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In the present work, anatase and rutile titanium dioxide (TiO2) coated lustrous mica pigments were prepared by heterogeneous nucleation method. Anatase-rutile phase transformation of the TiO2 on mica substrate was achieved by coating very thin layers of tin (IV) oxide on mica surfaces prior to TiO2 deposition. Muscovite mica, which was used in the experiments was sieved, pre-treated with sodium bicarbonate and decantated before coating process. The surface morphology of mica titania pigments and anatase-rutile phase transformation were investigated by SEM and XRD analyse, respectively. Also, microwave-assisted synthesis of copper phthalocyanine and tetracarboxamide copper phthalocyanine pigments were carried out with phthalic anhydride and trimellitic anhydride precursors, respectively. Molecular structures of these pigments were confirmed by FT-IR and UV-visible spectroscopy analyse. Furthermore, combination pigments were obtained by the process of deposition of copper phthalocyanine pigments on mica-titania pigment substrate in dimethyl formamide solvent. FT-IR analysis and XRD analyse were performed to observe the transformations in the crystal forms of copper phthalocyanines on the substrate. The surface morphologies of copper phthalocyanines on the mica titania pigments were investigated by SEM analysis. Varying amounts of copper phthalocyanines were deposited on the mica surfaces, and nitrogen elemental analysis was performed to determine the amount of copper phthalocyanines. The resulting pigments were incorporated into alkyd based resin to prepare paint samples. L*a*b* values, gloss property, and hardness of the paint samples were determined by color measuring device, gloss meter and hardness measuring device, respectively. The resulting combination pigments obtained in this study showed improved luster, hue, and color intensity. Furthermore, in literature it was reported that these pigments have very high bleed resistance. This can be attributed to large macromolecular structure of copper phthalocyanine on the surface of mica titania pigment that prevents bleeding of the pigment from the paint. Moreover, the paint samples obtained from combination pigments showed higher hardness with respect to the paint sample of the mica titania pigment.

Vertically aligned nanowire arrays of copper phthalocyanine (CuPc) and CuPc-Al Schottky diodes, of controllable diameter and length were fabricated by cathodic electrodeposition of CuPc into anodized alumina (AAO) templates, followed by annealing at 300 ºC in Argon. AAO over Aluminum tape and that over ITO-glass were both used as starting templates for the device fabrication. Depending on the dimensions of the starting AAO template, diameters of CuPc nanowires ranged from 30 nm to 40 nm and the lengths ranged from 500 nm to 1 μm. The temperature dependence of the phase and the absorption spectrum of the nanowires are reported. The electrodeposited nanowires (as prepared) had the preferred crystallite orientation of the α-phase. ITO formed the ohmic contact and Schottky contacts were formed between CuPc and aluminum. Insertion of a thin layer of PEDOT:PSS between CuPc nanowires and the ITO electrode improved the contact and reduced the series resistance by an order of magnitude. Schottky diodes were characterized and analyzed at room temperature and at cryogenic temperatures.

<p> This thesis consists of two projects: alignment of copper phthalocyanine compounds on Au(111) and sidewall functionalization of single-walled carbon nanotubes on graphite. Both of these projects are performed with scanning tunneling microscopy (STM), which is used to study the structure of modified surfaces that are of interest in molecular electronics.</p> <p> In the first project, copper phthalocyanine compounds are made into a thin film with different methods, such as solution deposition, self-assembly and Langmuir-Blodgett film deposition. Those films are important materials in photoelectric devices such as organic light emitting diodes (OLED's). Molecules in these films are aligned on the solid surface with face-on orientation or edge-on orientation. However, the films of molecules with face-on orientation are preferentially used in LED's. In this project, we focus on finding a method to force molecules with face-on orientation in the film. The structure of copper octakisalkylthiophthalocyanine films on Au(111) was investigated with STM under ambient conditions. Columns of molecules are commonly observed due to the π-π interaction between molecules. The presence and length of alkyl chains in the molecules affects the alignment of molecules on the gold surface. The weak interaction between molecules and substrate caused the structure to be easily modified by an STM tip.</p> <p> In addition, chemical sidewall functionalization of SWCNTs was also explored with STM under ambient conditions. It was found that the spatial distribution of functional groups on nanotube sidewall is not random. Understanding the rules behind the distribution of functional groups will allow scientists to better control carbon nanotube functionalization and improve the properties of nanotubes. High resolution STM images provide direct evidence of the distribution and the effects of functional groups on nanotubes. Possible mechanisms are proposed to elucidate the process of SWCNT functionalization by free radicals and via the Bingel reaction.</p> / Thesis / Master of Science (MSc)

Organic solar cells (OSC) are interesting as low cost alternative to conventional solar cells. Unsubstituted Metal-phthalocyanines (Pc) are excellent electron donating molecules for heterojunction OSC. Usually organic solar cells with Pcs are produced by vapor deposition, although solution based deposition (like spin casting) is cheaper and offers more possibilities to control the structure of the film. With solution based deposition several parameters (like temperature, solvent and etc.) affect the self-organized structure formation via nucleation and growth. The reason why vapor deposition is typically used is the poor solubility of the metal-phthalocyanines in most common solvents. Furthermore the process of nucleation and growth of Pc aggregates from solution is not well understood. For preparation of Pc films from solution, it is necessary to find the appropriate solvents, assess the solution deposition techniques, such as dip coating, and spin casting. It is necessary to understand the nucleation and growth process for aggregation/precipitation and to use this knowledge to produce nanostructures appropriate for OSC. This is important because the nanostructure of the films determines their performance. In this thesis, optical absorption and the stability of 8 different unsubstituted metal Pc’s were studied quantitatively in 28 different solvents. Among the several solution based deposited thin films produced based on this study, copper phthalocyanine (CuPc) dissolved in trifluoroacetic acid (TFA) is chosen as a model system for an in-depth study. CuPc has sufficient solubility and stability in TFA and upon solution processing forms appropriate structures for OSCs. CuPc molecules aggregate into layers of nanoribbons with a thickness of ~ 1 nm and an adjustable width and length. The morphology and the number of deposited layers in the thin films are controlled by different parameters, like temperature and solution concentration. Material properties of CuPc deposited from TFA are studied in detail via x-ray diffraction, UV-Vis and FT-IR spectroscopy. Atomic force microscopy was used to study the morphology of the dried film. The mechanism of the formation of CuPc nanoribbons from spin casted CuPc/TFA solution in ambient temperature is investigated and explained. The parameters (e.g. solution concentration profile) governing nucleation and growth are calculated based on the spin casting theory of a binary mixture of a nonvolatile solute and evaporative solvent. Based on this and intermolecular interactions between CuPc and substrate a nucleation and growth model is developed explaining the aggregation of CuPc in a supersaturated TFA solution. Finally, a solution processed thin film of CuPc is applied as a donor layer in a functioning bilayer heterojunction OSC and the influence of the structure on OSC performance is studied. / In den vergangenen Jahren wurden kosteneffiziente nasschemische Beschichtungsverfahren für die Herstellung organischer Dünnfilme für verschiedene opto-elektronische Anwendungen entdeckt und weiterentwickelt. Unter anderem wurden Phthalocyanin-Moleküle in photoaktiven Schichten für die Herstellung von Solarzellen intensiv erforscht. Aufgrund der kleinen bzw. unbekannten Löslichkeit wurden Phthalocyanin-Schichten durch Aufdampfverfahren im Vakuum hergestellt. Des Weiteren wurde die Löslichkeit durch chemische Synthese erhöht, was aber die Eigenschaften von Pc beeinträchtigte. In dieser Arbeit wurde die Löslichkeit, optische Absorption und Stabilität von 8 verschiedenen unsubstituierten Metall-Phthalocyaninen in 28 verschiedenen Lösungsmitteln quantitativ gemessen. Wegen ausreichender Löslichkeit, Stabilität und Anwendbarkeit in organischen Solarzellen wurde Kupferphthalocyanin (CuPc) in Trifluoressigsäure (TFA) für weitere Untersuchungen ausgewählt. Durch die Rotationsbeschichtung von CuPc aus TFA Lösung wurde ein dünner Film aus der verdampfenden Lösung auf dem Substrat platziert. Nach dem Verdampfen des Lösungsmittels, die Nanobändern aus CuPc bedecken das Substrat. Die Nanobänder haben eine Dicke von etwa ~ 1 nm (typische Dimension eines CuPc-Molekül) und variierender Breite und Länge, je nach Menge des Materials. Solche Nanobändern können durch Rotationsbeschichtung oder auch durch andere Nassbeschichtungsverfahren, wie Tauchbeschichtung, erzeugt werden. Ähnliche Fibrillen-Strukturen entstehen durch Nassbeschichtung von anderen Metall-Phthalocyaninen, wie Eisen- und Magnesium-Phthalocyanin, aus TFA-Lösung sowie auf anderen Substraten, wie Glas oder Indium Zinnoxid. Materialeigenschaften von aufgebrachten CuPc aus TFA Lösung und CuPc in der Lösung wurden ausführlich mit Röntgenbeugung, Spektroskopie- und Mikroskopie Methoden untersucht. Es wird gezeigt, dass die Nanobänder nicht in der Lösung, sondern durch Verdampfen des Lösungsmittels und der Übersättigung der Lösung entstehen. Die Rasterkraftmikroskopie wurde dazu verwendet, um die Morphologie des getrockneten Films bei unterschiedlicher Konzentration zu studieren. Der Mechanismus der Entstehung der Nanobändern wurde im Detail studiert. Gemäß der Keimbildung und Wachstumstheorie wurde die Entstehung der CuPc Nanobänder aus einer übersättigt Lösung diskutiert. Die Form der Nanobändern wurde unter Berücksichtigung der Wechselwirkung zwischen den Molekülen und dem Substrat diskutiert. Die nassverarbeitete CuPc-Dünnschicht wurde als Donorschicht in organischen Doppelschicht Solarzellen mit C60-Molekül, als Akzeptor eingesetzt. Die Effizienz der Energieumwandlung einer solchen Zelle wurde entsprechend den Schichtdicken der CuPc Schicht untersucht.

This work focuses on the solar cell based on the heterostructure formed between Copper Phthalocyanine (CuPc) and Cadmium Sulfide (CdS). Two different fabrication techniques were used for depositing the organic and inorganic layers of CuPc and CdS layers respectively. CuPc was deposited by electrodeposition while CdS was deposited by chemical bath deposition. Hybrid CdS/CuPc thin films were obtained from CdS films grown on Glass/ITO by chemical bath deposition followed by electrodeposition of CuPc onto these films and annealing at 250˚C after the deposition of each layer. The maximum open circuit voltage (Voc) and the short circuit current density (Jsc) obtained for this heterojunction solar cell are 0.59v and 0.7mA/cm2 respectively and these are the highest values achieved in literature till date. The materials characteristics and electrical performances of the device were analyzed. The effect of increasing the thickness of CuPc and CdS on the short circuit current density and open circuit voltage were also investigated.

Dyes for inkjet printing are typically of the chromonic type. Chromonic mesophases have gained considerable attention as a well-defined group of lyotropic mesogens with different properties from conventional amphiphiles. While extensive research has been dedicated to the field of surfactant liquid crystals, structural and aggregation studies of chromonics have only emerged as a topic of interest within the last few years. The liquid crystalline structures in aqueous solutions of commercial Cu - phthalocyanine and black dyes have been examined using a combination of optical microscopy, UV-vis spectroscopy, nuclear magnetic resonance, wide- and small-angle X-ray diffraction and electronic paramagnetic resonance with a view to examining the phase behaviour of the chromonic mesophases formed over a broad range of concentrations and temperatures. These studies were performed in order to resolve outstanding problems concerning structural properties of these systems. Optical microscopy allowed us to identify the liquid crystalline phases and to construct the phase diagram. The observations show that both of these dyes form nematic mesophase above 15% wt / wt% dye. The small-angle diffraction data confirmed that the nematic phase for the black dye is maintained throughout the 16-25% composition range. A further increase in concentration leads to the formation of the hexagonal phase. The Cu – phthalocyanine dye also formed a nematic phase at low concentrations, with the aggregates undergoing a phase transition to an orientationally ordered chromonic liquid crystal phase at high dye concentration. These studies showed that this ordered phase possessed hexagonal symmetry. The wide-angle X-ray results demonstrated that aggregation involved π-π stacking of the molecules into columns. An additional reflection at ca. 6.8Å was observed for the black dye, which is believed to arise from “head – to – tail” packing of the molecules within the aggregates (a similar phenomenon observed in other azo dyes, e.g. Edicol Sunset Yellow).The densities of both dyes were measured over the studied range of concentrations. This enabled us to calculate the parameters of the aggregates within the hexagonal mesophase. A comparison between the area of the molecule and the cross-section of the aggregates showed that the aggregates of both dyes were the unimolecular stacks.

Thin Film Transistors (TFTs) are widely used in large area electronics because they offer the advantage of low cost fabrication and wide substrate choice. TFTs have been conventionally used for switching applications in large area display arrays. But when it comes to designing a sensor actuator system on a flexible substrate comprising entirely of organic and inorganic TFTs, there are two main challenges – i) Fabrication of complementary TFT devices is difficult ii) TFTs have a drift in their threshold voltage (VT) on application of gate bias. Also currently there are no circuit simulators in the market which account for the effect of VT drift with time in TFT circuits. The first part of this thesis focuses on integrating the VT shift model in the commercially available AIM-Spice circuit simulator. This provides a new and powerful tool that would predict the effect of VT shift on nodal voltages and currents in circuits and also on parameters like small signal gain, bandwidth, hysteresis etc. Since the existing amorphous silicon TFT models (level 11 and level 15) of AIM-Spice are copyright protected, the open source BSIM4V4 model for the purpose of demonstration is used. The simulator is discussed in detail and an algorithm for integration is provided which is then supported by the data from the simulation plots and experimental results for popular TFT configurations. The second part of the thesis illustrates the idea of using negative feedback achieved via contact resistance modulation to minimize the effect of VT shift in the drain current of the TFT. Analytical expressions are derived for the exact value of resistance needed to compensate for the VT shift entirely. Circuit to realize this resistance using TFTs is also provided. All these are experimentally verified using fabricated organic P-type Copper Phthalocyanine (CuPc) and inorganic N-type Tin doped Zinc Oxide (ZTO) TFTs. The third part of the thesis focuses on building a robust amplifier using these TFTs which has time invariant DC voltage level and small signal gain at the output. A differential amplifier using ZTO TFTs has been built and is shown to fit all these criteria. Ideas on vertical routing in an actual sensor actuator interface using this amplifier have also been discussed such that the whole system may be “tearable” in any contour. Such a sensor actuator interface can have varied applications including wrap around thermometers and X-ray machines.