This dissertation focuses on the design, synthesis, and characterization of a variety of organic dyes, semiconducting materials, and surface redox-active modifiers of potential interest to organic-based emerging photovoltaics. A discussion of the materials’ optoelectronic properties, their ability to modify and promote electron transfer through an organic/transparent conducting-oxide interface, and finally their effect on the photovoltaic properties of devices utilizing them as light-harvesters is provided where relevant. The first two research chapters discuss mono-chromophoric asymmetric squaraine-based sensitizers and covalently linked, dual-chromophoric, porphyrin-squaraine sensitizers as light absorbers in dye-sensitized solar cells (DSSCs), in an attempt to address two problems often encountered with DSSCs utilizing this class of near infra-red sensitizers; The lack of panchromatic absorption and aggregation on the surface. Also, this dissertation discusses the design and synthesis of asymmetric perylene diimide phosphonic acid (PDI-PA) redox-active surface modifiers, and reports on the electron-transfer rates and efficiencies across the interface of an ITO electrode (widely used in organic-electronic devices) modified with these perylene diimides. Finally two series of hole-transport materials based on oligothiophenes and benzodithiophenes are reported: optoelectronic properties and preliminary performance of organic photovoltaic (OPV) devices fabricated with them is discussed.

This thesis investigates novel hole extraction interfaces and series interconnects for applications in organic photovoltaics, specifically in single junction solid-state dye-sensitized solar cells (DSSCs) and tandem DSSC/polymer bulk heterojunction solar cells. Improvements in hole extraction and device performance by using materials compatible with scalable deposition methods are presented, including tungsten- and molybdenum-disulphide (WS₂ and MoS₂), and p-type doped spiro-OMeTAD (2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene) nanoparticle dispersions. WS₂ and MoS₂ hole extraction layers increase averaged short circuit currents by 20% and 16% respectively, and power conversion efficiencies by 19% and 14% respectively when compared with control devices. Similarly, doped spiro-OMeTAD nano-particle layers improved short circuit current densities by 32% and efficiencies by 9%. Tandem device interconnects using these novel hole extraction formats have been fabricated, but although devices did exhibit rectification, overall performance was poor. Possible reasons for their limited success have been analysed. Dye-sensitized solar mini-modules are also reported. In order to assure the scalability of DSSC technology, these larger area devices were constructed using doctor blade coating to deposit the hole transporter material. As well as achieving a respectable maximum power conversion efficiency of 2.6%, it has also been shown that the extent to which hole transporter infiltrates the mesoporous photoanode of these devices may be tuned by altering substrate temperature during deposition. It was found that an optimal coating temperature of 70 degrees C produced the best efficiency, with a corresponding pore-filling fraction of 41%.

Στα πλαίσια της παρούσας διδακτορικής διατριβής μελετήθηκαν και αναπτύχθηκαν νανοδομημένα λεπτά υμένια διοξειδίου του τιτανίου (TiO2) και λευκόχρυσου (Pt) για χρήση σε ευαισθητοποιημένες φωτοβολταϊκές κυψελίδες. Αφού πραγματοποιήθηκε η μελέτη των υμενίων, παρασκευάστηκαν υμένια TiO2 και Pt και βελτιστοποιήθηκαν, ώστε να έχουν τις επιθυμητές ιδιότητες. Για το χαρακτηρισμό των υμενίων TiO2 χρησιμοποιήθηκε ηλεκτρονικό μικροσκόπιο σάρωσης (SEM) και περίθλαση ακτίνων X (XRD). Μάλιστα προτάθηκε η χρήση νιτρικού οξέος, ανάμεσα σε 4 διαφορετικά οξέα, για την αποτελεσματική διασπορά των σωματιδίων του TiO2 και την παρασκευή ομοιόμορφων υμενίων, χωρίς την παρουσία ρωγμών και με πάχος πάνω από 10 μm. Τα υμένια που παρασκευάστηκαν χρησιμοποιήθηκαν σε ευαισθητοποιημένες φ/β κυψελίδες και μελετήθηκε η επίδραση της δομής τους στην απόδοση των κυψελίδων. Για τα υμένια Pt αναπτύχθηκαν δυο διαφορετικοί τρόποι παρασκευής (θερμική διάσπαση αλάτων Pt, ηλεκτροαπόθεση). Τα υμένια που προέκυψαν αξιολογήθηκαν με βάση τη μορφολογία και τις καταλυτικές τους ιδιότητες ως προς την αναγωγή των ιόντων τριωδίου και προτάθηκαν τρόποι για τη βελτιστοποίησή τους. Ιδιαίτερη βαρύτητα δόθηκε στη σταθερότητα των υμενίων Pt κατά την παραμονή τους σε διάλυμα ηλεκτρολύτη, ίδιο με αυτό που χρησιμοποιείται στις ευαισθητοποιημένες κυψελίδες. Τέλος τα υμένια TiO2 και Pt ενσωματώθηκαν σε πρότυπες φωτοηλεκτροχρωμικές διατάξεις, στις οποίες η ενέργεια που απαιτείται για τη μεταβολή της διαπερατότητάς τους παρέχεται από την ενσωματωμένη φ/β κυψελίδα. Μάλιστα προτάθηκε και μελετήθηκε ένας νέος τύπος διάταξης. / In this PhD thesis we have studied and prepared nanostructured titanium dioxide (TiO2) and platinum (Pt) thin films, in order to use them for dye sensitized solar cells. The morphology and the structure of the TiO2 films were examined with scanning electron microscopy (SEM) and x-ray diffraction (XRD). We have proposed the use of nitric acid, among four other acids, in order to achieve a more efficient dispersion of TiO2 nanoparticles and to prepare uniform and crack free films, with thickness above 10 μm. The TiO2 films were used in dye sensitized solar cells and was examined the relation between the structure of the films and the efficiency of the cells. For the deposition of Pt films we have used two different methods (thermal decomposition of Pt salts and electrodeposition). The films were characterized according to their morphology and their catalytic activity towards triiodide ions reduction. Moreover we have proposed methods for improving the properties of Pt films and we have studied their stability, especially when the films were stored in the same electrolyte solution as that in dye sensitized solar cells. Finally the TiO2 and Pt films were used in photoelectrochromic devices, where the energy produced by the photovoltaic cell is used for the modulation of device’s transmittance. Also a new type of a photoelectrochromic device was introduced and studied.

Αντικείμενο της διπλωματικής εργασίας είναι μελέτη της ευαισθητοποίησης από κοινού (co-sensitization) με την χρήση απλών οργανικών χρωστικών με παρόμοιο φάσμα απορρόφησης. Για το λόγο αυτό αναπτύχθηκαν μείγματα διαφόρων χρωστικών ουσιών τα οποία χρησιμοποιήθηκαν για την ευαισθητοποίηση ηλιακών κυψελίδων (DSSCs) με ημιαγωγό νανοδομημένου ZnO. Οι χρωστικές που χρησιμοποιήθηκαν για την ευαισθητοποίηση ήταν απλές οργανικές, όπως η Rose-Bengal, η Rhodamine-B, η Eosin-B, η Coumarin 343 και η Malachite Green. Παρασκευάστηκαν μείγματα δυο και τριών χρωστικών ουσιών με σκοπό την επίτευξη υψηλότερης απόδοσης της ευαισθητοποιημένης ηλιακής κυψελίδας. / In this work we investigate co-sensitization effects by using simple organic dyes with complimentary absorption spectra. A combination of different organic dyes was used in this work to sensitize nanostructured ZnO films for Dye Sensitized Solar Cell (DSSC) devices. The dyes used to sensitize the films were the simple organic molecules Bengal Rose, Rhodamine B, Eosin B, Coumarin 343 and Malachite Green. Binary and ternary blends of these dyes were used in order to enhance the performance of ZnO DSSCs.

Photovoltaic technologies use light from the sun to create electricity, using a wide range of materials and mechanisms. The generation of clean, renewable energy using this technology must become price competitive with conventional power generation if it is to succeed on a large scale. The field of photovoltaics can be split into many sub-groups, however the overall aim of each is to reduce the cost per watt of the produced electricity. One such solar cell which has potential to reduce the cost significantly is the dye sensitised solar cell (DSC), which utilises cheap materials and processing methods. The reduction in cost of the generated electricity is largely dependent on two parameters. Firstly, the efficiency that the solar cell can convert light into electricity and secondly, the cost to deposit the solar cell. This thesis aims to address both factors, specifically looking at altering the transparent conducting oxide (TCO) and substrate in the solar cell. One method to improve the overall conversion efficiency of the device is to implement the DSC as the top cell in a tandem structure, with a bottom infra-red absorbing solar cell. The top solar cell in such a structure must not needlessly absorb photons which the bottom solar cell can utilise, which can be the case in solar cells utilising standard transparent contacts such as fluorine-doped tin oxide. In this work, transparent conducting oxides with high mobility such as titanium-doped indium oxide (ITiO) have been used to successfully increase the amount of photons through a DSC, available for a bottom infra-red sensitive solar cell such as Cu(In,Ga)Se2 (CIGS). Although electrically and optically of very high quality, the production of DSCs on this material is difficult due to the heat and chemical instability of the film, as well as the poor adhesion of TiO2 on the ITiO surface. Deposition of a interfacial SnO2 layer and a post-deposition annealing treatment in vacuum aided the deposition process, and transparent DSCs of 7.4% have been fabricated. The deposition of a high quality TCO utilising cheap materials is another method to improve the cost/watt ratio. Aluminium-doped zinc oxide (AZO) is a TCO which offers very high optical and electronic quality, whilst avoiding the high cost of indium based TCOs. The chemical and thermal instability of AZO films though present a problem due to the processing steps used in DSC fabrication. Such films etch very easily in slightly acidic environments, and are susceptible to a loss of conductivity upon annealing in air, so some steps have to be taken to fabricate intact devices. In this work, thick layers of SnO2 have been used to reduce the amount of etching on the surface of the film, whilst careful control of the deposition parameters can produce AZO films of high stability. High efficiency devices close to 9% have been fabricated using these stacked layers. Finally, transferring solar cells from rigid to flexible substrates offers cost advantages, since the price of the glass substrate is a significant part of the final cost of the cell. Also, the savings associated with roll to roll deposition of solar cells is large since the production doesn't rely on a batch process, using heavy glass substrates, but a fast, continuous process. This work has explored using the high temperature stable polymer, polyimide, commonly used in CIGS and CdTe solar cells. AZO thin films have been deposited on 7.5um thick polyimide foils, and DSCs of efficiency over 4% have been fabricated on the substrates, using standard processing methods.

The increasing demand for renewable energy has led to substantial research on different solar cell technologies. The dye-sensitized solar cell (DSC) is a technology utilizing dye molecules for light absorption. Dye molecules are adsorbed to a mesoporous semiconductor surface and after light absorption in the dye, charge separation occurs at this interface. Traditionally, DSCs have used layers of single dye species, but in recent efforts to enhance power conversion efficiency, more complex molecular layers have been designed to increase the light absorption. For example, the most efficient DSCs use a combination of two dye molecules, and such dye co-adsorption is studied in this thesis. A key to highly efficient DSCs is to understand the dye/semiconductor interface from a molecular perspective. One way of gaining this understanding is by using an element specific, surface sensitive technique, such as photoelectron spectroscopy (PES). In this thesis, PES is used to understand new complex dye/semiconductor interfaces. Dyes adsorbed to semiconductor surfaces are analyzed using PES in terms of geometric and electronic surface structure.  The investigations ultimately target the effects of co-adsorbing dyes with other dyes or co-adsorbents. PES shows that Ru dyes can adsorb in mixed configurations to TiO2. Co-adsorption with an organic dye affects the configuration of the Ru dyes. As a consequence, shifts in energy level alignment and increased dye coverage are observed. The dyes are affected at a molecular level in ways beneficial for solar cell performance. This is called collaborative sensitization and is also observed in todays most efficient DSC. Dye molecules are generally sensitive to high temperatures and the substantial decrease in power conversion efficiency after heat-treatment can be understood using PES. Furthermore, comparing two mesoscopic TiO2 morphologies used in DSCs show differences in trap state density in the band gap, explaining the photovoltage difference in DSCs comprising these morphologies. Using mixed molecular layers on NiO results in significant improvements of p-type DSC power conversion efficiency. PES shows that changed adsorption configuration contribute to this effect. This thesis shows that PES studies can be used to obtain insight into functional properties of complex DSC interfaces at a molecular level.

Dye-sensitized solar cells (DSSCs) and perovskite solar cells are emerging as promising potential low-cost alternatives to established crystalline silicon photovoltaics. Of the employed functional materials, however, many fundamental optoelectronic properties governing photovoltaic device operation are not sufficiently well understood. This thesis reports on a series of studies using ultrafast THz and photoluminescence spectroscopy on two classes of such materials, providing insight into the dynamics of charge-transport and recombination processes following photoexcitation. For TiO₂-nanotubes, which have been proposed as easy-to-fabricate electron transporters for DSSCs, fast, shallow electron trapping is identified as a limiting factor for efficient charge collection. Trapping lifetimes are found to be about an order of magnitude shorter than in the prevalently employed sintered nanoparticles under similar excitation conditions and trap saturation effects are not observed, even at very high excitation densities. In organo-lead halide perovskites - specifically CH₃NH₃PbI₃ and CH₃NH₃PbI_3-xCl_x, which have only recently emerged as highly efficient absorbers and charge transporters for thin-film solar cells, carrier mobilities and fundamental recombination dynamics are revealed. Extremely low bi-molecular recombination rates at least four orders of magnitude below the prediction of Langevin's model are found as well as relatively high charge-carrier mobilities in comparison to other solution-processable materials. Furthermore a very low influence of trap-mediated recombination channels was observed. Due to a combination of these factors, diffusion lengths reach hundreds of nanometres for CH₃NH₃PbI₃ and several microns for CH₃NH₃PbI_3-xCl_x. These results are shown to hold for both, solution processed and vapour-deposited CH₃NH₃PbI_3-xCl_x and underline the superb suitability of the materials as absorbers in solar cells, even in planar heterojunction architectures. The THz-frequency spectrum of the conductivity of the investigated perovskites is consistent with Drude-like charge transport additionally exhibiting weak signatures of phonon coupling. These coupling effects are also reflected in the luminescence of CH₃NH₃PbI_3-xCl_x, where they are believed to be the cause of the observed homogeneous spectral broadening. Further photoluminescence measurements were performed at temperatures between 4 K and room temperature to study the nature of recombination pathways in the material.

Dans le contexte de la mise au point de dispositifs photovoltaïques efficaces, bon marché et respectueux de l’environnement, la synthèse d’oxydes métalliques semi-conducteurs tels que SnO2, Zn2SnO4 et WO3 de morphologies et textures diverses a été développée afin d’élaborer des photoanodes poreuses pour cellules solaires à colorant. D’après les études réalisées par différentes méthodes (MEB, MET, DRX et BET), les matériaux obtenus présentent des caractéristiques texturales, morphologiques et structurales appropriées pour l’application visée. Des cellules solaires à colorant ont donc été réalisées à partir de ces oxydes, puis différents paramètres influençant leurs performances ont été optimisés afin d’améliorer l’efficacité de la conversion photovoltaïque. Notamment l’influence positive de différents traitements des photoanodes (i.e. solution aqueuse de TiCl4 ou traitement à l’eau) sur les rendements de conversion énergétique et la stabilité des dispositifs a été démontrée. Ainsi, des performances comparables ou supérieures à l’état de l’art ont été atteintes pour les systèmes à base de SnO2. Ces performances ont ensuite été interprétées en déterminant les processus électroniques et ioniques ayant lieu dans ces cellules par différentes méthodes physiques (mesures de tension de seuil et de décroissance de circuit-ouvert, spectroscopie d’impédance). Enfin, des électrodes réalisées à partir de WO3 déposé sur substrats flexibles ont démontré des propriétés électrochromes très prometteuses ce qui ouvre de nouvelles perspectives dans le domaine de l’affichage. / In the context of the development of efficient, low-cost and environmentally friendly photovoltaic devices, the synthesis of metal-oxide semiconductors such as SnO2, Zn2SnO4 and WO3 with various textures and morphologies have been developed in order to achieve nanoporous photoanodes for dye-sensitized solar cells. According to studies carried out by different characterization methods (SEM, TEM, XRD and BET), the resulting materials show interesting features for the expected application. Dye solar cells were then fabricated from photoanodes processed with these oxides and several parameters influencing their performance were optimized to improve the overall conversion efficiency. In particular, the beneficial effect of different treatments of the photoanodes (ie aqueous TiCl4 or water treatment) on the power conversion efficiency and the stability of the devices has been evidenced. Thus, state-of-the art or, even, record efficiencies were reached in the case of SnO2-based systems. These performances were then rationalized by determining the electronic and ionic processes occurring in these devices by various physical methods (threshold voltage and open-circuit photovoltage decay measurements, electrochemical impedance spectroscopy). Finally, electrodes based on WO3 and deposited on flexible substrates have shown very promising electrochromic properties, which opens up new prospects in the field of smart displays.

Cette thèse est divisée en trois parties. La première traite la synthèse de la polyaniline (PANI), un polymère conducteur de trou, utilisé dans plusieurs applications. En variant les quantités du monomère et de l’oxydant tout en fixant leur rapport molaire à 1:1,25, et en ajoutant de l’oxyde de magnésium, des aiguilles et des nouvelles structures semblables aux échinides sont formées. Le mécanisme de formation des structures unidimensionnelles est expliqué à l’aide de la théorie des multicouches. La deuxième partie est consacrée à la fabrication des monocouches photovoltaïques à faible coût en se basant sur le principe de fonctionnement des cellules à pigment photosensible (en anglais DSSC, Dye-Sensitized Solar Cell). En 1991, Grätzel a réintroduit l’effet photo-électrochimique en développant la première DSSC, une des cellules solaire troisième génération, formée d’un film de TiO2 (photo-anode) pigmenté à l’aide d’un colorant et d’un électrolyte qui sert à régénérer le pigment oxydé. Malgré leur faible coût, les DSSCs font face à de nombreux problèmes tels que le coût élevé du pigment, la fuite de l’électrolyte, la sublimation du couple I-/I3- à travers I2, etc. Afin de résoudre ces problèmes, des monocouches photovoltaïques ont été développées. Des composites formés de PANI et TiO2 sont la base de ces dispositifs nouvelle génération. La polymérisation in-situ de l’aniline en présence des nanoparticules de TiO2 conduit à une forte interaction entre la PANI et les particules de TiO2 où une structure « core (TiO2)/shell (PANI) » existe dans le composite. Dans le dispositif photovoltaïque basé sur le composite PANI-TiO2, PANI est considérée comme pigment à la photo-anode et comme poly-électrolyte plus profondément dans le composite. En plus, des textiles fabriqués utilisant ces composites photo-génèrent une tension de 0,6 V et un courant de 1 A/m2 lorsque l’éthanol est injecté dans le dispositif. Une nouvelle architecture a été développée qui sert à améliorer la performance de la cellule et en même temps stocker l’énergie pour des utilisations ultérieures. La dernière partie est consacrée à la fabrication des DSSCs basées sur les pigments naturels. L’anthocyane, un pigment naturel halochromique responsable de la couleur rouge dans les plantes, a été extrait du chou rouge et utilisé pour pigmenter les films de TiO2. Cette propriété se traduit par la fabrication des DSSCs de différentes couleurs et comportement photovoltaïque. Avec un pH égal à 0, une Vco et une Jcc de 520 mV et 185 μA/cm2 sont respectivement obtenues prouvant la possibilité d’utiliser le chou rouge comme source de pigment à très faible coût des DSSCs. / This thesis is divided in three parts. The first one deals with the synthesis of polyaniline (PANI), a hole conducting polymer, used in many applications. By varying the quantities of the monomer and the oxidant while fixing the molar ratio at 1:1.25, and by adding magnesium oxide, novel echinoid-like and PANI needles were formed. The formation mechanism of the 1D structures is explained using the multi-layer theory. The second section is devoted for the fabrication of low cost single-layered photovoltaic devices based on the working principle of dye-sensitized solar cells (DSSCs). In 1991, Grätzel reintroduced the photo-electrochemical effect by developing the first DSSC, one of the third generation solar cells, formed of a TiO2 film (photoanode) sensitized using a dye and an electrolyte regenerating the excited dye. Despite their low cost, DSSCs face many problems such as the high cost of the dye, leaking of the electrolyte, sublimation of the I-/I3- through I2, etc. To solve these problems a single layer photovoltaic device has been developed. Composites formed of PANI, and TiO2 are the basis of the new generation photovoltaics. The in-situ polymerization of aniline inside a titania solution results in a strong interaction between PANI and TiO2 particles where a core (TiO2)/shell (PANI) structure exists inside the composite. In the single-layered photovoltaic device based on PANI-TiO2 composite, PANI is considered as sensitizer at the photoanode and as polyelectrolyte deeper inside the composite layer. In addition, textiles fabricated using such composites generated a voltage of 0.6 V and a current of 1 A/m2 when ethanol is injected in the solar cell. A new architecture has been developed to enhance the performance of the device and at the same time to store the converted energy for later use. The final part is devoted to the fabrication of DSSCs based on natural dyes. Anthocyanin; a halochromic natural dye responsible for the red color in plants, extracted from red cabbage was used to sensitize TiO2 films. This property results in the fabrication of DSSCs with different colors and photovoltaic behavior. At a pH equal to 0, a Voc and Jsc of 520 mV and 185 μA/cm2 were respectively recorded proving the possibility of using red cabbages as a very low cost dye source for DSSCs.

Les cellules solaires à colorant (DSSC) sont une alternative sérieuse aux cellules à base de silicium. Le principe de fonctionnement repose sur la photosensibilisation d'un semi-conducteur par un colorant qui est en général un complexe polypyridinique du ruthénium (II). La modulation des propriétés de ces complexes permet d'optimiser les performances des cellules solaires correspondantes. Dans cette thèse, nous avons synthétisé et étudié l'effet de nouveaux ligands bipyridiniques à substituants électro-donneurs [pi]-délocalisés à base de dithiénylpyrroles (DTP). Ces motifs induisent, dans les complexes homoleptiques, bis- et tris-hétéroleptiques du Ru(II), des effets bathochromes (lorsque les motifs DTP sont liés par leur cycle thiophénique à la bipyridine) et d'importantes augmentations des coefficients d'extinction molaires. Les nouveaux composés ont été caractérisés par spectroscopies, électrochimie, photophysique et calcul théorique. Deux complexes hétéroleptiques ont été testés en cellule DSSC. Si la collecte de photons est excellente, les performances restent en dessous de celles de colorants de référence. Comme en attestent les courbes J/V et les courbes IPCE. Ce résultat peut-être dû à une limitation lors de l'injection dans la bande de conduction ou encore à une gêne stéréo-électronique provoquée par le ligand lors de la réduction du colorant oxydé (Ru(III) par le médiateur / Dye-sensitized Solar Cells (DSSC) appear to be promising devices. Operation principle relies on the photosensitization of a wide-gap semiconductor with a dye, the latter typically being a polypyridinyl ruthenium(II) complex. Modulation of the properties of such complexes enables the optimization of the corresponding solar cells' performances. In the present work, we synthesized and investigated the effect of new bipyridine ligands bearing electron-donating dithienylpyrroles (DTP). These moieties induced red-shifts of the absorption spectra in homoleptic, bis- and tris-heteroleptic Ru(II) complexes especially when the DTP was bound by its thiophene unit to the bipyridine ligand. A notable increase of the molar extinction coefficients was also obtained. All new compounds have been characterized by using spectroscopic, electrochemical, photophysical and computational chemistry techniques. Two heteroleptic complexes have been tested in DSSCs. Despite excellent light harvesting properties, performances were found lower than those of standard dyes as revealed by J/V and IPCE curves. Stereoelectronic effects could be involved since the bulky DTP moiety could impede an efficient access of the mediator to Ru(III) centers