Recent Advances in Conjugated Polymers for Light Emitting Devices

A recent advance in the field of light emitting polymers has been the discovery of electroluminescent conjugated polymers, that is, kind of fluorescent polymers that emit light when excited by the flow of an electric current. These new generation fluorescent materials may now challenge the domination by inorganic semiconductor materials of the commercial market in light-emitting devices such as light-emitting diodes (LED) and polymer laser devices. This review provides information on unique properties of conjugated polymers and how they have been optimized to generate these properties. The review is organized in three sections focusing on the major advances in light emitting materials, recent literature survey and understanding the desirable properties as well as modern solid state lighting and displays. Recently, developed conjugated polymers are also functioning as roll-up displays for computers and mobile phones, flexible solar panels for power portable equipment as well as organic light emitting diodes in displays, in which television screens, luminous traffic, information signs, and light-emitting wallpaper in homes are also expected to broaden the use of conjugated polymers as light emitting polymers. The purpose of this review paper is to examine conjugated polymers in light emitting diodes (LEDs) in addition to organic solid state laser. Furthermore, since conjugated polymers have been approved as light-emitting organic materials similar to inorganic semiconductors, it is clear to motivate these organic light-emitting devices (OLEDs) and organic lasers for modern lighting in terms of energy saving ability. In addition, future aspects of conjugated polymers in LEDs were also highlighted in this review

Kinetic Studies of Atom Transfer Radical Polymerisations of Styrene and Chloromethylstyrene with Poly(3-hexyl thiophene) Macroinitiator

Poly(3-hexyl thiophene)-b-poly(styrene-co-chloromethylstyrene) copolymers, to be used as a prepolymer for preparing donor-acceptor block copolymers for organic solar cells, have been synthesised by reacting P3HT macroinitiators with styrene and chloromethylstyrene via three types of atom transfer radical polymerisation (ATRP) systems, which are (1) a normal ATRP, (2) activators generated by electron transfer (AGET), and (3) a simultaneous reverse and normal initiation (SR&NI). The kinetics of these ATRP systems were studied as a function of monomers to the macroinitiator molar ratio. It was found that all of the three types of ATRP systems led to first order kinetics with respect to monomers. The highest rate constant (k) of 3.4 × 10−3 s−1 was obtained from the SR&NI ATRP system. The molecular weights of the product determined by the GPC were lower than were the theoretical values. The result was discussed in light of the chain transfer reaction to the poly(chloromethylstyrene) repeating units. Morphology of the synthesized block copolymers, examined by an atomic force microscopy (AFM), were also compared and discussed

Triplet-State and Singlet Oxygen Formation in Fluorene-Based Alternating Copolymers

Data are reported on the triplet states of a series of fluorene-based A-alt-B type alternating copolymers based on pulse radiolysis-energy transfer and flash photolysis experiments. From the pulse radiolysis experiments, spectra are given for eight copolymers involving phenylene, thiophene, benzothiadiazole, and oligothienylenevinylene groups. Quantum yields for triplet-state formation (ΦT) have been obtained by flash photolysis following laser excitation and in one case by photoacoustic calorimetry. In addition, yields of sensitized formation of singlet oxygen have been determined by time-resolved phosphorescence and are, in general, in excellent agreement with the ΦT values. In all cases, the presence of thiophene units is seen to increase intersystem-crossing quantum yields, probably because of the presence of the heavy sulfur atom. However, with the poly[2,7-(9,9-bis(2‘-ethylhexyl)fluorene)-alt-1,4-phenylene] (PFP), thiophene S,S-dioxide (PFTSO2) and benzothiadiazole (F8BT) copolymers, low yields of triplet formation are observed. With three of the copolymers, the energies of the triplet states have been determined. With PFP, the triplet energy is virtually identical to that of poly[2,7-(9,9-bis(2‘-ethylhexyl)fluorene)]. In contrast, with fluorene−thiophene copolymers PFaT and PF3T, the triplet energies are closer to those of thiophene oligomers, indicating that there is significant conjugation between fluorene and thiophene units but also that there is a more localized triplet state than with the homopolymers

Problèmes aux limites issus de la supraconductivité (estimations semi-classiques et comportement asymptotique des solutions)

Cette thèse est consacrèe à l'étude de plusieurs modèles de l'effet de proximité' dans le cadre de la thèorie de Ginzburg-Landau de la supraconductivité. Ces modèles proviennent des interfaces entre des supraconducteurs et des métaux normaux.Dans une première partie de cette thèse, nous estimons dans le régime semiclassique le bas du spectre d'un opérateur de Schrôdinger magnétique associé à une condition au bord du type Fourier (Robin), appelée dans ce contexte la condition au bord de de Gennes, et nous étudions également la localisation des états fondamentaux. Nous exhibons des cas où la condition au bord de de Gennes a des effets forts sur cette localisation.Dans une autre partie, nous construisons un problème spectral lié à l'apparition de la supraconductivité pour une fonctionnelle de Ginzburg-Landau généralisée ayant des coefficients discontinues, où le paramètre d'ordre' et le potentiel magnétique' sont définis dans l'espace entier. Pourle régime où le paramétre de Ginzburg-Landau est grand, nous estimons le champ surcritique corespondant au champ pour lequel les états normaux perdent leur stabilité. Dans d'autres régimes asymptotiques, nous retrouvons un développement limité déjà obtenu pour un autre modèle standard'.Dans la dernière partie, nous étudions de nouveau une fonctionnelle de Ginzburg-Landau généralisée mais dans le cas sans champ magnétique appliqué. Nous obtenons dans ce cas le comportement asymptotique du paramètre d'ordre pour le régime où le paramètre de Ginzburg-Landau est grand. Ceci montre en particulier que la supraconductivité persiste dans une bande mince dans le métal normal, près du bord du supraconducteur.This thesis is devoted to the study of various models for the proximity effect' in the frame work of the Ginzburg-Landau theory of superconductivity. These models arise in the situation when a superconductor is adjacent to a normal metal.In a first part of this thesis, we estimate in the semi-classical limit the ground state energy of a magnetic Schrôdinger operator associated to a Fourier (Robin) type boundary condition, called in this context the de Gennes boundary condition, and we study the localization of the ground states. We exhibit cases when the de Gennes boundary condition has strong effects on this localization.In another part, we formulate a spectral problem related to the onset of superconductivity for a generalized Ginzburg-Landau functional having discontinuous coefficients, where the order parameter and the magnetic potential are defined in the whole space In the regime when the Ginzburg-Landau parameter (of the superconducting material) is large, we estimate the critical applied magnetic field for which the normal state will lose its stability. In some asymptotic situations, we recover results related to the standard' Ginzburg-Landau model.In the final part, we study again a generalized Ginzburg-Landau functional in the case without an applied magnetic field. We determine in this case the asymptotic behavior of the order parameter in the regime when the Ginzburg-Landau parameter is large. This shows in particular that the superconductivity persists in a thin boundary sheath of the normal material, near the boundary of the superconductor.ORSAY-PARIS 11-BU Sciences (914712101) / SudocORSAY-PARIS 11-Bib. Maths (914712203) / SudocSudocFranceF

Effect of molecular weight on the structure and crystallinity of poly(3-hexylthiophene)

Recently, two different groups have reported independently that the mobility of field-effect transistors made from regioregular poly(3-hexylthiophene) (P3HT) increases strongly with molecular weight. Two different models were presented: one proposing carrier trapping at grain boundaries and the second putting emphasis on the conformation and packing of the polymer chains in the thin layers for different molecular weights. Here, we present the results of detailed investigations of powders and thin films of deuterated P3HT fractions with different molecular weight. For powder samples, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) were used to investigate the structure and crystallization behavior of the polymers. The GPC investigations show that all weight fractions possess a rather broad molecular weight distribution. DSC measurements reveal a strong decrease of the crystallization temperature and, most important, a significant decrease of the degree of crystallinity with decreasing molecular weight. To study the structure of thin layers in lateral and vertical directions, both transmission electron microscopy (TEM) and X-ray grazing incidence diffraction (GID) were utilized. These methods show that thin layers of the low molecular weight fraction consist of well-defined crystalline domains embedded in a disordered matrix. We propose that the transport properties of layers prepared from fractions of poly(3-hexylthiophene) with different molecular weight are largely determined by the crystallinity of the samples and not by the perfection of the packing of the chains in the individual crystallites