Nano-structured materials are widely applied for various applications like photovoltaics, electrochromics and sensors. A challenging task in all these fields is the functionalization of these materials with a molecule of interest for the desired application. This work demonstrate the post grafting of the most important and commonly used nano-structured material, mesoporous TiO2, with different bifunctional molecular linkers. These compounds basically have two functional groups, the phosphonic acid group which coordinates to the TiO2 surface and a positive and negative head group which controls the surface charge and the potential interaction of the surface with species in solution. These two groups are systematically separated by alkyl group of different chain length which controls the hydrophobicity of the surface. It is shown that the new surface modification technique simplifies the molecular requirements for functional surface modifiers considerably. Using a limited set of organic anchors with adjustable head group charge and hydrophobicity, broad range of molecules can be adsorbed onto TiO2. Different applications based on such modified surfaces were explored and demonstrated. The modified surfaces can be used to incorporate different charged guest molecules, electrochromophores and dyes which enable to probe their electrochemistry and photovoltaic properties on the surface. Supra-molecular self assembly inside the modified pores is possible which can be monitored by different methods. The study includes the prepartaion of the modified surfaces and their characterization using different electrochemical methods, FTIR spectroscopy, Quartz Crystal Microbalance, Contact angle and Scanning Electron Microscopy measurements.

DSSC est une technologie photovoltaïque de 3ème génération avec un fort potentiel économiquement et une efficacité importante de conversion des photons en électricité. Le DSSC à l'état solide à base d'électrolyte polymère solide prévient la perte et l'évaporation du solvant pendant la fabrication et le fonctionnement des cellules, ce qui prolongera efficacement la durée de vie de la cellule. Cependant, il souffre d'une faible conductivité ionique et d'une faible infiltration des pores.La présente thèse est dédiée au développement concomitant d'électrolytes polymères à base de polysiloxane d'un côté et de photoanodes TiO2 à porosité controlée de l'autre côté et leur incorporation dans des cellules solaires contrastants à l'état solide (ss-DSSC), dans le but d'améliorer leur efficacité photovoltaïque et la stabilité à long terme. À notre connaissance, les DSSC comprenant des couches de TiO2 bimodales et des électrolytes de polysiloxane n'ont jamais été rapportés.La conductivité ionique et le coefficient de diffusion des tri-iodures des liquides poly (ioniques) (PILs) à base de polysiloxane ont été largement améliorés par addition de liquides ioniques (ILs) ou de carbonate d'éthylène (EC), conduisant à des conductivités ioniques de l'ordre de 10-4 -10-3 Scm-1. Les DSSC fabriqués avec les électrolytes optimisés ont montré des rendements jusqu'à 6%, avec une stabilité à long terme pendant 250 jours.Des films de TiO2 bimodaux à double porosité (méso et macroporosité) ont été fabriqués par revêtement par centrifugation, en utilisant des modèles mous et durs. Les films à double matrice bénéficient d'une taille de pores accrue tout en maintenant une surface spécifique élevée pour l'adsorption de colorant. Les films bimodaux se sont révélés plus efficaces lorsqu'ils ont été testés avec des électrolytes polymères, ayant des efficacités comparables avec l'électrolyte liquide dans les DSSC, malgré une absorption plus faible de colorant.Cette thèse apporte une contribution significative dans le domaine des DSSC en tant que cellules solaires efficaces et stables qui ont été préparés à partir d'électrolytes polymères et de films bimodaux nouvellement synthétisés. / DSSC is a 3rd generation photovoltaic technology with potential to economically harvest and efficiently convert photons to electricity. Full solid state-DSSC based on solid polymer electrolyte prevents the solvent leaking and evaporation during cell fabrication and operation, which will effectively prolong the cell life time. However, it suffers from low ionic conductivity and poor pore infiltration.The present thesis is dedicated to the concomitant development of polysiloxane-based polymer electrolytes on one side, and TiO2 photoanodes with tuned porosity on the other side, and their incorporation in solid state dye sensitised solar cell (ss-DSSCs), with the aim to improve their photovoltaic efficiency and the long term stability. To best of our knowledge, DSSCs comprising bimodal TiO2 layers and polysiloxane electrolytes have never been reported.The ionic conductivity and tri-iodide diffusion coefficient of the polysiloxane-based poly(ionic) liquids (PILs) were largely improved by adding of ionic liquids (ILs) or ethylene carbonate (EC), achieving ionic conductivities of 10−4 -10−3 Scm−1. The DSSCs fabricated with the optimized electrolytes showed efficiencies up to 6%, with long term stability for 250 days.Bimodal TiO2 films with dual porosity (meso- and macro-porosity) were fabricated by spin-coating, by using soft and hard templating. The dual templated films benefit from increased pore size while maintaining high surface area for dye adsorption. Bimodal films were shown to be more efficient when tested with polymer electrolytes, having comparable efficiencies with liquid electrolyte when in DSSCs, despite lower dye uptake.This thesis brings a significant contribution to the field of DSSCs as efficient and stable solar cells were prepared from newly synthesized polymer electrolytes and bimodal films.

The solid-state mesoscopic solar cells (sMSCs) have been developed as a promising alternative technology to the conventional photovoltaics. However, the device performance suffers from the low hole-mobilities and the incomplete pore filling of the hole transport materials (HTMs) into the mesoporous electrodes. A variety of HTMs and different preparation methods have been studied to overcome these limitations. There are two types of sMSCs included in this doctoral thesis, namely solid-state dye-sensitized solar cells (sDSCs) and organometallic halide perovskite based solar cells. Two different types of HTMs, namely the small molecule organic HTM spiro-OMeTAD and the conjugated polymer HTM P3HT, were compared in sDSCs. The photo-induced absorption spectroscopy (PIA) spectra and spectroelectrochemical data suggested that the dye-dye hole conduction occurs in the absence of HTM and appears to be of significant importance to the contribution of hole transport. The PIA measurements and transient absorption spectroscopy (TAS) indicated that the oxidized dye was efficiently regenerated by a small molecule organic HTM TPAA due to its excellent pore filling. The conducting polymer P3HT was employed as a co-HTM to transfer the holes away from TPAA to prohibit the charge carrier recombination and to improve the hole transport. An alternative small molecule organic HTM, MeO-TPD, was found to outperform spiro-OMeTAD in sDSCs due to its more efficient pore filling and higher hole-mobility. Moreover, an initial light soaking treatment was observed to significantly improve the device performance due to a mechanism of Li+ ion migration towards the TiO2 surface. In order to overcome the infiltration difficulty of conducting polymer HTMs, a state-of-the-art method to perform in-situ photoelectrochemical polymerization (PEP) in an aqueous micellar solution of bis-EDOT monomer was developed as an environmental-friendly alternative pathway with scale-up potential for constructing efficient sDSCs with polymer HTMs. Three different types of HTMs, namely DEH, spiro-OMeTAD and P3HT, were used to investigate the influence of HTMs on the charge recombination in CH3NH3PbI3 perovskite based sMSCs. The photovoltage decay measurements indicate that the electron lifetime (τn) of these devices decreases by one order of magnitude in the sequence τspiro-OMeTAD > τP3HT > τDEH.