Les sources d'énergie renouvelable connaissent un essor grandissant. Parmi celles-ci se trouvent les cellules photovoltaïques. Elles ont pour objet la transformation de la lumière en électricité. Les dispositifs actuels, basés sur le silicium, nécessitent des matériaux de très grande pureté et de hautes températures de mise en œuvre, les empêchant de concurrencer les principales sources d’énergie actuelles (fossile, nucléaire). Une alternative pourrait provenir des matériaux semi-conducteurs organiques. En effet, l’utilisation de méthodes de mise en œuvre à partir de solutions pourrait permettre la fabrication de dispositifs flexibles et bon marché. Des résultats encourageants ont été obtenus avec des polymères conjugués et de petites molécules organiques. Les cristaux liquides discotiques CLDs forment une catégorie particulièrement intéressante de matériaux. Ils ont en effet la capacité de s’organiser spontanément en colonnes de molécules, formant des semi-conducteurs à une dimension. Leurs propriétés intéressantes en tant que semi-conducteurs, combinées à une mise en œuvre facile, en font de bons candidats pour de futures applications. Dans ce travail, deux familles complémentaires de matériaux discotiques ont été développées, formant une paire de semi-conducteurs de type n et p. Leurs structures chimiques ont été étudiées en vue d'obtenir des matériaux possédant un ensemble de propriétés choisies afin d’optimiser les paramètres clefs du processus de photo-génération de charges. Ces propriétés sont les suivantes: forte absorption de la lumière dans le visible, fort caractère semi-conducteur de type n ou p, pas de phase cristalline à température ambiante, présence d'une phase cristal liquide colonne, phase isotrope en dessous de 200°C. De plus, les matériaux doivent être accessibles en un nombre minimum d’étapes d’une synthèse efficace, et ce avec un haut niveau de pureté. Ils doivent également être fortement solubles dans les solvants organiques usuels. Cette étude comporte, pour chacune des deux familles de matériaux, le design de leur structure chimique, leur synthèse et la caractérisation de leurs propriétés physiques (thermotropes, optoélectroniques, électrochimiques). Comme possible semi-conducteur de type p, cinq dérivés tétrasubstitués de la phthalocyanine non-métallée ont été synthétisés, donnant un matériau possédant l’ensemble des propriétés recherchées. Comme possible semi-conducteur de type n, six dérivés hexasubstitués de l’hexaazatrinaphthylène ont été étudiés. L’un d’eux possède les propriétés requises. Finalement, les propriétés optoélectroniques et photovoltaïques de mélanges des deux matériaux les plus prometteurs, ensemble ou avec d’autres matériaux, ont été étudiées. Des cellules solaires de rendement maximum de 1 % ont été obtenues pour deux dispositifs de compositions différentes. Ces rendements, bien qu’inférieurs à ceux obtenus précédemment par d’autres groupes (jusqu’à 34 % à ce jour), sont néanmoins révélateurs des potentialités des matériaux organiques, et plus particulièrement des cristaux liquides discotiques, pour de futures applications dans le domaine des dispositifs électroniques.

No description available.

Polymer Light-Emitting Electrochemical Cells (PLECs) are solid state devices based on the in situ electrochemical doping of the luminescent polymer and the formation of a p-n junction where light is emitted upon the application of a bias current or voltage. PLECs answer the drawbacks of polymer light-emitting diodes as they do not require an ultra-thin active layer nor are they reliant on low work function cathode materials that are air unstable. However, because of the dynamic nature of the doping, they suffer from slow response times and poor stability over time. Frozen-junction PLECs offer a solution to these drawbacks, yet they are impractical due to their sub-ambient operation temperature requirement. Our work presented henceforth aims to achieve room temperature frozen-junction PLECS. In order to do that we removed the ion solvating/transporting polymer from the active layer, resulting in a luminescent polymer combined solely with a salt sandwiched between an ITO electrode and an aluminum electrode. The resulting device was not expected to operate like a PLEC due to the absence of an ion-solvating and ion-transporting medium. However, we discovered that the polymer/salt devices could be activated by applying a large voltage bias, resulting in much higher current and luminance. More important, the activated state is quasi static. Devices based on the well-known orange-emitting polymer MEH-PPV displayed a luminance storage half-life of 150 hours when activated by forward bias (ITO biased positively with respect to the aluminum) and 200 hours when activated by reverse bias. More remarkable yet, devices based on a green co-polymer displayed no notable decay in current density or luminance even after being stored for 1200 hours at room temperature! PL imaging under UV excitation demonstrates the presence of doping. These devices are described herein along with an explanation of their operating mechanisms. / Thesis (Master, Physics, Engineering Physics and Astronomy) -- Queen's University, 2013-11-29 17:40:19.152

The aim of investigating the 2D PbX6 inorganic organic hybrids was to study octahedral distortions, short interlayer spacing’s, and the effect of functionalized aliphatic’s terminal halogen on idealizing or destabilizing the octahedral arrangements and their effect on the band gap of the single layer 2D hybrid systems. It was found that the PbX6 metal centred distortions do display some impact on the band gap, the greater the distortion experienced in the Ieq-Pb-Ieq cis bond angles, the wider the band gap, as we suspect a decrease in I 5p antibonding character which lowers the top of the valence band. The terminal halogen interaction specifically in (BrC2)PbI4, clearly displayed some Br 4p/s character at the bottom of the conduction band, which may further explain the reduction of the band gap of this compound. This in conjunction with the shorter interlayer spacing serve to stabilize more idealized bridging angles, as seen in both the lead iodide and bromide analogues. In the short interlayer spacing compounds large idealizations of the Pb-X-Pb bridging angles are observed however display a large metal centred octahedral distortions in order accommodate the spatial occupation of the lone pair on lead. It was generally observed that the lead bromide hybrids appear to have a greater sensitivity to exciton lattice interactions, which give rise to red shifted emissions and absorptions with decreasing temperature. Structurally this behaviour is counterintuitive; because the structures increase in inorganic distortions with decreasing temperature and therefore a blue shift in the exciton absorption is expected. It should be noted that compounds displaying this phenomenon most, (C4, C6, C7)PbBr4 do display a large amount of structural disorder in their lower temperature phases. In the 1D systems investigated further structure to property correlations were made. Optically it was found that unlike the corner-shared perovskite type 1D wires of [NH2C(I)=NH2]3PbI5 and [CH3SC(=NH2)NH2]3PbI5 the first exciton absorption of the octahedral face sharing wires of (A)PbI3 appear to be largely insensitive to the inorganic structural distortions experienced as a result of the low temperature phase transitions. In one instance however a low temperature phase transition did result in a polaron emission which was directly related to a discontinuity in the inorganic wires. More generally experimental links between the STE luminescence emissions and the inter-wire spacing, organic dielectric constant, and the density of the crystal, were shown to influence the STE lattice interactions to a greater degree. This effect is increased through a decrease in crystal density and organic dielectric constant, with an associated increase in the inter-wire spacing. Therefore as the exciton lattice interactions increase, a red shift in the STE emissions is observed. In another series of systems strong 1- and interactions were present in particularly two 1D charge transfer compounds. It was noted that the inorganic wires promote interactions between the organic templates as has also been established in literature. Structurally it was also observed that the CT transitions of these compounds begin to largely coincide with the STE emission arising from the inorganic wire. Even though the CT compounds structurally have strong interactions the current experiments do not ascertain to what degree this interaction assists in electron transport. It was also established that as intermolecular interactions are absent in previously published MV and Et compounds with the dominant CT interaction was the I…N interaction which functions over a large range (4.9A). This long distance is substantiated from the strong covalent character of the I…N interaction observed in IR experiments completed on (MV)Pb2I6. It was also observed in our compounds that the position of the LUMO of the organic cation relative to the valence band of the inorganic wires appears to be largely dependent on the N…I distance and largely independent of the electron accepting templates HOMO-LUMO gap. The increased wire thickness observed in these compounds does appear to display a pronounced effect on the PL emissions as seen in three chain wide wires produced. The thicker chains begin to allow higher energy emission’s to occur i.e. the desired first exciton emission begins to become favored due to the relaxing of the wires spatial confinement on the electron-hole’s orbit. Further investigations are needed into even thicker chain wires, in order to ascertain the ideal size of the wire to obtain the desired high energy first exciton emission. To date the wire thickness that does give rise to the first exciton emission appears to still need at least six coordinated PbI6 octahedral units.

He, Zikai. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

Organic semiconductors exhibit exceptionally long spin lifetimes, and recent observations of the inverse spin hall effect as well as micrometer spin diffusion lengths in conjugated polymers have spiked interest in employing such carbon-based materials in spintronics applications. The charge transport and photophysics of organic semiconductors have been intensely studied for optoelectronic applications, revealing subtle relationships between molecular geometry, morphology and physical properties. Similar structure-property relationships remain mostly unknown for spin dynamics, where the charge carrier spins couple to their environment through hyperfine (HFI) and spin-orbit interactions (SOC). HFIs provide a pathway for spin relaxation while SOC plays a dual role in such materials: it couples the spin to its angular momentum and therefore enables both spin-to-charge conversion and spin relaxation. Understanding the molecular SOC, and finding a means to tune its strength, therefore is fundamentally important for materials design and selection. However, quantifying SOC strengths indirectly through spin relaxation effects has proven difficult due to competing relaxation mechanisms. We initially present a systematic study of the g-tensor shift in molecular semiconductors and establish it as a probe for the SOC strength in a series of high mobility molecular semiconductors. The results demonstrate a rich variability of molecular g-shifts with the effective SOC, depending on subtle aspects of molecular composition and structure. We then correlate the above g-shifts to spin-lattice relaxation times over four orders of magnitude, from 200 µs to 0.15 µs, for isolated molecules in solution and relate our findings to the spin relaxation mechanisms that are likely to be relevant in solid state systems. Isolated molecules provide an ideal model system to investigate a spin's interactions with its environment but device applications commonly employ thin films. The second half of this thesis investigates polaron spin lifetimes in field effect transistors with high-mobility conjugated polymers as active layers. We use field-induced electron spin resonance measurements to demonstrate that spin relaxation is governed by the charges' hopping motion at low temperatures while Elliott-Yafet-like relaxation due to short-range, rapid spin density dynamics likely dominates high temperature spin lifetimes. Such a microscopic relaxation mechanism is highly sensitive to the local conformation of polymer backbones and we show its dependence on the degree of crystallinity in a polymer film.

by Zhu, Ming. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 73). / Abstracts in English and Chinese. / ABSTRATE (ENGLISH) --- p.I / ABSTRATE (CHINESE) --- p.III / ACKNOWLEDGEMENTS --- p.V / TABLE OF CONTENTS --- p.VI / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Introduction to organic semiconductors --- p.1 / Chapter 1.2 --- Charge transport in organic semiconductors --- p.1 / Chapter 1.2.1 --- Polaron models --- p.2 / Chapter 1.2.2 --- Scher-Montroll model --- p.2 / Chapter 1.2.3 --- Gaussian disorder model --- p.3 / Chapter 1.3 --- Organic semiconductors in this thesis --- p.5 / Chapter 1.4 --- Several key issues --- p.6 / References --- p.7 / Chapter 2. --- Experimental Techniques --- p.9 / Chapter 2.1 --- Materials Purification --- p.9 / Chapter 2.1.1 --- Motivation --- p.9 / Chapter 2.1.2 --- Basic principle --- p.9 / Chapter 2.1.3 --- Purification setup --- p.10 / Chapter 2.1.4 --- Parameters optimization --- p.11 / Chapter 2.2 --- Sample Fabrication --- p.11 / Chapter 2.2.1 --- Substrate treatment --- p.12 / Chapter 2.2.2 --- Thermal vacuum evaporation --- p.12 / Chapter 2.2.3 --- Spin coating --- p.12 / Chapter 2.3 --- Electrical measurement techniques --- p.13 / Chapter 2.3.1 --- J-V characteristics --- p.13 / Chapter 2.3.1.1 --- Injection versus bulk limited current --- p.13 / Chapter 2.3.1.2 --- Space Charge Limited Current --- p.15 / Chapter 2.3.1.3 --- Trap controlled Space Charge Limited Current --- p.15 / Chapter 2.3.2 --- Admittance spectroscopy --- p.17 / References --- p.20 / Chapter 3. --- Steady state J-V characteristics of organic thin films in sandwiched structures --- p.22 / Chapter 3.1 --- Experimental --- p.22 / Chapter 3.2 --- Results and discussions --- p.23 / Chapter 3.2.1 --- J-V characteristics of CuPc and TPD-PS thin films --- p.23 / Chapter 3.2.2 --- J-V characteristics of CuPc thin films with different cathodes --- p.26 / Chapter 3.2.3 --- Variable temperature J-V characteristics of CuPc thin films --- p.28 / References --- p.31 / Chapter 4. --- Dynamic Properties of Organic Semiconductors Performed by Admittance Spectroscopy --- p.32 / Chapter 4.1 --- Introduction to admittance spectroscopy --- p.32 / Chapter 4.2 --- Theoretical models --- p.32 / Chapter 4.3 --- Experimental --- p.36 / Chapter 4.3.1 --- Experimental scheme --- p.36 / Chapter 4.3.2 --- Sample preparation --- p.36 / Chapter 4.4 --- Results and discussion --- p.37 / Chapter 4.4.1 --- Unpurified CuPc --- p.37 / Chapter 4.4.2 --- Purified CuPc --- p.40 / Chapter 4.5 --- Conclusion --- p.43 / References --- p.44 / Chapter 5. --- Air-induced Trap Effect in Organic Semiconductors --- p.45 / Chapter 5.1 --- Introduction to negative capacitance phenomenon --- p.45 / Chapter 5.2 --- Experimental --- p.46 / Chapter 5.3 --- Results and discussion --- p.46 / Chapter 5.3.1 --- Admittance spectroscopy with different electrodes --- p.46 / Chapter 5.3.2 --- Admittance spectroscopy with different concentrations of oxygen --- p.48 / Chapter 5.3.3 --- Admittance spectroscopy with different humidities --- p.50 / Chapter 5.4 --- Conclusion --- p.53 / References --- p.56 / Chapter 6. --- N-type Doping of Magnesium to Zinc-Phthalocyanine (ZnPc) --- p.58 / Chapter 6.1 --- Introduction --- p.58 / Chapter 6.2 --- Experimental --- p.60 / Chapter 6.3 --- Results and discussion --- p.61 / Chapter 6.4 --- Conclusion --- p.66 / References: --- p.67 / Chapter 7. --- Summary and future work --- p.68 / Summary --- p.68 / Future work --- p.69 / References: --- p.72 / Appendix --- p.73

This thesis deals with the synthesis of new organicmaterials for electronic applications. Several new ring-formingmethods are employed to construct sulphur heterocycles: Tandemelectrophilic aromatic substitution and acid-catalyzedtransetherification of methoxythiophene, double electrophilicaromatic substitutions with ethane-1, 2-disulphenyl chloride,and also, the reaction of dienes with sulphur dichloride. Twonew condensed thiophenes have been incorporated in end-cappedoligothiophenes. An improvement of the synthesis of [3,2-b:2’, 3-d]thiophene is reported, with some attempts toincorporate it in oligomers. A synthesis of substitutednaphthalenes is also described. A new method of producingdisubstituted thiophenes from substituted butadienes anssulphur dichloride is employed in a new route to 3, 4-ethylenedioxythiophene, a very important monomer for conductingpolymers. Keywords :Organic Semiconductors, Thiophenes,Heterocyclic Synthesis, Dithienothiophene, Naphthalene,Ethylenedioxythiophene

<p>This thesis deals with the synthesis of new organicmaterials for electronic applications. Several new ring-formingmethods are employed to construct sulphur heterocycles: Tandemelectrophilic aromatic substitution and acid-catalyzedtransetherification of methoxythiophene, double electrophilicaromatic substitutions with ethane-1, 2-disulphenyl chloride,and also, the reaction of dienes with sulphur dichloride. Twonew condensed thiophenes have been incorporated in end-cappedoligothiophenes. An improvement of the synthesis of [3,2-b:2’, 3-d]thiophene is reported, with some attempts toincorporate it in oligomers. A synthesis of substitutednaphthalenes is also described. A new method of producingdisubstituted thiophenes from substituted butadienes anssulphur dichloride is employed in a new route to 3, 4-ethylenedioxythiophene, a very important monomer for conductingpolymers.</p><p><b>Keywords :</b>Organic Semiconductors, Thiophenes,Heterocyclic Synthesis, Dithienothiophene, Naphthalene,Ethylenedioxythiophene</p>

Includes bibliographical references (p. 54-56).