This research is focused on preparation of polypyrrole (PPy) composite particles by using socalled template oxidative polymerization method. As a template, water-soluble polymers, polymeric microgels, latex particles or bulk gels can be used. The morphology and properties of the composite particles can be controlled effectively by the proper use of the template. By choosing the dopant anion or oxidation agent it is possible to vary the conductivity of the polymer. In the case when uncrosslinked PVME was used as stabilizer, core-type polypyrrole spherical particles in the range of 50-100 nm were formed in both aqueous ethanol and water. Results of the elementary analysis, IR spectroscopy confirmed that the anionic salts can be incorporated in the PPy particles and play as the dopants. The presence of dopants in polypyrrole enhances the conductivity, especially in the case of sodium benzoate the conductivity of the final product has been improved by 3 orders. Polymeric microgels were also applied as the templates for polypyrrole deposition. When crosslinked PVME microgels were used in the oxidation polymerization of pyrrole, large PPy fibrils (appr. 400nm) were formed. Needle-like particles were formed due to the porous structure of microgels, which play a template role in the pyrrole polymerization process. When poly(VCL/AAEM) microgels were used as a template for oxidative polymerization of pyrrole, "raspberry-like" composite particles will be formed with PPy domains located in swollen hydropholic particle shell. Obtained stable composite microgels show similar thermal sensitivity as poly(VCL/AAEM) particles with fully reversible collapse-swelling properties. Increase of PPy content in composite particles increases conductivity of the composite material. The conductivity of composite particles prepared in water was much higher than that of prepared in water : ethanol mixtures. Furthermore, monodisperse PS-PEGMA particles, which were prepared in water medium by polymerization with sodium peroxydisulfate have been used as a template for deposition of polypyrrole (PPy). Obtained composite particles possess core-shell morphology where shell is composed out of small PPy nano-domains. The shell thickness can be varied by changing PPy load, controlling the overall template surface area in the system, and by influencing the pyrrole polymerization kinetics in presence of different oxidants. The last possibility provides also incorporation of different anions into polypyrrole shell. The stability of composite particles decreases gradually if the deposited PPy amount increases. It has been established that obtained particles are intrinsically coloured and the colour can be changed by the PS-PEGMA core size. Conductivity measurement shows that PS/PEGMA/PPy composite particles prepared by using phosphomolybdate as the oxidant are much more conductive than the particles prepared by the other two oxidants. The conductivity increases with the increase of PPy load in the system. Overall, the proper design of the template should give a possibility to control effectively the morphology, particle size and provide sufficient stability to the composite particles. Different morphologies, such as spherical, core-shell, raspberry and needle-like, with different particle size are expected to be available in different cases. By choosing the dopant anion or oxidation agent it is possible to vary the conductivity of the polymer. The stable water-based dispersions are expected to be used as additives for paint formulations, in electrorheology, microelectronic, ion-separation or disease diagnostics.

Aramide and arylene ether multiblock copolymers of (AB)n-type with various degrees of sulfonation have been prepared for use in direct methanol fuel cells. / Aramid- und Arylethersulfon-Multiblockcopolymere vom Typ (AB)n mit unterschiedlichem Sulfonierungsgrad wurden hergestellt und hinsichtlich ihrer Eignung als Polymerelektrolyte in der Direkt-Methanol-Brennstoffzelle getestet.

In this work, hyperbranched aromatic polyesters-polyphenols based on 4,4-bis(4’ hydroxy¬phenyl)pentanoic acid (BHPPA) were prepared and, according to the authors knowledge, for the first time tested as precursors for polyurethane bulk resins and coatings. Comparison of poly-BHPPA with competing products The materials prepared in this work show better properties than their aliphatic polyester-polyol analoga based on 2,2-bis-(hydroxymethyl)propanoic acid (BHMPA). Especially, the solubility of poly-BHPPA in organic solvents is better and poly-BHPPAs also do not tend to microphase separation during their reaction with isocyanates, in contrast to poly-BHMPAs. The poly-BHPPA and the polyurethane networks made from them display higher Tg values than analogous poly- BHMPA compounds. Because of the high Tg of the reacting and final systems, curing must occur at elevated temperatures (90°C) in order to avoid undercure. The lower reactivity of phenolic OH groups prevents the reaction from being too fast at that temperature. A drawback of the polyurethanes based on the aromatic polyesters-polyols prepared is the lower thermal stability of their urethane bonds, if compared to aliphatic urethanes. An interesting possibility for future investigations would be the modification of the BHPPA monomer in order to change the OH functionality from phenolic to aliphatic OH, e.g. by replacement of the phenolic OH by hydroxymethyl or hydroxyethyl groups (requires a strong modification of the monomer synthesis) or simpler by reacting the phenolic OH of BHPPA with a suitable reagent like oxirane, which would lead to groups like O-CH2-CH2-OH in the place of the phenolic OH. Such a BHPPA modification should in turn yield modified “poly-BHPPA” polycondensates, which would combine the advantages of poly-BHPPA with those of aliphatic OH precursors of polyurethanes. Poly-BHPPA synthesis Hyperbranched polymers of the 4,4-bis-(4’-hydroxyphenyl)pentanoic acid (BHPPA) were synthesized successfully by the catalyzed (by dibutyltin diacetate) polycondensation of BHPPA. The products obtained were oligomers with number average molecular weight ranging from 1800 to 3400 g/mol (polymerization degree of ca. 6 to 12), displaying a first moment of functionality in the range 7 to 14. Such products were good OH precursors for the preparation of polyurethane coatings, because higher functional polymers would gel at low conversions. The analysis of the functional groups (determination of acid and hydroxyl numbers) and the 1H-NMR and the 13C-NMR spectroscopy were found to be good methods for the determination of molecular weights. The polydispersity of the poly-BHPPA products was in the range 3.5 to 6. Their degree of branching was found to be in the range 0.36 to 0.47. Poly-BHPPA containing aliphatic polyols as core monomers were also prepared successfully. Difunctional and trifunctional core monomers usually reached a full conversion of their OH groups, while the tetra- and hexafunctional core monomers were converted only to 89%. In all these products however, a considerable amount, usually even a majority, of the polymer molecules were core free. The poly-BHPPA products prepared displayed relatively high glass transition temperatures, in the range of 84°C to 114°C, obviously due to interactions between the phenol groups and to hydrogen bridging. The thermal stability of these products was also high, with decomposition occurring near 350°C (at a heating rate of 10°C / min) Kinetics investigations of the poly-BHPPA reactivity towards isocyanates The poly-BHPPA are polyphenols and were expectedly found to react significantly slower with isocyanates than aliphatic alcohols. The reactivity of poly BHPPA was also found to be somewhat lower than that of the monofunctional, low molar-mass 4 ethylphenol. Hexamethylene diisocyanate trimer, Desmodur N3300, was found to be more reactive than hexamethylene diisocyanate (HDI) or butyl isocyanate in all experiments, possibly due to a substitution effect. The substitution effect can be explained by a change of microenvironment caused by conversion of isocyanate group and OH group into urethane groups. The reactions of low-molecular-mass alcohols or phenols with low molecular weight isocyanates followed well the 2nd order kinetics, while the reactions of poly-BHPPA with isocyanates show deviations from ideal 2nd order kinetics at higher conversions. All the kinetics experiments were carried out under catalysis by dibutyltin dilaurate. This catalyst inhibits the undesired reaction of isocyanate groups with moisture. It was also found that the catalysis was necessary to reach reasonable curing times for poly-BHPPA based polyurethane networks. The uncatalyzed systems reacted extremely slowly. Preparation of polyurethane networks from poly-BHPPA The poly BHPPA products prepared were used successfully as OH functional precursors of polyurethane networks. The networks prepared contained only very low sol fractions. Acetone and also ethylene diglycol dimethylether (diglyme) were found to be good swelling solvents for the networks prepared, while methyl propyl ketone was a much poorer solvent and aromatic compounds like toluene or xylene practically did not swell the poly BHPPA based polyurethanes. The networks prepared contain a relatively high amount of cyclic bonds, 40 to 50% in the finally cured state, which is an expected result for systems with precursors of high functionality and with small distances between the functional groups. The temperature of glass transition (Tg) of the networks prepared (ranging from 68°C to 126°C) depends of the poly BHPPA precursor used: it increases with increasing molecular mass and with increasing core functionality. The choice of the isocyanate crosslinker also influences Tg: the networks made from HDI show higher Tg values, than networks made from the same poly BHPPA but crosslinked with Desmodur N3300 (Tri HDI). The urethane bonds in the networks prepared start to decompose near 140°C. The easier degradation of PU with aromatic urethane bonds is a disadvantage in comparison with aliphatic polyurethanes, whose decomposition starts at 200°C. The surfaces of polyurethane coatings prepared are smooth, displaying a roughness of ca. 20-25 nm, and relatively hydrophilic: the contact angle with water was found to be near 80°. The prepared networks are also relatively hard, possessing the Shore D hardness of 70.

Diese Dissertation beschreibt die Synthese und Charakterisierung neuartiger Hyperstern-Polymere (HSP) und deren Funktion als Reaktivbinder in Epoxy- bzw. PUR-Harzen. Hyperstern-Polymere sind Hybride aus hochverzweigten (hvz) und linearen Polymeren. Sie können über ihre reaktiven OH-Gruppen als multifunktionelle hochverzweigte Quervernetzer kovalent in ein kationisch härtendes Epoxyharz einbinden und thermische sowie thermomechanische Eigenschaften verbessern.:Theoretischer Teil Einleitung und Aufgabenstellung Grundlagen 1 Polymeraufbau 1.1. Radikalische Polymerisationen 1.1.1. Kontrolliert radikalische Polymerisation 1.1.2. NMRP 1.1.3. ATRP 1.1.4. RAFT 1.2. Anionische Polymerisation 1.3. Kationische Polymerisation 1.3.1. CROP von Oxazolinen 1.4. Koordinative Polymerisationen 2 Verzweigte Polymerarchitekturen 2.1. Dendritische Polymere 2.1.1. Dendrimere 2.1.2. Hochverzweigte Polymere 2.1.2.1 SCVP 2.1.3. Dendrigrafts 2.1.4. Dendronisierte Polymere 2.2. Spezielle Polymerarchitekturen 2.2.1. Hyperstern-Polymere (HSP) 3 Lacke 3.1. Lösungsmittelhaltige Lacke 3.1.1. Chemisch härtende Lacke 3.1.2. Physikalisch trocknende Lacke 3.2. Wässrige Lacke 3.3. Lösungsmittelfreie Lacke 3.3.1. Strahlenhärtende Lacke 3.3.2. Pulverlacke 3.4. Aliphatische Epoxylacke 3.4.1. UV-Härtung 3.4.2. Thermische Härtung 3.4.3. Thermische Härtung klassischer 2K-Polyepoxid-Lacke 3.5. 2K-PUR-Lacke 3.6. Aktuelle Herausforderungen 3.7. Wissenschaftliche Konzepte zur Schlagzähmodifizierung von Lacken Diskussion und Ergebnisse 4 Synthese hochverzweigter Makroinitiatoren 4.1. Polyester-Makroinitiatoren PE-MI1 und PE-MI2 4.1.1. Polyester-Kern (PE-OH) 4.1.2. Makroinitiatoren für die Oxazolinpolymerisation (PE-MI1) 4.1.3. Makroinitiatoren für die ATRP von Methacrylaten (PE-MI2) 4.2. Poly(vinylbenzylchlorid)-Makroinitiator (PVBC) 5 Hypersterne mit POxa-Armen 5.1. Lineare Polyoxazolin-Modellverbindungen (POxa) 5.1.1. Test der Initiatorfunktionen 5.1.2. Einfluss der Mikrowelle 5.1.3. Terminierung (Capping) 5.1.4. Polymerisation OH-tragender Oxazoline 5.1.5. Adamantan-funktionalisierte Polyoxazoline 5.2. Hypersterne aus Polyester-Kern sowie Polyoxazolin-Armen: PE-g-POxa 5.2.1. Einführung von OH-Gruppen über die Terminierung 5.2.2. Einführung von OH-Gruppen über die Wiederholeinheiten 5.3. Hypersterne aus Polyvinylbenzylchlorid-Kern sowie Polyoxazolin-Armen: PVBC-g-POxa 5.3.1. Modellinitiatoren 5.3.2. Einführung von OH-Gruppen über die Wiederholeinheiten 5.4. Ausblick: Arm first-Strategie 6 Hypersterne mit Polymethacrylat-Armen 6.1. Hypersterne aus Polyvinylbenzylchlorid-Kern sowie Polymethacrylat-Armen: PVBC-g-PHEMA 6.2. Hypersterne aus Polyester-Kern sowie Polymethacrylat-Armen: PE-g-(PMMA-b-HEMA) 7 Hypersterne als Quervernetzer-Additive in Lacken 7.1. PVBC-g-POxa in Epoxyharz 7.1.1. Thermische Härtung 7.2. PE-g-P(MMA-b-HEMA) in Epoxyharz 7.2.1. UV-Härtung 7.2.2. Thermische Härtung 7.3. PE-g-P(MMA-b-HEMA) in 2K-PUR-Harz Zusammenfassung – Ausblick Experimenteller Teil 8 Geräte, Methoden und Chemikalien 9 Synthesen 9.1. Monomere, Capper, Niedermolekulare Substanzen 9.2. Lineare Polyoxazoline 9.2.1. Niedermolekulare CROP-Initiatoren 9.2.2. Lineares Poly(2-methyloxazolin) (PMeOxa) 9.2.3. Adamantan-funktionalisierte Poly(2-methyloxazoline) 9.2.4. Lineare Poly(2-ethyloxazoline) 9.2.5. NMR-Modellverbindungen für PVBC-Kern 9.3. Hochverzweigte Polymere und Makroinitiatoren 9.4. Hyperstern-Polymere mit POxa-Armen 9.5. Hyperstern-Polymere mit PAlkMA-Armen 9.6. Lackproben Abkürzungsverzeichnis Literaturverzeichnis Publikationsliste

This work deals with the sensor application of polythiophenes, which belong to the group of the conducting polymers. The first part focuses on sensor application of poly(3,4-ethylenedioxythiophene) (PEDOT) for ion detection in aqueous electrolytes. The advanced electrochemical quartz crystal microbalance was used for investigating the electrochemical polymerisation and the redox cycling behaviour of the polymer films deposited on the liquid facing electrode of the quartz. This method is based on impedance analysis of a piezoelectric quartz crystal. The deposited polymer mass and surface roughness parameters were estimated from the electrical impedance shift of the quartz during the polymerisation using a new calculation procedure for rough and viscoelastic films. The PEDOT data were compared with results from the electrochemical polymerisation of 2,2?-bithiophene to demonstrate the influence of the substituent on morphology and electrochemical properties in organic electrolytes. With regard to electrogravimetric sensor applications the ion exchange of the polymer in aqueous electrolytes (LiClO4, NaClO4, NaNO3, and sodium toluenesulfonate) during redox cycling was investigated. From the mass/charge balance the apparent exchanged molar mass and the absolute exchanged mass of ions were calculated. The mass balance indicated a transfer of anions and solvent during oxidation. No remarkable cation exchange in the reduction scan was observed. For all investigated electrolytes the calculated exchanged molar mass can be explained with a reversible replacement of solvent by anions during oxidation. The molar solvent/anion ratio was roughly proportional to the sizes of the species. The second part of the work describes investigations on gas sensing properties of polythiophene films prepared by a new preparation method. This two-step procedure is based on electroless polymerisation of conducting polymers. In the first step the substrate is coated with an adhesion promoter and in a second step the chemical surface polymerisation of the monomer is performed. This deposition method was combined with new patterning techniques. The basis of this process is the patterned application of the adhesion promoter which was realised either by a photoresist lacquer mask or by micro contact printing of the adhesion promoter solution. These methods provide patterning down to submicrometer scale. The sensing properties of the polythiophene films were demonstrated with chemiresistors for the redox active gases NO2 and NH3. The reaction kinetics were investigated depending on humidity and temperature. / Die Arbeit befasst sich mit der Untersuchung von Polythiophenen, einer Gruppe der intrinsisch leitfähigen Polymere, für die Anwendung als sensitive Filme in chemischen Sensoren. Ziel war es dabei, ausgewählte Aspekte des Sensoreinsatzes dieser Polymere zu beleuchten, um Wege zu einer verbesserten Sensorcharakteristik solcher Systeme aufzuzeigen. Der erste Teil der Ergebnisse konzentriert sich auf den Einsatz von Poly(3,4-ethylendioxythiophen) in Sensoren für die Bestimmung von Ionenkonzentrationen in wässrigen Medien. Die elektrochemische Polymerisation auf Schwingquarzen und der potentialinduzierte Ionenaustausch an solchen Polymerfilmen wurden mit Hilfe der elektrochemischen Quarzmikrowaage charakterisiert. Diese beruht auf der Impedanzanalyse von Schwingquarzen in der Nähe ihrer Resonanzfrequenz, was neben der Erfassung der Änderung der Resonanzfrequenz der Quarze auch die Untersuchung des Dämpfungsverhaltens und somit eine halbquantitative Analyse der mechanischen Eigenschaften des Polymerfilmes ermöglicht. Aus den Daten Impedanzanalyse während der Polymerisation wurden mit einem neuen Berechnungsmodells, das viskoelastische und rauhigkeitsinduzierte Einflüsse berücksichtigt, die Polymermasse und vertikale und laterale Rauhigkeitsparameter bestimmt. Der Einfluss des Substituenten auf die Morphologie und das elektrochemische Verhalten in organischen Elektrolyten ist durch Vergleichsuntersuchungen an Poly(2,2?-bithiophen) illustriert. Die Sensormessungen erfolgten in wässrigen Modellelektrolyten mit unterschiedlich großen Anionen (LiClO4, NaClO4, NaNO3, Natriumtoluolsulfonat). Für die potentialabhängige Ionenaustauschreaktion konnte ein Einbau von Anionen bei der Oxidation des Polymers, der mit einem Ausstoß von Lösungsmittel verbunden war, nachgewiesen werden. Bei Reduktion des Polymers war der umgekehrte Vorgang zu beobachten. Kationen waren nicht nachweislich an den Austauschprozessen beteiligt. Als Sensorsignal wurde aus der bei Einbau der Ionen geflossenen Ladung und der reaktionsbedingten Masseänderung die ausgetauschte molare Masse und die inkorporierte Ionenmenge bestimmt. Die ausgetauschte molare Masse ergab für die unterschiedlichen Ionenspezies typische Werte, was eine Identifizierung der jeweiligen Analyten erlaubt. Die berechnete Analytmenge belegte eine erhöhte Empfindlichkeit für das in der Polymerisation verwendete Anion (Perchlorat) und eine geringe Empfindlichkeit für große Anionen (Toluolsulfonat) Für dünne, weniger poröse Filme war das Austauschverhältnis von Anion und Lösungsmittel annähernd proportional zu den Molekülgrößen der beteiligten Spezies. Ein zweiter Schwerpunkt der Arbeit war die Weiterentwicklung eines Verfahrens zur oxidativ?chemischen Abscheidung von Polythiophenfilmen unter Nutzung haftvermittelnder Substanzen. Dafür wurde die Filmqualität experimentell optimiert und Methoden zur strukturierten Abscheidung entwickelt. Zur Strukturierung der Polymerfilme wurden Methoden zur lokalen Aufbringung des Haftvermittlers auf Basis einer Maskierung des Substrates mit photostrukturierbaren Lackmasken bzw. auf Basis des Mikrokontaktdruckes der Haftvermittlerlösung entwickelt. Mit der Maskentechnik konnten Strukturen im Submikrometerbereich, mit dem Mikrokontaktdruck im Mikrometerbereich, erzielt werden. Der Nachweis der Sensitivität der chemisch polymerisierten Polythiophenfilme wurde für redoxaktive Gase mit Hilfe von Leitfähigkeitssensoren erbracht, und die Reaktionskinetik in Abhängigkeit von Feuchte und Temperatur untersucht.

The thesis aims to synthesize hyperbranched poly(urea-urethane) polymers (HPU) in one-pot method using commercially available monomers which are 2,4-toluylene diisocyanate (TDI) as aromatic diisocyanate and isophorone diisocyanate (IPDI) and 2(3-isocyanatopropyl) cyclohexylisocyanate (IPCI) as aliphatic diisocyanates. Those proposed diisocyanates were reacted with diethanolamine (DEA) or diisopropanolamine (DIPA). Conditions of polymerisation reactions were optimised. Complete structural analysis using 1H and 13C NMR for the obtained aromatic polymers was carried out. Degree of branching up to 70% was calculated. Aliphatic polymers have spectra with overlapped signals therefore, no full structural analysis was possible. Molar masses were determined using SEC/RI detector which shows that the prepared polymers have Mw values between 1600 g/mol and 106000 g/mol. Thermal analysis for different polymer systems showed that aliphatic HPU are more thermally stable and have values of glass transition temperature higher than aromatic ones. Modification of the end groups in the prepared hyperbranched polymers was carried out using three different modifiers and degree of modification up to 100%. Linear polymers based on the same diisocyanate monomers were prepared to compare the properties of hyperbranched systems with their linear analogs. Measurements of solution viscosity showed that HPU have lower solution viscosity values than their linear analogs of comparable molar masses. Rheological measurement of some polymer samples of different systems were carried out and showed that our hyperbranched systems exhibit a more elastic behavior than the linear polymers. Surface studies for thin films prepared from different polymer systems (hyperbranched, linear and modified) were carried out and the obtained thin films were characterized using light microscope, microglider, GC-MS, and AFM. Contact angle measurements showed that HPU have a relatively hydrophilic character. The modified polymers have higher contact angle values than the unmodified ones due to the lack of OH end groups. Networks based on aliphatic and aromatic HPU were prepared through the reaction of HPU with trimer of 1,6-diisocyanatohexane and characterised by DSC, GC-MS, DMA and AFM. The domain size in aromatic networks was found to be larger than in aliphatic networks. Tensile test was carried out and it was found that aliphatic network is more elastic than aromatic one.

Cette thèse rapporte l'étude de fibres composites nanotubes de carbone/polymère qui présentent des propriétés originales, dont notamment une très forte énergie de rupture potentiellement utile pour de futures applications balistiques. En effet, leur capacité d'absorption d'énergie est la plus importante jamais observée pour un matériau. Cette propriété est liée à la structure composite des fibres, qui est plus proche de celle des fibres naturelles comme la soie d'araignée, que de celle des fibres synthétiques hautes performances usuelles. La thèse présente des études de l'influence de modifications structurales sur les propriétés mécaniques, électriques et thermomécaniques des fibres, qui ont mis en évidence de nouvelles propriétés, comme des effets mémoire de forme et de température. Nous espérons que les résultats fondamentaux obtenus dans ce travail aideront au développement de diverses applications, notamment dans le domaine des textiles et matériaux de protection balistique.

We review the current state on the thermodynamic behavior and structural phases of self- and mutually-attractive dilute semiflexible polymers that undergo temperature-driven transitions. In extreme dilution, polymers may be considered isolated, and this single polymer undergoes a collapse or folding transition depending on the internal structure. This may go as far as to stable knot phases. Adding polymers results in aggregation, where structural motifs again depend on the internal structure. We discuss in detail the effect of semiflexibility on the collapse and aggregation transition and provide perspectives for interesting future investigations.

This thesis contains several contributions to the theoretical description and interpretation of biophysical single-molecule measurements: (i) For semiflexible polymers, we derive an efficient formulation of their local transverse dynamics in terms of a Generalized Langevin Equation. The elastic and frictional properties of the polymer are condensed into a memory kernel that is a function of the polymer\'s length and stiffness, the level of backbone tension, the position of the force probe along the polymer backbone and the boundary conditions at the polymer ends. At short times, the memory kernel attains a universal limiting form that depends neither on the polymer length nor on the boundary conditions; we obtain analytical results that accurately describe this regime. We discuss how to quickly and reliably evaluate the memory kernel for arbitrary times using a spectral decomposition method, and use an extensive body of numerical data to obtain analytical approximations to the memory kernel that cover the complementary long-time limit wherein polymer friction can be subsumed under a renormalized drag coefficient. (ii) Based on a systematic nonequilibrium treatment of an overdamped, one-dimensional stochastic escape process driven by external force, we develop a theory of Dynamic Force Spectroscopy (DFS) that generalizes previously available DFS theories to the high loading rates realized in novel experimental assays and in computer simulations. (iii) Extrapolating to future DFS experiments that may operate at far higher time resolution than presently achievable, we discuss the fast nonequilibrium relaxation of a semiflexible linker after bond rupture. Based on a rigorous theory of tension propagation in semiflexible polymers, we predict the relaxation of force within the force actuator, show that this relaxation is dominated by linker contraction, and demonstrate quantitative agreement of our predictions with experimental data obtained by a collaborating experimentalist group.

L'effet photovoltaïque est une des voies qui s'est significativement développée au cours des dernières années afin de trouver une alternative à la production d'énergies non-renouvelables. Afin de diminuer le coût de fabrication de ces dispositifs photovoltaïques, une solution consiste à remplacer le silicium par des matériaux organiques. Les cellules solaires organiques sont une technologie en pleine émergence qui ambitionne la fourniture de cellules solaires plus flexibles dans tous les sens du terme : mécanique, fabrication, propriétés électro-optiques. Un défi auquel la recherche est confrontée aujourd'hui est l'obtention de matériaux organiques stables et solubles qui absorbent aux longueurs d'ondes du proche infrarouge. Ce travail de thèse réalisé dans l'Équipe de Recherche Technologique CSPVP de l'Université d'Angers a pour objectif de relever le défi. La première partie de notre travail est consacrée à l'utilisation de nouveaux dérivés de fullerènes. Afin d'améliorer l'absorption du fullerène C60 ou/et de chercher de possibles alternatives au PCBM, des nouveaux composés ont été synthétisés. Ces nouveaux dérivés peuvent être répartis en: dyades C60-PDI(R=OPhtBu, Cl), cyclopropano[60]fullerènes et cyclopropano[70]fullerènes de type Bingel porteurs de deux groupes esters C60(ou 70)>(CO2R1)(CO2R2), et l'adduit-1,4 C60(CH2CO2tC4H9)2. Ces dérivés de fullerènes ont été incorporés dans les couches photo-actives des cellules solaires à base du polymère conjugué poly(3-hexylthiophène) (P3HT), en tant que matériau de type accepteur. Tous ont été utilisés en cellules solaires pour lesquelles nous avons cherché à préciser la relation entre structure moléculaire et performances photovoltaïques via la morphologie de la couche active. Des études supplémentaires ont été effectuées afin de corroborer les résultats photovoltaïques (PV) avec les propriétés physico-chimiques des matériaux. La deuxième partie est consacrée à des études physico-chimiques réalisées sur des différents nanotubes de carbones mono-feuillets (SWCNT) fonctionnalisés par des groupements esters. Ces nanotubes fonctionnalisés présentent une meilleure dispersion dans les solvants organiques. Ils ont été étudiés et comparés à différentes concentrations dans des cellules solaires à base de P3HT :PCBM. Des travaux complémentaires ont été effectués sur des dérivés de poly(phénylène vinylène) (PPV) et des dérivés de polythiophène, et des cellules élaborées à partir de dérivés de carbazole attaché sur le noyau de C60 et déposés sur des substrats ITO/PEDOT :PSS par électropolymérisation. En conclusion, nous passons en revue les paramètres qui contribuent directement aux performances photovoltaïques des cellules étudiées.