Various synthetic methods have been developed to produce metal nanostructures including copper and iron nanostructures. Modification of nanoparticle surface to enhance their characteristic properties through surface functionalization with organic ligands ranging from small molecules to polymeric materials including organic semiconducting polymers is a key interest in nanoscience. However, most of the synthetic methods developed in the past depend widely on non-aqueous solvents, toxic reducing agents, and high temperature and high-pressure conditions. Therefore, to produce metal nanostructures and their nanocomposites with a simpler and greener method is indeed necessary and desirable for their nano-scale applications. Hence the objective of this thesis work is to develop an environmentally friendly synthesis method to make welldefined copper and iron nanostructures on a large-scale. The size and shape-dependent optical properties, solid-state crystal packing, and morphologies of nanostructures have been evaluated with respect to various experimental parameters. Nanostructures of copper and iron were prepared by developing an aqueous phase chemical reduction method from copper(II) chloride and Fe(III) chloride hexahydrate upon reduction using a mild reducing agent, sodium borohydride, under an inert atmosphere at room temperature. Well-defined copper nanocubes with an average edge length of 100±35 nm and iron nanochains with an average chain length up to 1.70 μm were prepared. The effect of the molar ratios of each precursor to the reducing agent, reaction time, and addition rate of the reducing agent were also evaluated in order to develop an optimized synthesis method for synthesis of these nanostructures. UV-visible spectral traces and X-ray powder diffraction traces were obtained to confirm the successful preparation of both nanostructrues. The synthesis method developed here was further modified to make poly(3-hexylthiophene) coated iron nanocomposites by surface functionalization with poly(3-hexylthiophene) carboxylate anion. Since these nanostructrues and nanocomposites have the ability to disperse in both aqueous-based solvents and organic solvents, the synthesis method provides opportunities to apply these metal nanostructures on a variety of surfaces using solution based fabrication techniques such as spin coating and spray coating methods.

elementares da eletrônica orgânica, vêm sendo desenvolvidos e integrados para realização de dispositivos eletrônicos de baixo custo, alto volume e flexíveis. Nesta tese foi proposta uma tecnologia para a construção de OFETs sobre substrato flexível e a caracterização destes dispositivos foi feita. Transistores com diferentes comprimentos de canal (L= 5, 10, 20 e 40 μm) foram construídos e avaliados. As características e configuração do poli (álcool vinílico) (PVA) como dielétrico de porta foram definidas através da otimização da reticulação, grau de hidrólise e peso molecular. O PVA utilizado como dielétrico de porta foi de alto peso molecular, hidrolização incompleta e reticulado com dicromato de amônia. O desafio de compatibilização entre os filmes de PVA e poli (3-hexiltiofeno) (P3HT) com diferentes polaridades foi superado e abriu caminho para construção de OFETs e capacitores, estes últimos usados para extrair a capacitância por unidade de área do conjunto PVA-P3HT. Os processos desenvolvidos de fotolitografia e de oxidação por plasma de oxigênio possibilitaram a construção de transistores flexíveis inéditos de Ni-P3HT-PVA-Al com uma arquitetura top-gate, bottom-contacts. Os transistores apresentaram boas características de saída, baixa tensão de operação (< |-6 V|), boa mobilidade (0,015 cm2/V*s) e razões ION/IOFF aceitáveis (~300). A resistência de contato e mobilidade efetiva foram obtidas através do método de linhas de transmissão. Uma boa estabilidade temporal foi atingida, porém ocorreram instabilidades na operação quando os transistores foram testados. A corrente do transistor não se manteve estável, primeiramente aumentou e depois diminuiu com a realização de sucessivas medidas. As razões deste comportamento foram discutidas. Inversores foram demonstrados e caracterizados. O aperfeiçoamento da tecnologia desenvolvida possibilitará a construção de circuitos orgânicos analógicos e digitais para aplicações cotidianas que demandem baixo custo e alto volume. / Organic field effect transistors (OFETs), the elementary components of organic electronics, are constantly developed and integrated to realize low cost, high volume, flexible electronic devices. In this thesis a technology for creating OFETs on flexible substrates is proposed and their characterization is performed. Flexible transistors with different channel lengths (L= 5, 10, 20 and 40 μm) were built and evaluated. The characteristics and configurations of the poly (vinyl alcohol) (PVA) as gate dielectric were defined through the optimization of crosslinking, the degree of hydrolysis and the molecular weight. The chosen PVA is cross-linked with ammonium dichromate, has a high molecular weight and incomplete hydrolization. The challenge of integrating polymers of different polarities: PVA and poly (3-hexyl thiophene) (P3HT), the chosen organic semiconductor, was overcome and opened a path to the construction of OFETs and capacitors. From the later capacitance per unit area was extracted. The developed processes of photolithography and oxygen plasma etching allowed the construction of unprecedented Ni-P3HT-PVA-Al flexible top-gate, bottomcontacts transistors. The transistors showed good output characteristics, low operation voltages (< |-6 V|), acceptable carrier mobilities (0,015 cm2/V*s) and ION/IOFF fractions (~300). Contact resistance and effective mobility were extracted through transmission line method. The transistors showed great temporal stability, but when operated instabilities occurred. The transistor output current first increased and later degraded with successive testing. Organic PMIS inverters were demonstrated and characterized. The optimization of this technology may lead to construction of flexible logic organic devices for everyday applications.

The presented study investigated the Induced Density of Interface States (IDIS) model at different polymer interfaces by using photoemission spectroscopy in combination with electrospray deposition. In recent years, organic electronics have attracted considerable attention due to their advantages of low-cost and easy-fabrication. The performance of such devices crucially depends on the energy barrier that controls the interface charge transfer. A significant effort has been made to explore the mechanisms that determine the direction and magnitude of charge transfer barriers in these devices. As a result of this effort, the IDIS model was developed to predict the energy alignment at metal/organic and organic/organic interfaces. The validity of the IDIS model on molecular interfaces was confirmed by the results of a series of experiments with small molecular materials, which are in good agreement with the theoretical calculations from the IDIS model. The charge neutrality level (CNL) and screening factor for various organic materials can be determined from the linear correlation between the hole injection barrier at metal/organic interface and the work function of its corresponding metal substrate, which stands as one of the most important features of the IDIS model. The study presented here explores whether the IDIS model is also valid for polymer interfaces. Two prototypical polymer materials: poly(3-hexylthiophene) (P3HT) and poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) were selected for the investigation. In the first part of this study, a series of metal/polymer interfaces were prepared using electrospray and investigated with photoemission spectroscopy. The linear relationship between the hole barriers extracted from the metal/polymer interface and the work function of its respective metal substrate suggests that the IDIS model is also valid for metal/polymer interfaces. The CNLs and the screening factors of P3HT and MEH-PPV are determined respectively. The experiment results are also discussed with regard to the Integer Charge Transfer (ICT) model. The comparison between the two models suggests that the IDIS model should be applied to interfaces prepared in vacuum while the ICT model works on interfaces with an ambient contamination layer present. The second part of the dissertation discusses the photoemission results of the MEH-PPV/P3HT heterojunction from the perspectives of the two models. The results indicate that the IDIS model is valid for polymer/polymer heterojunctions. The IDIS model more accurately predicted the measured orbital line up by using its principles for organic/organic heterojunction than the ICT model.

Conjugated polymers represent the next generation of conducting materials that will enable technological devices incorporating thin film transistors, photovoltaic cells etc., in a cost-effective roll-to-roll manner. Given the importance of microstructure on charge transport, ordered self-assembly in polymeric semiconductors assumes paramount relevance. This thesis thus focuses on a fundamental investigation of the correlations between the morphology and microstructure of the first high mobility solution processable semiconducting polymer, poly(3-hexylthiophene)(P3HT), and its corresponding charge transport properties. The evolution of polymer chain conformations is first studied, leading up to the formation of the conducting channel. An intermediate lyotropic liquid crystalline phase is identified, characterized by anisotropic ordering of the polymer chains. Methods for tuning the microstructure of P3HT thin films are also discussed, with an emphasis on understanding the role of molecular parameters, such as regioregularity and process parameters such as the film formation method. An ultrasound based technique for inducing the formation of ordered π-stacked molecular aggregates is also introduced. The results presented here not only provide understanding of microstructure-charge transport correlations, but also the very process of film formation in solution processable organic semiconductors, which could in turn hold the key to approaching the mobility benchmark represented by single crystals.

Ce travail est consacré à la synthèse de dérivés du polythiophène de faibles gaps conservant des potentiels d'oxydation élevés. Des thiophènes disubstitués et des bithiophènes « Donneur-Accepteur » ont été synthétisés puis polymérisés. Les chaines latérales de ces polymères, groupements donneurs ou attracteurs, ont été modifiées afin de moduler les propriétés optiques et électrochimiques du matériau. Ces polymères ont également été testés en mélange avec le PCBM en cellules photovoltaïques en réseaux interpénétrés. Les Voc délivrées par les dispositifs ont montré une dépendance linéaire en fonction du potentiel d'oxydation des polymères atteignant des valeurs de 0,8 V avec les copolymères à base de cyanothiophène et d'alkyl- ou alkoxythiophène. Malgré des rendements de 1 %, ces performances restent inférieures à celle du P3HT. Des optimisations en termes de morphologie sont certainement nécessaires. <br />En effet, la morphologie des couches actives joue un rôle primordial dans l'obtention de hauts rendements de conversion. Une technique originale de structuration du polymère à l'échelle nanométrique a été développée conduisant à l'élaboration de fibrilles de P3HT. Ces nanostructures, présentant un degré d'ordre important, se forment spontanément en solution. Leur taux par rapport au matériau amorphe est parfaitement contrôlable et ajustable en solution et sous forme de film. Les mesures de mobilités montrent une forte amélioration du transport de charge au sein de ces couches fibrillaires par rapport à un film classique de P3HT obtenu sans recuit. Des rendements de conversion photovoltaïque de 3,6 % sur verre et 3,3 % sur plastique ont été atteints sans recuit.

P3HT (Poly(3-hexylthiophene)) is an organic polymer that shows promise as an active material in semiconducting electronics. It is important to study the electronic properties of this material in order to determine its efficacy in such devices. However, many current studies of thiophene only examine the oligomer, since it is a simpler material to investigate. In this study, several P3HT interfaces were analyzed to determine their electronic properties. The P3HT was deposited on Au, highly-ordered pyrolitic graphite (HOPG), and indium tin oxide (ITO) substrates via electrospray deposition. The depositions were performed in several steps, with x-ray photoemission spectroscopy (XPS) and ultraviolet photoemission spectroscopy (UPS) measurements taken between each step without breaking the vacuum. The resulting series of spectra allowed orbital line-up diagrams to be generated for each interface, giving detailed analysis of the interfacial properties, including the charge injection barriers and interface dipoles. The results, when compared to similar oligomer-based investigations, show a difference in the orbital line-up between oligomeric and polymeric P3HT junctions.

Developing a fundamental understanding of photocurrent generation processes at organic-inorganic interfaces is critical for improving hybrid solar cell efficiency and stability. This dissertation explores processes at these interfaces by combining data from photovoltaic device performance tests with characterization experiments conducted directly on the device. The dissertation initially focuses on exploring how morphologically and chemically modifying the organic-inorganic interface, between poly(3-hexylthiophene) (P3HT) as the electron donating light absorbing polymer and titanium dioxide (TiO₂) as the electron acceptor, can result in stable and efficient hybrid solar cells. Given the heterogeneity which exists within bulk heterojunction devices, stable interfacial prototypes with well-defined interfaces between bilayers of TiO₂ and P3HT were developed, which demonstrate tunable efficiencies ranging from 0.01 to 1.6 %. Stability of these devices was improved by using Cu-based hole collecting electrodes. Efficiency values were tailored by changing TiO₂ morphology and by introducing sulfide layers like antimony trisulfide (Sb₂S₃) at the P3HT-TiO₂ interface. The simple bilayer device design developed in this dissertation provides an opportunity to study the precise role played by nanostructured TiO₂ surfaces and interfacial modifiers using a host of characterization techniques directly on a working device. Examples introduced in this dissertation include X-ray photoelectron spectroscopy (XPS) depth profiling analysis of metal-P3HT and P3HT-TiO₂ interfaces and Raman analysis of bonding between interface modifiers like Sb₂S₃ and P3HT. The incompatibility of TiO₂ with P3HT was significantly reduced by using P3HT derivatives with -COOH moieties at the extremity of a polymer chain. The role of functional groups like -COOH in interfacial charge separation phenomena was studied by comparing the photovoltaic behavior of these devices with those based on pristine P3HT. Finally, for hybrid solar cells discussed in this dissertation to become commercially viable, high temperature processing steps of the inorganic TiO₂ layer must be avoided. Accordingly, this dissertation demonstrates the novel use of electromagnetic radiation in the form of microwaves to catalyze growth of anatase TiO₂ thin films at temperatures as low as 150 °C, which is significantly lower than that used in conventional techniques. This low temperature process can be adapted to a variety of substrates and can produce patterned films. Accordingly, the ability to fabricate TiO₂ thin films by the microwave process at low temperatures is anticipated to have a significant impact in processing devices based on plastics. / text

A novel UHV microcalorimeter has been used to study the interaction between calcium and three polymers: MEH-PPV, MEH-PPP and P3HT. All three polymers behave differently in their reaction kinetics with calcium. On MEH-PPV we measure 45 μJ/cm² of heat generated in excess of the heat of bulk metal growth, 120 μJ/cm² for MEH-PPP, and 100 μJ/cm² for P3HT. Comparison of the MEH-PPV and MEHPPP data indicate that the initial reaction of calcium with MEH-PPV occurs at the vinylene group. We propose, based on hypothetical models, that calcium reacts with the vinylene groups of MEH-PPV with a reaction heat of 360 kJ/mol and at a projected surface density of 1.7 sites/nm², while it reacts with the phenylene groups of MEH-PPP in a two-step process with reaction heats of 200 and 360 kJ/mol respectively, at a projected surface density of 3.5 sites/nm². Optical absorption experiments, using either a 1.85 eV diode laser or a xenon lamp coupled to a scanning monochromator, have also been performed using the same calorimeter sensor. In the case of MEH-PPV, using the laser we find an optical absorption cross-section of 3E-¹⁷ cm² per incident calcium atom at low coverages. The change in absorptance at higher coverages correlates perfectly with the population of reacted Ca atoms determined calorimetrically. The size of the absorbance cross-section, and its position just within the band gap of the polymer, are consistent with the reaction being one of polaron formation. Calcium does not appear to dope P3HT, while the photon energy range of 1.5 to 3.75 eV used in these experiments is likely too small for probing polaronic energy states in MEH-PPP.

A novel UHV microcalorimeter has been used to study the interaction between calcium and three polymers: MEH-PPV, MEH-PPP and P3HT. All three polymers behave differently in their reaction kinetics with calcium. On MEH-PPV we measure 45 μJ/cm² of heat generated in excess of the heat of bulk metal growth, 120 μJ/cm² for MEH-PPP, and 100 μJ/cm² for P3HT. Comparison of the MEH-PPV and MEHPPP data indicate that the initial reaction of calcium with MEH-PPV occurs at the vinylene group. We propose, based on hypothetical models, that calcium reacts with the vinylene groups of MEH-PPV with a reaction heat of 360 kJ/mol and at a projected surface density of 1.7 sites/nm², while it reacts with the phenylene groups of MEH-PPP in a two-step process with reaction heats of 200 and 360 kJ/mol respectively, at a projected surface density of 3.5 sites/nm². Optical absorption experiments, using either a 1.85 eV diode laser or a xenon lamp coupled to a scanning monochromator, have also been performed using the same calorimeter sensor. In the case of MEH-PPV, using the laser we find an optical absorption cross-section of 3E-¹⁷ cm² per incident calcium atom at low coverages. The change in absorptance at higher coverages correlates perfectly with the population of reacted Ca atoms determined calorimetrically. The size of the absorbance cross-section, and its position just within the band gap of the polymer, are consistent with the reaction being one of polaron formation. Calcium does not appear to dope P3HT, while the photon energy range of 1.5 to 3.75 eV used in these experiments is likely too small for probing polaronic energy states in MEH-PPP.

Cette thèse présente un travail exploratoire sur des cellules solaires hybrides, basées sur un matériau inorganique (le silicium) et un polymère (le P3HT). Cette structure a été imaginée pour améliorer les cellules à bas coûts à base de matériaux organiques. Nous démontrons ici sa faisabilité expérimentale et analysons son fonctionnement. L'hétérojonction entre le silicium et le P3HT a été étudiée sur des dispositifs en bicouches planes. Nous montrons qu'elle fournit de l'énergie électrique et que les deux matériaux peuvent contribuer au photocourant. Des rendements de 1,6 % ont été obtenus. Un effort constant a été fait pour simplifier et fiabiliser les procédés de fabrication. Deux nouveaux types de silicium nano-structuré ont été développés. Des ``nano-éponges'', dont la taille typique des pores est de 20 nm, ont été obtenues à l'aide de catalyseurs métalliques par dépôts assistés par plasma à 175 °C. Des nanofils de silicium ont été formés par un procédé inédit : les substrats sont des oxydes transparents conducteurs, les catalyseurs sont générés in situ et la température de croissance est inférieure à 300 °C. La phase würtzite a été mise en évidence dans certains fils, et divers modes de croissance ont été observés. Ces deux nouveaux types de couches minces pourront aussi être utilisées dans des cellules solaires inorganiques.