Zinc oxide, with its direct wide bandgap and high exciton binding energy, is a promising material for optoelectronic devices. Quantum confinement effect and high surface to volume ratio of the nanowires imparts unique properties to them and makes them appealing for researchers. So far, zinc oxide nanowires have been used to fabricate various optoelectronic devices such as light emitting diodes, solar cells, sensors and photodetectors. To fabricate those optoelectronic devices, many different synthesis methods such as metal organic chemical vapor deposition, chemical vapor deposition, pulsed laser deposition, electrodeposition and hydrothermal method have been explored. Among them, hydrothermal method is the most feasible one in terms of simplicity and low cost. In this thesis, hydrothermal method was chosen to synthesize zinc oxide nanowires. Synthesized zinc oxide nanowires were then used as electrically active components in light emitting diodes and ultraviolet photodetectors. Hybrid light emitting diodes, composed of inorganic/organic hybrids are appealing due to their flexibility, lightweight nature and low cost production methods. Beside the zinc oxide nanowires, complementary poly [2- methoxy -5- (2- ethylhexyloxy) - 1,4 -phenylenevinylene] MEH-PPV and poly (9,9-di-n-octylfluorenyl-2,7-diyl) (PFO) hole conducting polymers were used to fabricate hybrid light emitting diodes in this work. Optoelectronic properties of the fabricated light emitting diodes were investigated. Zinc oxide emits light within a wide range in the visible region due to its near band edge and deep level emissions. Utilizing this property, violet-white light emitting diodes were fabricated and characterized. Moreover, to take advantage over the responsivity of zinc oxide to ultraviolet light, ultraviolet photodetectors utilizing hydrothermally grown zinc oxide nanowires were fabricated. Single walled carbon nanotube (SWNT) thin films were used as transparent electrodes for the photodetectors. Optoelectronic properties of the transparent and flexible devices were investigated. A high on-off current ratio around 260000 and low decay time about 16 seconds were obtained. Results obtained in this thesis reveal the great potential of the use of solution grown zinc oxide nanowires in various optoelectronic devices that are flexible and transparent.

This dissertation describes a novel methodology to prepare, functionalize, and assemble polymer-coated ferromagnetic cobalt nanoparticles (PS-CoNPs) and cobalt oxide nanowires. This research demonstrated the ability to use dipolar nanoparticles as `colloidal monomers' to form electroactive 1-D mesostructures via self- and field-induced assembly. The central focus of this dissertation is in developing a novel methodology termed as `Colloidal Polymerization', in the synthesis of well-defined cobalt oxide nanowires as nanostructured electrode materials for potential applications in energy storage and conversion.Ferromagnetic nanoparticles are versatile building blocks due to their inherent spin dipole, which drive 1-D self-assembly of colloids. However, the preparation and utilization of ferromagnetic nanoparticles have not been extensively examined due to the synthetic challenges in preparing well-defined materials that can be easily handled. This dissertation has overcome these challenges through the hybridization of polymeric surfactants with an inorganic colloid to impart functionality, colloidal stability and improved processing characteristics. This modular synthetic approach was further simplified to prepare ferromagnetic nanoparticles in gram scale, which enabled further investigations to develop new chemistry and materials science with these materials. These polymer-coated magnetic nanoparticles self-assembled into extended linear chains due to strong dipolar attractions between colloids. Additionally, novel dipolar assemblies, such as, flux-closure nanorings and lamellae type mesostructures were demonstrated by controlling the interparticle of attractive forces (dipolar versus van der Waals).The research presented herein focused on utilizing polymer-coated ferromagnetic cobalt nanoparticles as `colloidal molecules' to form interconnected 1-D mesostructures via `Colloidal Polymerization'. This process exploited the magnetic organization of dipolar colloids into 1-D mesostructures followed by a facile oxidation reaction to form interconnected electroactive cobalt oxide nanowires. This facile and template free approach enabled the large scale synthesis of semiconductor cobalt oxide nanowires, in which the electronic and electrochemical properties were confirmed for potential applications for energy storage and conversion. This work served as a platform in fabricating a wide range of semiconductor heterostructures, which allowed for structure-property investigation of new nanostructured electrodes.

A new class of electrodes with nanometer-scale contact spacing can be produced at the edge of patterned metal/insulator/metal this film structures. A key challenge is to produce insulator layers with low leakage current and have pristine metal contacts for controlled molecular contacts. Atomic layer deposition of high quality Al2O3 thin films onto Au electrodes was enabled by surface modification with a self-assembled monolayer of -OH groups that react with a monolayer of trimethylaluminum gas source. Ar ion milling was then used to expose the edge of the Au/dielectric/Au structure for molecular electrode contacts. The junctions are characterized by atomic force microscope and tunnel current properties. The Au/self-assembled monolayer/Al2O3/Au tunnel junction, with a very thin oxide insulator layer (15.4 Å), is stable and has a small tunneling current density of about 0.20 ~ 0.75 A/cm2 at 0.5 V. Organometalic cluster molecules were attached to bridge the electrodes. Through tunnel current modeling, low temperature and photo current measurements, molecular current was found to be consistent with direct tunneling through the organic tethers to available states at the metal center. This novel electrode was also used to study the efficiency of organic conducting thin films where the photovoltaic efficiency can be improved when the electrode separation distance is below the exciton diffusion length. Copper (II) phthalocyanine (CuPc) was thermally evaporated between the nano-gap electrodes formed by Au/Al2O3/Au tunnel junctions. A large photocurrent enhancement over 50 times that of bulk CuPc film was observed when the electrode gap distance approached 10 nm. CuPc diffusion length is seen to be 10 nm consistent with literature reports. All devices show diode I-V properties due to a large Schottky barrier contact resistance between the small top Au electrode and the CuPc film. To add another dimension of nm-scale patterning, nanowires can be used as line-of-sight shadowmasks provided that nanowire location and diameter can be controlled. Lateral ZnO nanowires were selectively grown from the edge of a Si/Al2O3/Si multi-layer structure for potential integration into devices utilizing Si processing technology. Microstructural studies demonstrate a 2-step growth process in which the tip region, with a diameter ~ 10 nm, rapidly grew from the Al2O3 surface. Later a base growth with a diameter ~ 22 nm overgrew the existing narrow ZnO nanowire halting further tip growth. Kinetics studies showed surface diffusion on the alumina seed surface determined ZnO nanowire growth rate.

Nanofios semicondutores de óxido metálico apresentam enorme potencial em aplicações de nano-sensoriamento de diferentes gases e substâncias químicas e biológicas, bem como na aplicação a detectores UV-visível. Neste trabalho, desenvolvemos e aperfeiçoamos a síntese de nanofios de ZnO em substratos de safira (001), silício (111) e silício (100) sob diferentes concentrações de oxigênio usando o processo de transporte de vapor-liquido-sólido (VLS). No presente trabalho, investigamos a influência da concentração de oxigênio no crescimento de nanofios de ZnO por Espectroscopia de Fotoluminescência a temperatura variável com a finalidade de estudo da mudança na concentração de defeitos. Apresentamos, ainda, caracterizações elétricas (IxV e Ixt) de nanoestruturas de ZnO sob diferentes pressões com o objetivo de estudar os defeitos envolvidos nos processos de transportes eletrônicos. Por último, propomos o desenvolvimento de micro-contatos através da técnica de microfeixe iônico e através de nanolitografia por feixe de elétrons com a finalidade de aplicações a sensores químicos, gasosos e fotodetectores. / Metal oxide nanowires semiconductors have enormous potential in high-sensitive, fast and selective sensing applications. It may be used to selectively detect different gases, chemical and biological substances and also in UV-visible photodetectors. The described processes involve the synthesis as well as the characterization of ZnO nanowires grown on sapphire (001), silicon (100) e silicon (111) substrates by the Vapor-liquid-solid transport method. In the present work, we describe the influence of oxygen concentration introduced in the growth step measured by photoluminescence at variable temperature to demonstrate the change in defect levels emission (DLE). Furthermore, we have shown electrical characterization (IxV and Ixt) in order to study the ambient effect for transport mechanisms in ZnO nanowires. We also report the development of crucial steps in the fabrication for an upcoming ZnO nanowire sensor device (gas, chemical and photodetector) using lithography techniques such as ion micro-beam and electron beam with the purpose of fabricating metallic micro-pads.

Neste trabalho se realiza a síntese e caracterização de nanofios de óxido de zinco. Adicionalmente se apresenta o processo de montagem de um dispositivo para medidas elétricas deste material. Estuda-se complementarmente o efeito do tratamento de plasma sobre as propriedades de fotoluminescência do material. Nanofios foram sintetizados pelo mecanismo vapor-líquido-sólido (VLS), utilizando ouro como catalizador e safira c-plane como substrato. As amostras foram caracterizadas utilizando microscopia eletrônica de varredura, fotoluminescência a temperatura ambiente, difração de raios X, e microscopia eletrônica de transmissão. Os nanofios obtidos têm seção transversal com formato quase hexagonal, e larguras de aproximadamente 46 nm. O comprimento deles varia de 3 a 10 μm. Os resultados de difração de raios x e microscopia eletrônica de transmissão mostram que eles são monocristalinos com rede cristalina tipo wurtzita, e com direção de crescimento no eixo c. Foram estudados os efeitos da potência de plasma de oxigênio (O2) na fotoluminescência dos nanofios a temperatura ambiente. A diferença na fotoluminescência após diferentes tratamentos de plasma de O2 mostra que a razão entre a emissão da região do band gap e da banda do visível pode ser modificada pelo tratamento. Este efeito corrobora com a hipótese de que a banda verde de luminescência está relacionada às vacâncias de zinco. A variação percentual da razão entre as duas regiões apresenta uma dependência linear com a potência do plasma. / In this work, we performed the synthesis and characterization of zinc oxide nanowires. We also report an assembly process to measure the electrical properties of this material. We study the plasma treatment effect on the photoluminescence spectra of the nanowires. Nanowires were synthesized via vapor-liquid-solid mechanism, using gold as catalyst and c-plane sapphire as substrate. The samples were characterized using scanning electron microscopy, room temperature photoluminescence, x-rays diffraction and transmission electron microscopy. Our nanowires show a quasi-hexagonal cross section, with diameters of approximately 46 nm. Their lengths ranged from 3 to 10 μm. Our results show monocrystalline wurtzite crystal nanowires with c growth direction. We also study the plasma power effect of oxygen (O2) plasma treatment on the room temperature photoluminescence spectra of the nanowires. Our results show that the deep level emission to near band emission ratio decreases with the plasma treatment. This effect supports the hypothesis that claims the green band luminescence is related to the oxygen vacancies. Furthermore, the relative ratio change depends linearly on the plasma power.

Neste trabalho se realiza a síntese e caracterização de nanofios de óxido de zinco. Adicionalmente se apresenta o processo de montagem de um dispositivo para medidas elétricas deste material. Estuda-se complementarmente o efeito do tratamento de plasma sobre as propriedades de fotoluminescência do material. Nanofios foram sintetizados pelo mecanismo vapor-líquido-sólido (VLS), utilizando ouro como catalizador e safira c-plane como substrato. As amostras foram caracterizadas utilizando microscopia eletrônica de varredura, fotoluminescência a temperatura ambiente, difração de raios X, e microscopia eletrônica de transmissão. Os nanofios obtidos têm seção transversal com formato quase hexagonal, e larguras de aproximadamente 46 nm. O comprimento deles varia de 3 a 10 μm. Os resultados de difração de raios x e microscopia eletrônica de transmissão mostram que eles são monocristalinos com rede cristalina tipo wurtzita, e com direção de crescimento no eixo c. Foram estudados os efeitos da potência de plasma de oxigênio (O2) na fotoluminescência dos nanofios a temperatura ambiente. A diferença na fotoluminescência após diferentes tratamentos de plasma de O2 mostra que a razão entre a emissão da região do band gap e da banda do visível pode ser modificada pelo tratamento. Este efeito corrobora com a hipótese de que a banda verde de luminescência está relacionada às vacâncias de zinco. A variação percentual da razão entre as duas regiões apresenta uma dependência linear com a potência do plasma. / In this work, we performed the synthesis and characterization of zinc oxide nanowires. We also report an assembly process to measure the electrical properties of this material. We study the plasma treatment effect on the photoluminescence spectra of the nanowires. Nanowires were synthesized via vapor-liquid-solid mechanism, using gold as catalyst and c-plane sapphire as substrate. The samples were characterized using scanning electron microscopy, room temperature photoluminescence, x-rays diffraction and transmission electron microscopy. Our nanowires show a quasi-hexagonal cross section, with diameters of approximately 46 nm. Their lengths ranged from 3 to 10 μm. Our results show monocrystalline wurtzite crystal nanowires with c growth direction. We also study the plasma power effect of oxygen (O2) plasma treatment on the room temperature photoluminescence spectra of the nanowires. Our results show that the deep level emission to near band emission ratio decreases with the plasma treatment. This effect supports the hypothesis that claims the green band luminescence is related to the oxygen vacancies. Furthermore, the relative ratio change depends linearly on the plasma power.

Nanofios semicondutores de óxido metálico apresentam enorme potencial em aplicações de nano-sensoriamento de diferentes gases e substâncias químicas e biológicas, bem como na aplicação a detectores UV-visível. Neste trabalho, desenvolvemos e aperfeiçoamos a síntese de nanofios de ZnO em substratos de safira (001), silício (111) e silício (100) sob diferentes concentrações de oxigênio usando o processo de transporte de vapor-liquido-sólido (VLS). No presente trabalho, investigamos a influência da concentração de oxigênio no crescimento de nanofios de ZnO por Espectroscopia de Fotoluminescência a temperatura variável com a finalidade de estudo da mudança na concentração de defeitos. Apresentamos, ainda, caracterizações elétricas (IxV e Ixt) de nanoestruturas de ZnO sob diferentes pressões com o objetivo de estudar os defeitos envolvidos nos processos de transportes eletrônicos. Por último, propomos o desenvolvimento de micro-contatos através da técnica de microfeixe iônico e através de nanolitografia por feixe de elétrons com a finalidade de aplicações a sensores químicos, gasosos e fotodetectores. / Metal oxide nanowires semiconductors have enormous potential in high-sensitive, fast and selective sensing applications. It may be used to selectively detect different gases, chemical and biological substances and also in UV-visible photodetectors. The described processes involve the synthesis as well as the characterization of ZnO nanowires grown on sapphire (001), silicon (100) e silicon (111) substrates by the Vapor-liquid-solid transport method. In the present work, we describe the influence of oxygen concentration introduced in the growth step measured by photoluminescence at variable temperature to demonstrate the change in defect levels emission (DLE). Furthermore, we have shown electrical characterization (IxV and Ixt) in order to study the ambient effect for transport mechanisms in ZnO nanowires. We also report the development of crucial steps in the fabrication for an upcoming ZnO nanowire sensor device (gas, chemical and photodetector) using lithography techniques such as ion micro-beam and electron beam with the purpose of fabricating metallic micro-pads.

Nanofios semicondutores de óxido metálico apresentam enorme potencial em aplicações de nano-sensoriamento de diferentes gases e substâncias químicas e biológicas, bem como na aplicação a detectores UV-visível. Neste trabalho, desenvolvemos e aperfeiçoamos a síntese de nanofios de ZnO em substratos de safira (001), silício (111) e silício (100) sob diferentes concentrações de oxigênio usando o processo de transporte de vapor-liquido-sólido (VLS). No presente trabalho, investigamos a influência da concentração de oxigênio no crescimento de nanofios de ZnO por Espectroscopia de Fotoluminescência a temperatura variável com a finalidade de estudo da mudança na concentração de defeitos. Apresentamos, ainda, caracterizações elétricas (IxV e Ixt) de nanoestruturas de ZnO sob diferentes pressões com o objetivo de estudar os defeitos envolvidos nos processos de transportes eletrônicos. Por último, propomos o desenvolvimento de micro-contatos através da técnica de microfeixe iônico e através de nanolitografia por feixe de elétrons com a finalidade de aplicações a sensores químicos, gasosos e fotodetectores. / Metal oxide nanowires semiconductors have enormous potential in high-sensitive, fast and selective sensing applications. It may be used to selectively detect different gases, chemical and biological substances and also in UV-visible photodetectors. The described processes involve the synthesis as well as the characterization of ZnO nanowires grown on sapphire (001), silicon (100) e silicon (111) substrates by the Vapor-liquid-solid transport method. In the present work, we describe the influence of oxygen concentration introduced in the growth step measured by photoluminescence at variable temperature to demonstrate the change in defect levels emission (DLE). Furthermore, we have shown electrical characterization (IxV and Ixt) in order to study the ambient effect for transport mechanisms in ZnO nanowires. We also report the development of crucial steps in the fabrication for an upcoming ZnO nanowire sensor device (gas, chemical and photodetector) using lithography techniques such as ion micro-beam and electron beam with the purpose of fabricating metallic micro-pads.

This work investigates the feasibility of developing a self-powered structural health monitoring (SHM) smart tire using piezoelectric materials. While this work is divided into two components: SHM and energy harvesting, the context of smart tire in this work is defined as the development of a SHM system that (i) has self-powering capabilities, and (ii) addresses the potential of embedding sensors. The use of impedance based SHM on a tire is severely limited due to the low stiffness and high damping characteristics of the tire. This work propose the use of a high voltage impedance analyzer, and the addition of electrical circuit to enhance the damage detection process. Experimental work was conducted on an aluminum beam and on a tire section with commercially available piezoelectric sensors. The use of a high voltage impedance analyzer was demonstrated to provide insight on damage type and damage location. Two sensors were connected in parallel as an effective sensory system, and was shown to reduce interrogation time, but reduce damage identification sensitivity. With added electrical circuits, a belt separation on the tire was successfully detected by the shift in electrical impedance signature. For the energy harvesting portion of this work, a bimorph piezoelectric energy harvester model was derived using extended Hamilton's principle and the linear constitutive relations of piezoelectric materials. Comparison of model with experimental data at increasing loading conditions demonstrated the monotonic increase in voltage output, with linear asymptotes at extreme loading conditions (short-circuit and open-circuit). It also demonstrated the existence of an optimal resistive load for maximum power output. To address the ability to embed sensors, an existing fabrication process to grow arrays of ZnO nanowires in carbon fiber reinforced polymer was used in this work. Comparison of power generation from a composite beam with ZnO nanowires with a composite beam without ZnO nanowires demonstrated the power generation capabilities of the nanowires. A maximum peak voltage of 8.91 mV and peak power of 33.3 pW was obtained. After the application of 10V DC, a maximum of 45 pW was obtained. However, subsequent application of 20V DC reduced the maximum peak power output to 2.5 pW. Several attempts to increase power generation including adding a tip mass and changing the geometry of the composite beam were conducted. Finally, the theoretical voltage frequency response function obtained from the theoretical piezoelectric constant and dielectric constant of a single ZnO nanowire were compared to the experimental voltage frequency response function. The discrepancies were discussed. / Master of Science

The goal of this work is to investigate the piezoelectricity of composite laminates embedded with layers of zinc oxide (ZnO) nanowires. ZnO nanowire embedded composites have the potential to sense and actuate giving the potential for these smart composites to serve the function of being load bearing structures and monitoring the integrity of the structure. This work examines the piezoelectric characteristics of composite beams by investigating their electromechanical coupling in the form of vibration under the presence of electrical excitation. With the help of a mathematical model, piezoelectric constants are estimated for these samples. A layer of ZnO nanowires were grown on plane woven fiberglass fabric that was incorporated into a carbon fiber epoxy composite. The beam deflection velocity was measured as a varying voltage was applied to the composite. Using Hamilton's Principle and Galerkin's method of weighted residuals, a mathematical model was derived to estimate piezoelectric constants for the composites from the experimental data. Piezoelectric properties were determined using vibrational testing and a mathematical model. Piezoelectric constants h31, g31, and d31 were estimated to be 9.138 E7 V/m, 6.092 E-4 Vm/N, and 2.46 E-14 respectively. To demonstrate the electromechanical coupling, ZnO nanowire composites were bonded to Al beams that were progressively damaged to determine if a change in electrical impedance could be observed to correspond to the change in structural impedance of the host beam. Changes in impedance were detected by a change in root mean squared deviation damage metric M. A significant correlation was shown between increasing damage in the host beam and an increase in damage metric M. / Master of Science