ABSTRACT Optoelectronics of polymer light emitting diode (LED) depends significantly on polymer molecular structure and charge conjugation. This study focused on the optoelectronics of freestanding films and LEDs of a colinear, fully conjugated heterocyclic aromatic rigid-rod polymer (PBT) and its mixtures with a partially conjugated coil-like polymer (Pbi). A deuterated PBTd4 was also mixed with a fully conjugated coil-like polymer (ABPBI) for UV-Vis absorption spectrum, photoluminescence (PL), diodic current-voltage response, and electroluminescence (EL). Rigid-rod PBT was only soluble in strong protic acid. PBT films were processed using methanesulfonic acid. PBT free-standing films showed maximum absorptions at 468 nm and 640 nm; PBTd4 having all hydrogen atoms on the phenylene moiety substituted by deuterium retaining same electron orbitals thus showed same absorption and PL spectra. It was likewise for the PBTd4 and ABPBI mixtures at ABPBI concentrations of 1 % and 10 %. For mixtures of PBT and Pbi, the absorption spectra indicated super- position of individual optical absorption response and no energy transfer. However, PL spectra showed a blue shift with increasing Pbi content. This was attribed for PBT rod-like configuration, or PBT aggregation perturbed by mixing with Pbi. Monolayer LED of Al/PBT/ITO and Al/Pbi/ITO yielded a threshold voltage of 4 V. When PBT/Pbi mixtures of 75/25, 50/50, 25/75, were used as the light emitting layer, the threshold voltage altered to 10 V, 7 V and 17 V, respectively. This threshold voltage deviation from 4 V is due mainly to difference in layer thickness, or phase separation affecting the tunneling effect. To enhance LED stability, an Ag layer was evaporated onto the Al electron injection electrode. For Ag/Al/PBT/ITO devices and mixed PBT/Pbi (75/25,50/50,25/75) devices, the maximum EL wavelength exhibited no systematic change at 753 nm, 714 nm, 727 nm, and 697 nm, respectively, due to using different bias voltage.

Molecular light emitting diode, including organic light emitting diode (OLED) and polymer light emitting diode (PLED), is commonly consist of one or several molecular layer(s) sandwiched between an anode and a cathode. When electrons and holes are injected respectively from cathode and anode into the molecular layer by a bias voltage, these two types of carriers migrate towards each other and a fraction of them recombine to form light emission. The focus of this study is electrode modifications of molecular light emitting diode. The electrode modifications include using a low work function cathode material, a high work function anode material or inserting a very thin electrode modifier between molecular layer and electrode for enhancing the electron or the hole injection efficiency leading to higher electroluminescence emission and/or lower threshold voltage. Low work function metal, Mg, could effectively reduce the electron injection barrier between molecular layer and cathode leading to better emission brightness and threshold voltage. A monolayer rigid-rod poly-p-phenylenebenzobisthiazole (PBT) or poly-p-phenylenebenzobis- oxazole (PBO) PLED with Mg cathode demonstrated a low threshold voltage of 3 V. Besides, a very thin layer of LiF (or Al2O3) inserted between molecular layer and Al cathode was applied to enhance the electron injection efficiency leading to a stronger electroluminescence intensity and a low threshold voltage of 2.8 V. On anode modification, a thin PBO layer was inserted between molecular layer and the indium-tin-oxide (ITO) substrate for improving the electroluminescence emission brightness and the threshold voltage. The PBO modified anode could effectively enhance the electro- luminescence intensity and lower the threshold voltage to 1 V~ 3 V on several mono- or multi-layer molecular light emitting diodes. Besides, a novel ITO substrate cleaning method via acid treatment was applied for increasing the work function of ITO to effectively enhance the hole injection efficiency.

Les ionomères aromatiques sont considérés comme une alternative prometteuse à Nafion pour les PEMFCs en raison de leur bonne stabilité à l'oxydation, d'excellentes propriétés thermomécaniques et de faibles coûts, etc. La plupart des ionomères aromatiques sulfonés rapportés au cours des dernières décennies présentent cependant des performances inférieures à celles de Nafion. Avec une capacité d'échange ionique (CEI) similaire, d'une part, les ionomères aromatiques sont beaucoup moins conducteurs que Nafion, notamment à faible humidité relative. Les ionomères aromatiques ayant une CEI suffisante pour donner une conductivité équivalente à celle de Nafion, d'autre part, présentent un comportement excessivement gonflant dans l'eau. Les inconvénients des ionomères aromatiques sulfonés proviennent de (i) la répartition aléatoire de groupes acides sur un squelette de polymère rigide conduisant à une séparation hydrophile-hydrophobe faible, (ii) la proximité de fractions conductrices de protons à la chaîne principale de polymère conduisant à une nanostructure basse de composés ioniques, et (iii) la faible acidité de l'acide arylsulfonique. Dans le but de surmonter ces inconvénients, mon travail de doctorat se concentre sur le développement de nouveaux ionomères aromatiques avec une morphologie et des propriétés améliorées grâce à la conception de l'architecture moléculaire, en combinaison avec une condition optimisée de traitement de la membrane. A base de cet objectif, deux séries d'ionomères aromatiques à base de copoly (arylène éther sulfone) partiellement fluoré portant des chaînes latérales pendantes d'acide perfluorosulfonique (séries InX/Y) ou perfluorosulfonimide (SiX/Y) ont été développées et caractérisées. De plus, les PEM basés sur le mélange Nafion/InX/Y ont également été ciblés. Une grande attention a été portée à l'optimisation de l'état de traitement des membranes et à l'élucidation de la relation structure-morphologie-propriété des matériaux. / Aromatic ionomers are considered as a promising alternative to Nafion for PEMFCs due to their good oxidative stability, excellent thermomechanical properties, and low cost, etc. Most sulfonated aromatic ionomers reported over the past decades, however, show lower performance than that of Nafion. With similar ion-exchange capacity (IEC), on one hand, aromatic ionomers are much less conductive than Nafion, notably at low relative humidity. Aromatic ionomers with sufficient IEC to give equivalent conduction to that of Nafion, on the other hand, exhibit excessively swelling behavior in water. The shortcomings of sulfonated aromatic ionomers derive from (i) the random distribution of acidic groups on rigid polymer backbone leading to poor hydrophilic-hydrophobic separation, (ii) the proximity of proton-conducting moieties to the polymer main chain resulting in low nanostructure of ionic clusters, and (iii) the low acidity of aryl sulfonic acid. With the aim of overcoming these drawbacks, my PhD work focuses on developing new aromatic ionomers with improved morphology and properties via molecular architecture design, in combination with optimized membrane processing condition. Based on this objective, two series of aromatic ionomers based on partially-fluorinated multi-block copoly(arylene ether sulfone)s bearing pendant perfluorosulfonic acid (InX/Y series) or perfluorosulfonimide (SiX/Y series) side chains have been developed and characterized. Moreover, PEMs based on Nafion/InX/Y blend have also been focused. Much attention has been paid to optimizing the membrane processing condition and elucidating the structure-morphology-property relation in these materials.

Dans le cadre de ces travaux, l’objectif fixé était de développer des polymères aromatiques possédant des propriétés de conduction protonique. Pour y parvenir des motifs de type acide sulfonique ont été introduits le long des chaînes macromoléculaires. La méthodologie de synthèse de ces polymères qui a été choisie, consistait à polymériser des précurseurs contenant dans leur structure un motif perfluoroalkyle sulfoné. Quatre précurseurs originaux ont ainsi été initialement synthétisés. Différents polymères aromatiques ont été préparés à partir de ces précurseurs en faisant varier le taux de séquences perfluoroalkyles sulfonées. Ces polymères ont ensuite été mis en oeuvre sous la forme de membranes denses selon un procédé de coulée évaporation. A partir de ces membranes, des études de gonflement à l’eau et de conductivité ionique ont été réalisées. / As part of this work, the objective was to develop aromatic polymers with proton conduction properties. To achieve this, the sulfonic acid motifs were introduced along the macromolecular chains. The methodology of synthesis of these polymers was to polymerise the precursor containing in their structure a perfluoroalkyl sulfone moieties. Four novel precursors have been initially synthesized. Different aromatic polymers were prepared from these precursors by varying the rate of perfluoroalkyl sulfonated sequences. These polymers were then used in the form of dense membranes obtained by a casting process of evaporation. From these membranes, swelling studies in water and ionic conductivity were carried out.