superscript]2+, and C[subscript]7OPDI[superscript]+, respectively. The C[superscript]7OPDI[superscript]+ solution was the most aggregated only having one charge group, which makes it more hydrophobic. Thin films prepared from the solutions all displayed an absorbance spectrum similar to the aggregated form. All the composites displayed linear growth in film thickness and fiber width with bilayer number. However, the three composites gave unique surface morphologies. The PDISO[subscript]3[supercript]2-[dot in middle of line]PDDA+ composite was found to incorporate highly curled intertwined fibers compared to the PDIDI[superscript]2+[dot in middle of line]PA[superscript]- composite, where the fibers were not intertwined. The fiber structure was found to change after 15 bilayers. This change in morphology was attributed to the fibers grafting together and overlapping causing the loss of original fiber structure. The two symmetric composites differed in the film thickness with the PDISO[subscript]3[superscript]2-[dot in middle of line]PDDA[superscript]+ being thicker than the PDIDI[superscript]2+[dot in middle of line]PA[superscript]- composite. This was attributed to the molecular weights (MW) of the polyelectrolytes investigated during thin film deposition, with the PDDA[superscript]+ having a much higher MW. C[subscript]7OPDI[superscript]+[dot in middle of line]PA[superscript]- thin film composite had a film thickness approximately equal to the PDISO[subscript]3[superscript]2-[dot in middle of line]PDDA[superscript]+ composite, indicating precursor aggregation also influences deposition rate. The C[subscript]7OPDI[superscript]+[dot in middle of line]PA[superscript]- composite incorporated wavy thin fibers that appeared aligned in the dipping direction. This alignment was visible for bulk samples in UV-vis absorption dichroism studies. The alignment was parallel to the dipping direction of the substrate.

Chapter 1: Amphiphilic self-assembled systems as nanocarriers Nanocarriers are the nanometric size molecular assemblies that are used for the transport of small molecules into their non-solvating environments. These systems find major applications as drug delivery systems (DDS) in pharmacological research. These drug delivery systems improves solubility and stability of the drug molecules through encapsulation and also offer additional advantages like target specificity and stimuli responsive release of the drug molecules. Several types of DDS are reported in the literature, which can be prepared by a variety of processing techniques. Of these, molecular self- Chart 1: Developments in the design of amphiphilic nanocarriers assembly has attained considerable attention due to its greater tunability and control in the preparation of nanocarriers. In this chapter we discussed about the amphiphilic nanocarriers which are prepared through self-assembly of amphiphiles through hydrophobic interactions. Several developments in the area of amphiphilic nanocarriers such as di-block polymeric systems, dendritic systems and core-shell architectures are also mentioned. We also highlighted some recent developments in the design of amphiphilic nanocarriers through supramolecular interactions and advantages of such systems. Chapter 2: Bile acid derived dendrons and their application as nanocarriers Host-guest chemistry is well known for dendritic systems. To understand the influence of steric crowding, dendritic effect and importance of number of hydroxyl groups on the bile acid backbone in the host-guest chemistry of bile acid dendrons, we designed and synthesized a new series of C3 symmetric systems and studied the above-mentioned objectives through extraction of polar dyes into nonpolar media. Dye extraction experiments performed using trimeric molecules suggested that only the cholate derivatives (3 and 4) showed considerable extraction of the polar dyes into chloroform; deoxycholate derivatives did not show any extraction, thus emphasizing the importance of the number of hydroxyl groups for dye extraction in these molecular architectures. The effect of steric crowding at the core of these trimeric molecules was shown by efficient extraction of the dyes with the triethylbenzene core (4) compared to the benzene core (3). Greater influence of the aggregates in the case of triethylbenzene core on the extracted dye was also manifested in the Chart 2: Structures of the designed molecules 1-6 value of the induced circular dichroism signal. Surprisingly, a higher analogue in these molecular architectures showed lesser efficiency in dye extraction (on a per bile acid residue basis) compared to the trimers, suggesting a more compact structure for the higher analogue. This was supported by molecular modeling studies. Generality of these systems as nanocarriers for hydrophilic dyes was investigated by screening several other dyes and polar molecules, which are diverse in their structure and functionalities. All these experiments suggested a dependency of the extraction profile on the size of the dye molecule. This was also examined by dynamic light scattering studies, which showed larger size and wider distribution in the size of the aggregates in the case of larger dyes. We also demonstrated selective extraction of a single dye molecule from a blended food color (apple green) using one of the trimer (4) and demonstrated solvent dependent morphological changes in these compounds using electron microscopy. The self-assembly of these amphilic molecules at the air-water interface was studied through Langmuir monolayer studies. Chart 3: Structure of polar guest molecules (Cresol red (7). Erioglaucine (8), Eriochrome black T (9),) phenyl β-D-glucopyranoside (10) and Eosin B (11) Chapter 3: Design and synthesis of bile acid derived surfactants: Study of their aggregation and potential applications Bile acids are facially amphiphilic systems and their amphiphilicity can be improved by attaching polar groups on the bile acid back bone or by synthesizing oligomeric systems which show better self-assembly compared to their monomeric units. To study and improve the amphiphilicity of bile acids, we designed and synthesized a new tripodal surfactant system, with a phosphine oxide based central core to which the bile acids were attached through the C-3 position using click chemistry. Our molecular design also offers added advantage of studying the influence of the stereochemistry at the C-3 position on the aggregation of these molecular architectures. We synthesized trimeric systems with both cholic and deoxycholic acids attached to the central phosphine oxide core with α and β stereochemistry at the C-3 position. Aggregation of these molecules was studied by surface tension measurements, dye extraction studies and NMR. All these compounds showed aggregation at micromolar concentrations. NMR studies suggested changes in the structure of the aggregates at higher temperature and these changes were studied by DLS, which suggested thermodynamically stable monodispersed aggregates for cholic acid derivatives (13 and 15) at higher temperature. These aggregates are stable even after cooling to room temperature and with time. The aggregates of these derivatives were also characterized by atomic force microscopy. Gelation was observed in the case of α derivatives (12 and 13) in phosphate buffer (0.1 M) at pH 7.5 for both deoxy and cholic derivatives, which emphasized the influence of stereochemistry at C-3 position in these architectures. These gels were characterized by rheology experiments. Finally, the possible utility of these micellar systems as model systems to study photophysical processes was demonstrated through lanthanide sensitization experiments in these micellar solutions. Chart 4: Structure of the designed molecules Chapter 4: Synthesis of oligomeric bile acid-taurine conjugates: Study of their aggregation and efficiency in cholesterol solubilization Bile acids are bio-surfactants that are used for the emulsification of fats, vitamins etc. in our body. Bile salts also solubilize the excess cholesterol in our body through mixed micelle formation in the bile and when the bile gets saturated with cholesterol, it leads to cholesterol gallstone formation, which needs to be treated. Ursodeoxycholic acid (UDCA) is used as drug in some cases for the solubilization of (small) cholesterol gallstones, even though the efficiency to solubilize cholesterol is less for UDCA compared to the other bile acids (UDCA is less toxic than the others). So there is a need to develop new cholesterol solubilizing agents. Since oligomeric systems can aggregate better, we designed and synthesized two tetramer taurine conjugates, which differ in the spacer between the bile acid units. Since these conjugates are not soluble in water, their solubility and aggregation was studied in 10% MeOH/Water using pyrene fluorescence experiments. Aggregation studies suggested better aggregation for these molecules compared to their monomeric analogues. These aggregates were also characterized byDLS and electron microscopy. These systems were subsequently studied as nanocarriers for liphophilic dye molecules into aqueous media. Finally, the influence of oligomeric effect in cholesterol solubilization was investigated by cholesterol solubilization studied using these two tetramer taurine compounds and a control, sodium taurocholate. These studies suggested efficient solubilization of cholesterol by oligomers compared to monomeric analogues.(For structural formula pl see the abstract file)

Les dérivés arène-carboxyliques sont des matériaux intéressants dans le but d’obtenir une cellule solaire organique efficace à base de cristaux liquides : Ils présentent à la fois des propriétés électroniques modulables en fonction de la structure chimique, une tendance aux larges plages de températures de présence d’une mésophase colonnaire et souvent un alignement homéotrope au contact de surfaces polaires telles que l’ITO ou le verre. Nous montrons avec cette thèse que des couples donneur-accepteur colonnaires à température ambiante peuvent être obtenus, avec des propriétés suffisamment complémentaires pour prévoir des dissociations d’excitons en charges séparées à leur jonction dans des cellules solaires. / Carboxylic derivatives of polycyclic aromatics are interesting materials in order to obtain efficient organic solar cells based on liquid crystals: They have adjustable electronic properties depending on the chemical structure, a tendency to form a columnar mesophase over wide ranges of temperatures and often a homeotropic alignment in contact with polar surfaces such as ITO or glass. We show with this thesis that donor-acceptor pairs of room-temperature columnar liquid crystals with adjusted properties can be obtained in view of efficient exciton dissociation into separate charges at their junction in solar cells.

Qu’il s’agisse de s’éclairer, de se chauffer, de s’alimenter sainement, de se soigner, de se véhiculer, de s’informer ou encore de se distraire, l’énergie a toujours été au centre des préoccupations et sa conversion en électricité est désormais omniprésente. Le lourd constat environnemental à la suite de l’exploitation intensive de sources fossiles a mené à une indispensable transition vers les énergies renouvelables. Souvent intermittentes, il est nécessaire de les stocker, généralement grâce à des batteries. Parmi les différentes technologies, cette thèse traite des batteries lithium-ion pour le stockage de l’énergie solaire. En effet, cette thèse a pour but l’étude d’un dispositif « tout-en-un » capable de convertir l’énergie solaire et de la stocker. Pour se faire, un semi-conducteur organique photoactif de la famille des pérylènes diimides (PDI) a été emprunté au domaine des cellules solaires organiques et couplé à un matériau phare et durable des batteries lithium-ion : le LiFePO4 (LFP). Cette thèse se décompose en trois parties selon une méthodologie qui vise à la compréhension fondamentale de transferts électroniques photoinduits, en amont du développement d’un dispositif. Pour aboutir à une preuve de concept, une étude de l’extinction de fluorescence du PDI en présence de LFP a d’abord été menée, afin de vérifier l’injection d’électrons en provenance du matériau de batterie dans le semi-conducteur excité. Ce travail a été fait en solution puis à l’état solide, pour la mise au point d’une photoélectrode. Ces deux études ont permis de comprendre les pré-requis du matériau d’électrode positive de batterie pour qu’il soit photoxydé, puis des résultats de spectroscopie Raman ont démontré l’importance des interfaces dans la mise en contact du PDI et du LFP. Finalement, forts d’une première preuve expérimentale de photocharge au sein d’un dispositif « photobatterie », le PDI a été polymérisé et son implémentation dans une photoélectrode de batterie lithium-ion a pu être optimisée. Ses rôles multiples (photoactif, photooxydant, conducteur électronique et liant) ont permis de générer un photocourant sans que cela ne soit au détriment du fonctionnement de la batterie. / Converting energy to electricity is ubiquitous because it plays a vital role in daily life whether for lighting, heating, health, transport, information or entertainment. Societal energy demands are often met with fuel fossils that have had deleterious environmental effects. Transitioning to renewables can mitigate these adverse outcomes. Renewable energy is often intermittent, requiring it to be stored for use during periods when the energy is unavailable. Batteries have become viable means to this end. Among the different technologies, this manuscript examines lithium-ion batteries for solar energy storage. Indeed, this work puts forward an all-in-one device: a device capable of converting and storing solar energy. To this end, a well-known photoactive organic semi-conductor in solar cells (perylene diimide; PDI) was coupled to a conventional and durable electrode material (LiFePO4; LFP) for lithium-ion batteries. This manuscript is divided into three discrete parts following the methodology to demonstrate the fundamental underlying processes of the future all-in-one device before its development: light harvesting and electron transfer. Towards a proof of concept, the thesis systematically studied the light mediated processes in solution, in the solid state, and in an operating device. Initial studies examined the fluorescence quenching of PDI with LFP. This was to validate the injection of electrons from the battery material to the photoexcited semi-conductor indeed occurred. The same emission studies were applied in the solid state for developing a photoelectrode. The two studies generated knowledge about the compositional and architectural requirements of the positive electrode material for it be photoxidized by PDI. Raman spectroscopy further demonstrated the importance of interfaces between the battery material and the organic semiconductor. These enabled a photocharge when the photobattery was illuminated. The PDI was next polymerized and enabled a photocurrent in the battery, courtesy of its collective properties (light harvester, photo-oxidant, electronic conductor, and binder).

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