Conducting metallopolymers are a new and fascinating class of materials that incorporate metals into conducting polymer systems. These new materials combine the processing advantages of polymers with the electronic, optical and catalytic properties provided by the presence of metal centers. A large number of conducting metallopolymers have been synthesized and studied and have found applications in areas such as sensors, memory and light-emitting devices, solar cells, and catalysis. Among the various applications, conducting metallopolymers as emitting layers in high-efficiency polymer light-emitting diodes (PLEDs) attract great research interest. In order to get PLEDs with long lifetime, high quantum efficiency, and excellent color purity, we have developed an approach to synthesize well-defined conducting metallopolymers that incorporate lanthanide complexes in an inner sphere fashion. As such, we aim to take full advantage of the properties of both organic and inorganic components with high efficiency due to the direct electronic interface this configuration creates. Lanthanide complexes with polymerizable groups have been synthesized, characterized and utilized as precursors for conducting metallopolymers. These lanthanide monomers and corresponding metallopolymers display visible and near-infrared luminescence at room temperature that is consistent with efficient energy transfer from the organic polymer matrix to the lanthanide metal ion followed by lanthanide luminescence. As a second but closely related area, electrogenerated chemiluminescence (ECL) of polymers is attractive for light-emitting devices. Up to now, there are limited studies dealing with ECL from pure active materials deposited as solid films on electrodes. The operation theory and degradation mechanism are still under investigation. To advance the development of ECL of conducting metallopolymers, we prepared cyclometalated Pt(II) complexes with polythiophene system. Conducting metallopolymer films are prepared through controlled electropolymerization. ECL of the Pt(II) containing conducting polymers are observed for the first time. Finally, a preliminary study of magnetism and conductivity of conducting metallopolymers has been done. We incorporate Fe(II)/Fe(III) into our newly designed ligand systems with polymerizable thiophene derivatives. Three complexes show spin crossover (SCO) phenomena with the highest transition temperature at 265 K, which are further verified by variable temperature electron paramagnetic resonance spectra. / text

The work in this thesis examines the effects of the application of oxide coatings on the performance of the single crystalline silicon photovoltaic solar cells. A variety of potential oxide materials for solar cells performance enhancement are investigated. These films are silicon oxide, titanium oxide and rare earth ion-doped gadolinium oxysulfide phosphor. This study compares the electrical characteristics, optical properties and surface chemical composition of mono-crystalline silicon cells before and after coating. The first study investigates the potential for using single and double layers of silicon oxide films produced by low-temperature Plasma Enhanced Chemical Vapour Deposition (PECVD) using tetramethylsilane as a silicon precursor and potassium permanganate oxidising agent for efficiency enhancement of solar cells at low manufacturing cost. Deposition of the films contributes to the increase of the conversion energy of the solar cells on one hand while the variety of colours obtained in this study can be of great importance for building-integrated photovoltaic application on the other hand. The obtained results demonstrated a relative enhancement of 3% in the conversion efficiency of the crystalline silicon solar cell. In the second study, the effects of using a single layer of titanium oxide and a stack of silicon oxide and titanium oxide on the performance of solar cell are demonstrated. Moreover, this study shows the use of different sputtering configurations and oxidation methods. The experimental results showed a relative enhancement of 1.6% for solar cells coated with a stack of silicon oxide/titanium oxide. In the third study, silicon cells were coated with a luminescent layer consisting of down-converting phosphor, gadolinium oxysulfide doped with erbium and terbium, and a polymeric binder of EVA using doctor-blade screen printing technique. A relative enhancement of 4.45% in the energy conversion efficiency of PV solar cell was achieved. Also, the effects of combining silicon oxide layers together with the luminescent composite are also presented in this study.

付記する学位プログラム名: 充実した健康長寿社会を築く総合医療開発リーダー育成プログラム / 京都大学 / 新制・課程博士 / 博士(工学) / 甲第23227号 / 工博第4871号 / 新制||工||1760(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 田中 一生, 教授 秋吉 一成, 教授 古賀 毅 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Ce manuscrit décrit la synthèse et la caractérisation de nouvelles molécules incluant un cœur organophosphoré, le phosphole. Certaines de ces molécules ont été utilisées pour la fabrication de dispositifs OLEDs ou de cellules photovoltaïques organiques. Le premier chapitre fait un état de l'art de la chimie du phosphole dans le domaine des matériaux organiques entre 2010 et 2013. Le second chapitre décrit la synthèse et l'étude physico-chimique de molécules qui permettent de moduler l'angle de torsion dans les systèmes π conjugués pour faire varier les propriétés optiques et rédox. Une de ces molécules a permis la fabrication d'une diode blanche organique. Le troisième chapitre de ce manuscrit présente une structure tridimensionnelle intéressante, le 1,1-biphosphole. En plus de posséder une structure tridimensionnelle, ces structures présentent un mode de conjugaison original, la conjugaison σ-π, qui permet de réduire l'écart HO-BV de nos systèmes. Une de ces molécules a permis la fabrication de la première cellule photovoltaïque organique avec un dérivé du phosphole inséré dans la couche active. Dans une deuxième partie, ce chapitre traite également de la réactivité originale du 1,1'-biphosphole qui permet de fonctionnaliser l'atome de phosphore par une simple substitution nucléophile, permettant d'insérer une grande variété de substituants pour moduler les propriétés des molécules. Pour finir, ce manuscrit présente un quatrième chapitre qui implique le phosphole comme unité coordinante afin de réaliser des nouveaux complexes qui permettent de réaliser une ortho-métallation par activation C-H. De nouveaux complexes ortho-métallés d'Ir(III) et de Rh(III) ont été synthétisés et caractérisés. / This thesis describes the synthesis and the characterization of new molecules including an organophosphorous unit, the phosphole ring. Some molecules have been used to build devices like organic light emitting diodes or organic photovoltaic cells.The first chapter describes the state of the art of the phosphole chemistry in organic materials between 2010 and 2013. The second chapter describes molecules having a tuneable twist angle allowing a fine control of the properties of the molecules like the HOMO-LUMO gap. One of those molecules has been used to build a white organic light emitting diode. The third chapter of this thesis presents an interesting three dimensional structure, the 1,1'-biphosphole. Beside this three dimensional structure, the molecules possess an original conjugation mode, the σ-π conjugation which allows a decrease of the HOMO-LUMO gap. One molecule from this chapter was used as absorber in organic photovoltaic cell. In the second part of this chapter, the 1,1'-biphosphole structure shows an interesting reactivity toward nucleophilic attack in order to functionalize the phosphorus center. This reactivity has been used to make new molecules and offer the opportunity to attach a wide range of substituents to the phosphorus atom in order to tune the properties of the molecules. The fourth chapter deals with the coordination chemistry of the phosphole in order to realize new ortho-metalated complexes. New Ir(III) and Rh(III) complexes have been synthesized and characterized.