This dissertation describes the study of organic thin-film solar cells in pursuit of affordable, renewable, and environmentally-friendly energy sources. Particular emphasis is given to the molecular ordering found in liquid crystalline or polycrystalline films as a way to leverage the efficiencies of these types of cells. Maximum efficiencies estimated based on excitonic character of organic solar cells show power conversion efficiencies larger than 10% are possible in principle. However, their performance is often limited due to small exciton diffusion lengths and poor transport properties which may be attributed to the amorphous nature of most organic semiconductors.Discotic liquid crystal (DLC) copper phthalocyanine was investigated as an easily processible building block for solar cells in which ordered molecular arrangements are enabled by a self-organization in its mesophases. An increase in photocurrent and a reduction in series resistance have been observed in a cell which underwent an annealing process. X-ray diffraction (XRD) and atomic force microscopy (AFM) measurements suggest that structural and morphological changes induced after the annealing process are related to these improvements.In an alternative approach, p-type pentacene thin films prepared by physical vapor deposition were incorporated into heterojunction solar cells with C60 as n-type layers. Power conversion efficiencies of 2.7 % under broadband illumination (350-900 nm) with a peak external quantum efficiency of 58 % have been achieved with the broad spectral coverage across the visible spectrum. Analysis using an exciton diffusion model shows this efficient carrier generation is mainly due to the large exciton diffusion length of pentacene films. Joint XRD and AFM studies reveal that the highly crystalline nature of pentacene films can account for the observed large exciton diffusion length. In addition, the electrical characteristics are studied as a function of light intensity using the equivalent circuit model used for inorganic pn-junction solar cells. Dependences of equivalent-circuit parameters on light intensity are further investigated using a modified equivalent circuit model, and their effects on the overall photovoltaic performance are discussed.

Proefschr. Rijksuniversiteit Groningen. / Met lit. opg.-Met bibl.-Met samenvatting in het Nederlands.

Thesis (Ph.D.)--York University, 2007. Graduate Programme in Physics and Astronomy. / Typescript. Includes bibliographical references (leaves 120-124). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:NR32065

Submitted by MAIZA DA SILVA OZÓRIO null (ozoriounesp@gmail.com) on 2018-02-26T15:23:33Z No. of bitstreams: 1 dissertação_maiza_versão_final_corrigida.pdf: 3955466 bytes, checksum: 08f98a38963076999f04ee08c2e89954 (MD5) / Approved for entry into archive by Claudia Adriana Spindola null (claudia@fct.unesp.br) on 2018-02-26T16:14:51Z (GMT) No. of bitstreams: 1 ozorio_ms_me_prud.pdf: 3955466 bytes, checksum: 08f98a38963076999f04ee08c2e89954 (MD5) / Made available in DSpace on 2018-02-26T16:14:51Z (GMT). No. of bitstreams: 1 ozorio_ms_me_prud.pdf: 3955466 bytes, checksum: 08f98a38963076999f04ee08c2e89954 (MD5) Previous issue date: 2016-06-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Um dos atuais desafios da eletrônica orgânica é a obtenção de semicondutores com alta mobilidade que forme filmes com boa morfologia quando depositado/impresso por solução, resultando em boa uniformidade e reprodutibilidade dos dispositivos. O poli(3- hexiltiofeno) (P3HT) e o 6,13-(triisopropilsililetinil)pentaceno (TP) estão entre os semicondutores orgânicos mais utilizados. O TP tem como característica a formação de estruturas cristalinas, e desse modo, apresenta mobilidade muito maior que o P3HT, no entanto é difícil de obter filmes com boa morfologia e resultados reprodutíveis. Visando um material semicondutor que apresente mobilidade significativamente melhor que a do P3HT e uma morfologia melhor que a do TP, estudou-se compósitos a partir da mistura destes materiais (P3HT:TP) para aplicação em transistores orgânicos de efeito de campo (OFETs), utilizando óxido de alumínio anodizado (Al2O3) tratado com HMDS como dielétrico de gate. Para análise da morfologia dos compósitos semicondutores de P3HT:TP usou-se microscopia eletrônica de varredura (MEV), microscopia de força atômica (AFM) e microscopia óptica (MO). Análise óptica foi feita através de medidas de fotoluminescência (PL) e de tempo de decaimento por fotoluminescência. Espectroscopia Raman e FTIR foram utilizadas para análises estruturais. No modo transistor a caracterização foi feita através de curvas de saída e transferência. Através das caracterizações elétricas determinou-se os parâmetros do semicondutor, tais como, mobilidade, voltagem limiar de chaveamento e razão entre o estado ligado e desligado. A morfologia da blenda semicondutora apresentou características específicas de cada material, ressaltando a formação de aglomerados. Observou-se diferenças bastantes consideráveis na morfologia do compósito em função da variação do solvente e da cinética de deposição dos filmes. Imagens de MEV mostram regiões cristalinas do TP dispersas na matriz polimérica do P3HT, onde o tamanho, forma e distribuição dos cristalitos dependem do tratamento dado à superfície do isolante. O aumento da concentração de TP dificulta a formação de compósitos com boas características. A melhor mobilidade foi obtida com o compósito 50P3HT:50TP, apresentando valores na ordem de 10- 3 cm2V -1 s -1 . / One of the current challenges of organic electronics is the development of semiconductors with high mobility to form films with good morphology when deposited/printed by solution, resulting in good uniformity and reproducibility of the devices. The poly (3-hexylthiophene) (P3HT) and 6,13-(triisopropilsililetinil)pentacene (TP) are among the most widely used organic semiconductors. The TP films are constituted by crystalline lamellar structures, and thus has greater mobility than the P3HT, however, it is difficult handling it to obtain films with good morphology and reproducible results. Targeting a semiconductor material with significantly better mobility than that of P3HT and better morphology than that of TP, we studied composites of these materials (P3HT: TP) for using in organic field effect transistors (OFETs). The transistor was prepared depositing the solution of the semiconductor composite, by spin coating, on the aluminium oxide, obtained by anodization and treated with HMDS, followed by the thermal evaporation of gold on the top, to form the drain and source electrodes. For analysis of the morphology of the composites semiconductors (P3HT: TP) was used scanning electron microscopy (SEM), atomic force microscopy (AFM) and optical microscopy (OM). Optical analysis was performed using photoluminescence (PL) measurements and decay time by photoluminescence. FTIR and Raman spectroscopy were used to structural analysis. In mode transistor, characterization was performed using output and transfer curves. Through the electrical characterizations determined the semiconductor parameters such as mobility, threshold-switching voltage and the ratio between the current in “on” and “off” states. The morphology of the semiconductor composite presented specific characteristics of each material, emphasizing the formation of agglomerates. It has been observed quite considerable differences in the morphology of the composite depending on the solvent and the variation of the film deposition kinetics. SEM images show crystalline regions TP dispersed in the polymeric matrix of P3HT, where the shape, size and distribution of crystallites depend on the treatment of the surface of the dielectric. The increase in TP concentration hinders the formation of composites with good characteristics. The best mobility was obtained with the composite 50P3HT: 50TP, with values in the order of 10- 3 cm2V -1 s -1 .

Benzannulation to porphyrin 2,3 positions has previously been accomplished using various methodologies in the past century, yet there remain limited methodologies to both annulate to the porphyrin periphery and add functional moieties that can then be derivatized for diverse applications. This dissertation describes the development of synthetic routes and characterization of a variety of linearly-annulated, functionalized, β,β'-π-extended porphyrins. There are five chapters in this dissertation, the first of which introduces synthesis and properties of porphyrins and π-extended porphyrins. Chapter 2 describes synthesis of pentacenequinone-fused and pentacene-fused poprhyrins with distinct and new optical absorbance properties. In chapter 3, synthesis and characterization of benzimidazole-fused porphyrins displaying external metal binding capability is described. The synthetic method developed in chapter 3 is extended in chapter 4 to synthesis of bisbenzimidazole-fused porphyrin dimers that show split Soret character, likely due to excitonic coupling between porphyrins of the dimer. Chapter 5 summarizes this dissertation and describes future directions that this dissertation provides foundation for.

This master´s thesis deals with possibilities of application of new organic molecular materials for electronic devices. Nowadays it is a very attractive field of research, because of the tendencies in industry to miniaturize, reduce production costs and develop new, eco-friendlier, processes of production. The theoretical part of the thesis provides a short overview of organic materials suitable for smart applications and thin films issues including their characterization. The experimental part is dedicated to means how to prepare thin-film electronic components to silicon wafers for thin films field effect transistors. The obtained results in the last part of thesis are discussed about properties of prepared thin films, in the concrete about the electrical transport properties, in the connection with the condition of preparation.

In chapter I Photo-retro-Diels-Alder (PrDA) reactions of a variety of Diels Alder (DA) adducts were studied. Experimental results showed that the photoreactivity (quantum yield) depends on the electron-donating ability of the diene component and the electronwithdrawing ability of the dienophile component. The mechanism was studied by trapping the reaction intermediate, O2 quenching and femtosecond time-resolved absorption spectroscopy. All the results support a mechanism that involves a charge-separated intermediate generated from a singlet excited state. The PrDA reaction may find applications in photoresponsive materials, photolithography, drug delivery and mechanistic research. Chapter II shows two applications of the PrDA reaction. The first, being the formation of the 2 nd -ring DA adduct together with the central-ring adduct in a reaction of pentacene and tetracyanoethylene (TCNE) at room temperature. DFT calculations showed that the difference between the free energy of the two isomers is about 3.9 kcal/mol. Photo- and thermally induced isomerization between the central-ring adduct and the 2nd -ring adduct were studied in solutions and in polymer films. In solution, the less stable 2nd -ring adduct can be completely converted to the more stable central-ring adduct either thermally or photochemically, but the reverse transformation does not occur. In a polymer matrix, isomerization can be photochemically induced in both directions at different wavelengths, which results in a photoswitchable system. Formation of pentacene in the photochemical experiments was also observed, which supports an isomerization process involving a photoretro-Diels Alder (PrDA) reaction. iv The second application was the design and synthesis of a polymer with an anthracene diketone moeity which could undergo a PrDA reaction which should result in significant conductivity changes. Although the synthesis of this type of polymer was unsuccessful during this study, we still believe in the theoretical soundness of the synthesis and utility of this type of polymer. Chapter IV undertakes the study of a class of photoacids which are based on a merocyanine core. These photoacids have been studied and characterized using UV-Vis spectroscopy and the pH of two photoacids have been shown to decrease by 2.0 units upon irradiation with blue light. In addition, the relaxation times of these photoacids have been studied in water and ethanol. We have taken one step further and synthesized and characterized three polymers which have a photoacid moeity in them. These polymers respond to visible light reversibly in solution and in solid state.

No description available.

No description available.

Heterogeneous reactions between gas-phase oxidants and particulate-phase organic compounds impact many important atmospheric chemical processes. For example, little is known about the reaction dynamics of gaseous oxidants with organic compounds found in the atmosphere. The first step of the reaction between gaseous ozone and solid pentacene was investigated using Reflection Absorption Infrared Spectroscopy (RAIRS). Ozone was found to add to pentacene non-selectively and form a range of products after heavy ozone exposure. The rate limiting step had an activation energy of 17 kJ/mol, which is consistent with the findings of previous ozone oxidation studies for the cleavage of a carbon-carbon double bond. Unfortunately the products could not be used to distinguish between probable reaction mechanisms. Hydroxyl radicals (•OH) play a major role processing atmospheric hydrocarbons. Due to their short lifetimes, not much is known about the dynamics of the first steps of •OH reactions. To investigate these reactions, a rotational state-selector was constructed to filter a molecular beam of •OH for reaction dynamics investigations with organic surfaces. The rotational state-selector was designed to leverage the linear Stark effect to pass only suitable molecules in a particular rotational state and block the flow of any other atoms, molecules and ions in a molecular beam. The state-selector was validated and used to positively deflect molecular beams of methyl iodide and D₂O via the linear Stark effect. Future studies with the rotational state-selector will investigate the initial steps of •OH reactions with solid organic compounds. / Master of Science