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Dans le cadre de la fabrication de dispositifs pour l’électronique organique à grande échelle, les besoins en matériaux conducteurs stables à l’air libre, de coût réduit et compatibles avec les techniques d’impression sont croissants. Ces matériaux sont destinés à remplacer les couches métalliques déposés par des méthodes telles que la gravure ou l’évaporation sous vide. Les travaux présentés dans cette thèse ont pour objectif la mise au point d’une encre imprimable stable à l’air libre, composée de polyaniline dispersée en phase aqueuse. L’originalité de cette thèse est de décrire l’intégralité de ce processus, depuis la synthèse chimique de la charge, à partir du monomère jusqu’à l’intégration de l’encre conductrice dans une cellule solaire organique sous forme d’électrode imprimée, en passant par la formulation de l’encre. La première partie des travaux consacrés à la synthèse chimique de la charge a permis d’obtenir un matériau nano structuré, de taille et morphologie contrôlée, dispersable en phase aqueuse et conducteur. Cette dispersion a ensuite été formulée pour lui conférer des propriétés compatibles avec l’impression jet d’encre et lever des verrous critiques comme la granulométrie. La phase d’essai d’impression jet d’encre a permis de valider l’étape de formulation et d’optimiser la morphologie des gouttelettes éjectées. Les couches minces imprimées ont permis d’atteindre des résistances surfaciques inférieures à 1000 Ω/□. Finalement l’encre conductrice a pu être imprimée en tant qu’électrode supérieure dans des cellules solaires organiques. / Considering large-scale development and fabrication of organic electronic devices, needs for low cost conductive printable materials are growing. These materials are designed to replace thin metallic layers deposited via gravure or thermal evaporation. The objective of the work presented in this report is to obtain a conductive and inkjet printable aqueous stable dispersion of polyaniline. Originality of this PhD work is to describe all the steps from the chemical synthesis of polyaniline starting from the monomer, until the integration of the conductive ink in an organic solar cell as a conductive top electrode, through formulation of the ink to meet inkjet printing requirements. During the first part of work dedicated to chemical synthesis of PANI, we managed to produce a nanostructured and conductive material, with controlled size and morphology, which was dispersed in water. This aqueous dispersion was formulated to meet inkjet printing requirements and break technological locks such as particle size in the PANI dispersion. Formulation step was then validated during printing trials, which allowed optimising shape of ejected droplets. Printed PANI thin layers showed sheet resistance below 1000 Ω/□ after 20 printing passes. Finally, conductive ink was printed as a top electrode in fully solution–processed printed organic solar cell.

Philosophiae Doctor - PhD / The thesis presents a simple, sensitive, low cost and a novel graphenated polyaniline doped tungsten trioxide nanocomposite, as an electrochemical sensor for the detection and quantitative and determination of PAHs, which are ubiquitous, toxic, as well as dangerous organic pollutant compounds in the environment. The selected PAHs (anthracene, phenanthrene and pyrene) in wastewater were given priority as a result of their threat to human nature and that of the environment. In order for a healthy, non-polluted and well sustainable environment, there is need for an instrument that is capable of detecting and quantifying these organic pollutants onsite and also for constant monitoring. The nanocomposites were developed by chemical and electrochemical methods of preparations, exploiting the intrinsic properties of polyaniline, graphene and tungsten trioxide semiconducting materials. Chemically, graphene-polyaniline (GR-PANI) nanocomposite was synthesised by in situ polymerisation method, then casted on a surface of glassy carbon electrode to form GR-PANI modified electrode. The properties of the prepared electrode were investigated through morphological and spectroscopic techniques, which confirmed the formation of the composite. The electroactivity of the prepared modified electrode revealed great improvement in cyclic and square wave voltammetric response on anthracene. A dynamic range of 2.0 × 10-5 to 1.0 × 10-3 M and detection limit of 4.39 x 10-7 M was established.

Ces travaux de thèse consistent à élaborer des nanocomposites Polyaniline/hexaferrite pour l’absorption des micro-ondes. L’idée principale est la mise en œuvre de matériaux composites à base de polymères conducteurs intrinsèques telle la Polyaniline que nous avons dopée avec différents types d’acides (HCl, CSA, NSA et TSA…) et l’hexaferrite de baryum de type magnétoplombite (M) stœchiométrique ou substitué. Au niveau de l’hexaferrite de baryum, la substitution du Fe3+ s’est faite par les ions Al3+, Bi3+, Cr3+ et Mn3+.L’hexaferrite de baryum et les hexaferrites substitués par les différents ions cités ci-dessus ont été synthétisés par voie hydrothermale dynamique en faisant varier divers paramètres au cours de la synthèse (pH, température, temps, rapport [OH-]/[NO3-]…).L’élaboration des composites Polyaniline/hexaferrite (pur ou substitués) a été effectuée par polymérisation oxydative en utilisant plusieurs techniques de synthèse : la polymérisation chimique en solution (en tenant compte de la nature de l’acide utilisé) avec ou sans agitation (Aqueous-Based Polymerization with or without stirring) et la polymérisation oxydative par voie solide (Solid-Based Polymerization). L’optimisation de ces différentes techniques de synthèse après caractérisations physicochimiques (DRX, FTIR, ATG, MEB, EDX), diélectriques (ε’, ε’’, σdc) et magnétiques (Mr, Ms, Hc, Tc, µ’, µ’’) des échantillons, a montré que la polymérisation par voie solide se trouve la méthode la plus facile, économique et respectueuse de l’environnement. Elle est aussi adaptée à la production du composite Pani/BaFe12O19 avec de bonnes propriétés structurales, physiques et magnétiques. L’étude de la substitution du Fe3+ dans le BaFe12O19 par Al3+, Bi3+, Cr3+ et Mn3+ a montré une forte dépendance des propriétés structurales et magnétiques avec la distribution de ces ions dans la maille cristalline hexagonale. En effet, les ions Al3+, Cr3+ et Mn3+ ont une tendance à occuper les sites tétraédriques, alors que le Bi3+ occupe les sites octaédriques. Une augmentation de Hc associée à la taille des cristallites a été observée pour les particules substituées avec l'Al et le Cr alors qu’une modification de l'anisotropie magnetocristalline (fort terme d'ordre supérieur) a été mise en évidence pour les substitutions Bi et Mn, dû à leur grand rayon ionique. L’incorporation des hexaferrites substitués dans la Polyaniline pour obtenir des composites Pani/BaMeFe11O19, où Me = Al, Bi, Cr et Mn, révèle une variation des propriétés électromagnétiques dans la gamme de fréquences allant de 1 à 18 GHz. En effet, ces variations sont dues à la formation de dipôles entre l’ion de substitution et les cations O2- dans le ferrite qui sont responsables de la résonance ferromagnétique, de l'anisotropie magnétocristalline et des interactions avec la matrice polymérique. Le composite Pani/BaFe12O19 présente des absorptions dans la bande X qui se déplacent vers la bande Ku avec la substitution du fer confirmant / This thesis deals with the formulation of Polyaniline/hexaferrite nanocomposite for absorbing electromagnetic waves. The main idea is the process of composite materials based on polymers intrinsic conductors such as polyaniline that we doped with different types of acids (HCl, CSA, NSA, and ... TSA) and barium hexaferrite with magnetoplumbite structure with or without substitution according to desired stoichiometries. In the barium hexaferrite, the substitution of Fe 3+ is made by Al3+, Bi3+, Cr3+ and Mn3+ ions.The barium hexaferrite and its substitutions by different ions mentioned above were synthesized dynamic hydrothermal method by varying various parameters during the synthesis (pH, temperature, time, ratio [OH-]/[NO3-] ...).The elaboration of polyaniline/hexaferrite composite (pure or substituted) was carried out by oxidative polymerization using various synthesis techniques: Aqueous-Based Polymerisation with or without agitation (taking into account the nature of the acid used) (ABP) and Solid-Based Polymerization (SBP). The optimization of these various synthesis techniques after physicochemical (XRD, FTIR, TGA, SEM, EDX), dielectric (ε ', ε' ', σdc) and magnetic (Mr, Ms, Hc, Tc, µ', µ'') characterizations of the samples showed that the solid route is the easiest method, economical and environmentally friendly. It is also suitable for the production of composite Pani/BaFe12O19 with good structural, physical and magnetic properties.The study of the substitution of Fe 3+ in the BaFe12O19 by Al3+, Bi3+, Cr3+ and Mn3+ showed a strong dependence of the structural and magnetic properties with the distribution of these ions in the hexagonal crystal lattice. In fact, Al3+, Cr3+ and Mn3+ ions tend to occupy the tetrahedral sites, while the Bi3+ favoured the octahedral sites. An increase in Hc associated with the small crystallite size observed for particles substituted with Al and Cr and the enhancement magnetocristalline anisotropy (strong higher order term) for Bi and Mn due to their high ionic radius.The incorporation of the substituted hexaferrite in the polyaniline to obtain Pani/BaMeFe11O19 composite, where Me = Al, Bi, Cr and Mn, reveals a variation in electromagnetic properties in the frequency range from 1 to 18 GHz. In fact, these variations are due to the formation of dipoles between the substituting ion and surrounding O2- cations in the ferrite which are responsible for the ferromagnetic resonance, the magnetocrystalline anisotropy and the exchange interaction with the polymer. The composite Pani/BaFe12O19 shows absorption bands at the X-band that shift to the Ku-band with the substitution of iron, confirming the potential of these materials for microwave applications.

In organischen Leuchtdioden (OLEDs) werden üblicherweise anorganische Materialien wie Indium-Zinn-Oxid (ITO) als transparente leitfähige Anoden verwendet. ITO besitzt allerdings eine geringe Austrittsarbeit und kann deshalb Löcher nicht effizient in organische Materialien injizieren. Weiterhin ist ITO eine Quelle von Indium- und Sauerstoff-Ionen, die in die organischen Materialien diffundieren und dort mit der Organik reagieren bzw. als effiziente Exzitonenvernichter agieren. Eine mögliche Alternative zu ITO sind hoch leitfähige Polymere wie PEDOT:PSS und Polyaniline. Diese Studie untersucht die physikalischen Aspekte von OLEDs mit elektrisch dotierten Ladungstransportschichten auf Polymeranoden. Hierbei werden pin-OLEDs auf ITO mit OLEDs auf Polymeranoden direkt verglichen und mit dem derzeitigen Stand der Technik diskutiert. Die Untersuchungen zeigen, daß OLEDs auf PEDOT:PSS Anoden eine höhere Effizienz erreichen als OLEDs auf ITO Anoden. Um die physikalischen Unterschiede von pin-OLEDs auf ITO und PEDOT:PSS Anoden zu untersuchen, werden optische Simulationen sowie Ultraviolett-Photoemissions-Spektroskopie (UPS) und Lebensdauermessungen durchgeführt. Die optischen Simulationen zeigen, daß die Polymeranoden durch ihren geringen Brechungsindex eine höhere Lichtauskopplungseffizienz besitzen als OLEDs mit einer ITO-Anode. Außerdem finden UPS-Messungen eine geringere Löcherinjektionsbarriere von PEDOT:PSS zu dotierten und undotierten Lochtransportschichten. Aus diesem Grund ist die Ladungsträgerinjektion an der Anoden-Organik-Grenzfläche effizienter, wenn eine PEDOT:PSS-Anode verwendet wird. Lebensdauermessungen von pin-OLEDs auf PEDOT:PSS-Anoden zeigen eine vergleichbare Lebensdauer zu OLEDs auf ITO-Anoden. Die Ergebnisse dieser Untersuchungen zeigen eindeutig, daß Polymeranoden das Potential besitzen, ITO als Anode zu ersetzen und zusätzlich die OLED-Effizienz zu erhöhen.

Today, smart innovation has become an essential part of human life; thus, contemporary technologies are always looking for intelligent, responsive, and efficient materials to satisfy these demands. Consequently, synthetic "metals" or, more precisely, intrinsically conducting polymers (CPs) have begun to find a place as valuable and practical materials for a new generation of devices. Amongst all intrinsic conducting polymers, polyaniline (PANI) has attracted significant attention due to its outstanding air and moisture stability, simple preparation technique, and high electrical conductivity (chapter I). Chapter II represents the synthesis of a new PANI derivative that contains a phenoxazine unit co-polymerized with p-phenylenediamine derivatives by the Buchwald/Hartwig reaction. These polymers are soluble in many common organic solvents, which permit their full characterization and allow for solution processing. The polymers' optical properties mimicked PANI; however, they were more electrochemically stable and soluble compared to PANI. In addition, the analogous PANI emeraldine base forms a large bathochromic shift in the absorption spectra upon acidic doping to form analogues of PANI emeraldine salts. Chapter III describes our strategy to prepare economical, electrochemically stable, and processable PANI derivatives from carbazole and 1,4-aryldiamines for supercapacitor device. The polymers exhibit good solubility in various organic solvents, enabling a scalable spray-coating method to fabricate electrodes. The polymers were used to fabricate electrodes for supercapacitor devices and exhibit a maximum area capacitance of 64.8 mF cm−2 and specific capacitance of 319 F g−1 at a current density of 0.2 mA cm−2. Chapter IV MXene has been recently widely applied to energy storage devices due to its metallic conductivity and excellent electrochemical Activities. However, MXene sheets suffer from the restacking phenomena during cycling. Restacking restricts the ion diffusions and storage capability between the MXene layers, which lowers the accessible surface area. The restacking phenomena of MXene sheets was shown to be eliminated by the deposition of conductive polymers on the surface of MXene sheets.

Metal ion contamination in surface and ground water is a major threat as it has a direct implication on the health of terrestrial and aquatic flora and fauna. Lead (Pb2+), mercury (Hg2+), cadmium (Cd2+), nickel (Ni2+), copper (Cu2+) and cobalt (Co2+) are few of these metal ions which are classified under the high risk category. Of these, lead and mercury are of greater concern, as even nanomolar concentrations can be lethal, as they can be bio-accumulated and result in physiological as well as neurological disorders. In Asian countries like India and China, heavy metal pollution is more prevalent, as a consequence of poor governmental policies or ineffective or inadequate measures to combat this problem. In recent times, the monitoring and assessment of water pollution is a critical area of study, as it has a direct implication for its prevention and control. The major techniques used for metal ion detection are atomic absorption spectroscopy (AAS), X-ray fluorescence, ion chromatography, neutron activation, etc. Alternatively, the electrochemical, optical and electrical methods provide a platform for the fabrication of portable devices, which can facilitate the on-site analysis of samples in a rapid and cost-effective manner. This has led to a new field of research called chemical sensors or chemo sensory devices. The main aim of this study is to develop various chemosensory materials and test their response towards metal ion sensing. In this study, electroactive polymers have been synthesized for various sensor applications. The focus has been to design synthesize and test various functionalized electroactive polymers (FEAP) for the development of electrochemical, optical and chemoresistive sensors. Electroactive polymers like polyaniline, polypyrrole, polypyrrole grafted to exfoliated graphite oxide and dipyrromethene conjugated with p-(phenylene vinylene) have been synthesized and evaluated after functionalizing with metal coordinating ligands. These metal coordinating ligands were selected, in order to enhance their metal uptake capacity. Various metal ligands like imidazole, tertiary amine group, iminodiacetic acid, and dipyrromethene incorporated either in the polymer backbone or as a part of the backbone have been chosen for the metal binding. These functionalized electroactive polymers (FEAP) served as active material for metal ion sensing. The present investigation is subdivided into three sections. The first part includes design and chemical synthesis of the functionalized polymers by a series of organic reactions. The synthesis has been followed up by characterization using spectroscopic methods including NMR, FTIR, GCMS and Mass spectrometry. In the second part of the investigation, the synthesized polymer has been characterized for the changes in electronic, electric and optical properties after interaction with the selected metal ions. For this, the FEAP is allowed to interact with various metal ions and the changes in the relevant properties have been measured. This includes the study of changes in the conductivity, electronic properties like absorption or emission of the polymer, changes in the redox properties, etc. The third phase of investigation deals with the fabrication of the devices using the active FEAP. The sensor devices comprised of either films, or electrode modified with FEAP or solution of the FEAP, in combination with an appropriate technique has been used for the sensing. The major objectives are enumerated below 1. Functionalzation of polyaniline with imidazole functional group to get imidazole functionalized polyaniline (IMPANI) and study of the electronic, electrical and optical properties of the same. 2. Preparation of films of IMPANI and study of the change in conductivity of the film upon interaction with various metal ions, namely Cu2+, Co2+ and Ni2+ in their chloride form. 3. Synthesis of amine functionalized aniline monomer and chemical graft polymerization onto exfoliated graphite oxide as a substrate to synthesise the amine funtionalised polyaniline grafted to exfoliated graphite oxide (EGAMPANI). Modification of the carbon paste electrode (CPE) with EGAMPANI and study of the electrode characteristic. 4. Study of the electrode properties of EGAMPANI modified carbon paste electrode. 5. Evaluation of the EGAMPANI modified carbon paste electrode as a multi-elemental voltammetric sensor for Pb2+, Hg2+ and Cd2+ in aqueous system. 6. Functionalization of polypyrrole with iminodiacetic acid and characterization of the polymer to synthesis iminodiacetic acid functionalized polypyrrole (IDA-PPy). 7. Modification of the CPE with IDA-PPy by drop casting method and evaluation of the Pb2+ sensing properties. 8. Study of the effect of other metal ions say Hg2+, Co2+, Ni2+, Zn2+, Cu2+ and Cd2+ on the anodic stripping current of Pb2+ using EGAMPANI modified CPE. 9. Synthesis of dipyrromethene-p-(phenylene vinylene) conjugated polymer for heavy metal ion sensing. 10. Study of the changes in the optical absorption and emission properties of the polymer in THF and evaluation of the change in these optical properties upon interaction with the metal ions as analyte. The salient findings of the research work are highlighted as follows, In the first synthesis, aniline has been functionalized with imidazole group and this monomer has been chemical oxidatively polymerized to obtain imidazole functionalized polyaniline (IMPANI). The synthesized polymer possesses a nano-spherical structure, as confirmed from the morphological characterisation using scanning electron microscopy. The IMPANI has been interacted with a representative metal ion, copper (II) chloride, and the copper complexed polymer (Cu-IMPANI) has been subjected to various studies. The coordination of copper with IMPANI results in an increase of molecular weight of the polymer as a result of aggregation, as observed from dynamic light scattering measurements. Apart from this, a significant finding is the decrease of the pH of the system after copper ion coordination attesting to the generation of a secondary hydrochloride ion during the coordination of the copper to the imidazole side chain. This is further confirmed by an increase in conductivity of the Cu-IMPANI compared to IMPANI, measured using the four-probe technique. The increase of conductivity due to copper coordination is one order of magnitude higher. The films which have been prepared from IMPANI and Cu-IMPANI exhibit different morphology. The Cu-IMPANI film prepared by prior co-ordination of Cu ion with IMPANI powder shows a flaky structure, which is not preferable for the conductivity measurements, as a consequence of discontinuity in the medium. To overcome this problem, IMPANI films were initially prepared and then interacted with copper ions for a desired duration, before measurement of the conductivity. This latter procedure enabled the preparation of smooth films for the development of chemoresistive sensors. In continuation of the initial study highlighted above, IMPANI films of thickness 0.02 ± 0.001 mm have been prepared using IMPANI and PANI in DMPU in the ratio of 7:3 by mass. After exposure of the films with respective metal chlorides, such as Ni2+, Co2+ and Cu2+, a change in conductivity is observed in the concentration range of 10-2 to 1 M of metal chlorides. The sensor response may be arranged in the sequence: Ni2+ > Cu2+ > Co2+ at 1M concentration. On the contrary, films prepared from PANI-EB under identical conditions do not exhibit any appreciable change in conductivity. The optimum exposure time is determined to be 10 min for a maximum change in conductivity, after exposure to the chosen metal ions. In the second system taken up for investigation, a tertiary amine containing polyaniline (AMPANI) has been grafted to exfoliated graphite oxide. The amine containing polyaniline grafted to exfoliated graphite oxide (EGAMPANI) has been characterised for structural, morphological and elemental composition. The grafting percentage has been determined to be 7 % by weight of AMPANI on the EGO surface. The synthesized EGAMPANI (5 weight %) has been used to modify carbon paste electrode (CPE) for electrochemical sensor studies. Based on the differential pulse anodic stripping voltammetric studies, the electrochemical response may be arranged in the following sequence: Pb 2+>Cd 2+>Hg 2+ The minimum detection levels obtained are 5×10-6, 5×10-7, and 1.0×10-7 M for Hg2+, Cd2+ and Pb2+ ions respectively. In the next study, an iminodiacetic acid functionalized polypyrrole (IDA-PPy) has been synthesized and characterised for its elemental and structural properties. This has been further used to modify the CPE by drop casting method and used for the specific detection of Pb2+ in acetate buffer. Various parameters governing the electrode performance such as concentration of depositing solution, pH of depositing solution, deposition potential, deposition time, and scan rate, have been optimized to achieve maximum performance and found to be 20 μl, 4.5, -1.3 V, 11 min, 8 mV s-1 respectively for the chosen parameters. Additionally, the influence of other heavy metal ions on the lead response has been studied and it is observed that Co, Cu and Cd ions are found to be interfering. Further, the response of Cd, Co, Cu, Hg, Ni and Zn on IDA-PPy functionalized electrode has been evaluated. The selectivity of IDA-PPy modified electrode for Pb2+ is observed in the concentration range of 1 × 10-7 M and below. The IDA-PPy modified CPE shows a linear correlation for Pb2+ concentration in the range from 1×10-6 to 5×10-9 M and with a lowest limit of detection (LLOD) of 9.6×10-9 M concentration. The efficacy of the electrode for lead sensing has also been evaluated with an industrial effluent sample obtained from a lead battery manufacturing unit. The fourth synthesis pertained to the development of an optical sensor for Fe2+, and Co2+ ions. For this, dipyrromethene as a metal coordinating ligand in conjugation with p-phenylenevinylene has been synthesized and tested for its structural as well as optical properties. It is observed that the polymer shows three absorptions, namely at 294 nm, 357 nm and a major absorption observed as a broad band ranging from 484 to 670 nm. The emission spectrum of the polymer excited at 357 nm shows a characteristic blue emission with a maximum intensity centered at 425 nm. The emission quenching in the presence of various metal ions have been tested and are found to be quenched in presence of Fe2+ and Co2+ ions. All the other metal ions tested namely, Cr3+, Cu2+, and Zn2+ are not found to exhibit any change in the emission spectra below the concentration of 1 × 10-4 M. The linear correlation of the emission intensity with the concentration of the Co2+ and Fe2+ ions has been determined using Stern-Volmer plot. For Co2+ the Stern-Volmer regime is observed from 1×10-4 to 9×10-4 M concentration and the quenching constant Ksv is determined to be 8.67 ×103 M-1. For Fe2+, the linearity is found to be in the regime of 1×10-5 to 9×10-5 M and the quenching constant Ksv is determined to be 7.90 × 103 M-1. In conclusion, different electroactive polymers functionalized with metal coordinating ligands have been synthesized, characterised and evaluated for metal sensing applications. Techniques like electrochemical, optical and conductivity have been used to characterise the response of these FEAP towards metal sensing. It is can be concluded that the electrochemical sensors are more reliable for sensing especially at very low concentrations of metal ions such as Pb, Cd and other techniques like optical and conductimetric are good for detecting metal ions namely Fe, Co, Ni, Cu. The selectivity towards the metal ions is a function of the metal chelating ligand and the extent of sensitivity is dependent upon the technique employed.

Polyaniline (PANI), when doped with small-molecule acids, is an attractive candidate for organic and polymer electronics because of its high electrical conductivity. Its utility as functional components in electrical devices, however, has been severely restricted because such PANI has limited processibility stemming from its limited solubility in common solvents. To overcome this barrier, we have developed water dispersible PANI that is template polymerized in the presence of a polymer acid, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), or PAAMPSA. The polymer acid serves two roles: it acts as a dopant to render PANI conductive and excess water soluble pendant groups provide dispersibility of PANI in aqueous media. While the introduction of polymer acids renders the conducting polymer processible, such gain in processibility is often accompanied by a significant reduction in conductivity. As such, PANI that is doped with polymer acids has only seen limited utility in organic electronics. Given the promise of conducting polymers in organic electronics in general, this thesis focuses on the elucidation of processing-structure-property relationships of PANI-PAAMPSA with the aim of ultimately improving the electrical conductivity of polymer acid-doped PANI. By controlling the molecular weight and molecular weight distribution of the polymer acid template, we have improved the conductivity of PANI-PAAMPSA from 0.4 to 2.5 S/cm. The conductivity increases with decreasing molecular weight of PAAMPSA, and it further increases with narrowing the molecular weight distribution of PAAMPSA. Strong correlations between the structure and the conductivity of PANI-PAAMPSA are observed. In particular, the crystallinity of PANI increases with increasing the conductivity of PANI-PAAMPSA. Given that the crystallinity qualifies the molecular order in PANI-PAAMPSA, we observe a linear correlation between molecular order and macroscopic charge transport in PANI-PAAMPSA. PANI-PAAMPSA forms electrostatically stabilized sub-micron particles during polymerization due to strong ionic interactions between the sulfonic acid groups of PAAMPSA and aniline. When cast as films, the connectivity of these particles must play an important role in macroscopic conduction. The size and size distribution of PANI-PAAMPSA particles is strongly influenced by the molecular characteristics of polymer acid template. Templating the synthesis of PANI-PAAMPSA with a higher molecular weight PAAMPSA results in larger particles, and templating with a PAAMPSA having a larger molecular weight distribution results in a large size distribution in the particles. Because conduction in PANI-PAAMPSA films is governed by how these particles pack, the macroscopic conductivity of PANI-PAAMPSA films increases with increasing particle density, that is reducible from the molecular characteristics of PAAMPSA. Moreover, PANI-PAAMPSA particles are structurally and chemically inhomogeneous. The conductive portions of the polymer preferentially segregate to the particle surface. Conduction in these materials is therefore mediated by the particle surface and conductivity thus scales superlinearly with particle surface area per unit film volume. We further have improved the electrical conductivity of PANI-PAAMPSA by more than two orders of magnitude via post-processing solvent annealing with dichloroacetic acid (DCA). Since DCA is a good plasticizer for PAAMPSA and its pKa is lower than that of PAAMPSA (pKas of DCA and PAAMPSA are 1.21 and 2.41, respectively, at room temperature), DCA can effectively moderate the ionic interactions between PANI and PAAMPSA, thereby relaxing the sub-micron particulate structure arrested during polymerization. PANI-PAAMPSA can thus rearrange from a “compact coil” to an “extended chain” conformation upon exposure to DCA. Efficient charge transport is thus enabled through such “extended chain” PANI-PAAMPSA structure. DCA-treated PANI-PAAMPSA exhibits an average conductivity of 48 S/cm. The DCA treatment is not only specific to PANI-PAAMPSA. This treatment can also enhance the conductivity of commercially-available poly(ethylene dioxythiophene) that is doped with poly(styrene sulfonic acid), or PEDOT-PSS. Specifically, DCA-treated PEDOT-PSS exhibits a conductivity of 600 S/cm; this conductivity is the highest among polymer acid-doped conducting polymers reported so far. PANI-PAAMPSA can effectively function as anodes in organic solar cells (OSCs) whose active layer is a blend of poly(3-hexylthiophene), P3HT, and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Specifically, the OSCs with PANI-PAAMPSA anodes exhibit an average short circuit current density of 1.95 mA/cm², open circuit voltage of 0.52 V, fill factor of 0.38, and efficiency of 0.39 %. The use of DCA-treated PANI-PAAMPSA as anodes increases device performance (i.e., short circuit current density and thereby efficiency) of OSCs by approximately two and a half fold. The OSCs with DCA-treated PANI-PAAMPSA anodes exhibit short circuit current density and efficiency as high as 4.95 mA/cm² and 0.97 %, respectively. We demonstrated several factors that govern the electrical conductivity of polymer acid-doped conducting polymers. Design rules, such as those illustrated in this study, can enable the development of conducting polymers that is not only easily processible from aqueous dispersions, but also sufficiently conductive for electronic applications, and should bring us closer to the realization of low-cost organic and polymeric electronics. / text

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.