This thesis presents applications of the layer-by-layer (LbL) assembly technique in fabrication of thin films with a primary focus on design and development of electrochromic devices. The optical properties of electrochromic materials change as they alter between redox states. The morphology and properties of LbL-assembled thin films can be modified by varying several processing factors such as dipping duration, ion type, ion concentration, pH, molecular weight, and ionic strength. In the present work, several factors of LbL assembly process were manipulated to tailor electrochromic thin films of desired attributes. An electrochromic device (ECD) with fast optical switching speed was designed and constructed based on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). This device exhibited optical switching speeds of 31 and 6 ms for coloration and decoloration respectively, on a 60 mm2 area. Poly(aniline 2-sulfonic acid) (PASA) is a relatively new ionic polymer, and its electrochromic properties have not been previously investigated in much detail. PASA thin film showed several redox states corresponding to color changes from dark blue to gray as it passed different redox states. One particularly interesting and promising design for ECDs is dual electrochrome. Dual electrochrome ECDs based on PANI and polyaniline (PASA) are investigated in this thesis. The PANI/PASA thin film showed superior spectroelectrochemical properties compare to other ECDs reported here or elsewhere. An electrode with single wall carbon nanotubes (SWCNTs) coating was tested as the substrate for an ECD based on poly[2-(3-thienyl) ethoxy-4-butylsulfonate] (PTEBS) to examine performance of the electrochromic polymer on a substrate other than an indium tin oxide (ITO) electrode. Compared to ITO, the SWCNT based device exhibited superior properties. / Master of Science

"This work presents a novel method to efficiently factorize the combination of multiple factor graphs having common variables of estimation. The fast-paced innovation in the algebraic graph theory has enabled new tools of state estimation like factor graphs. Recent factor graph formulation for Simultaneous Localization and Mapping (SLAM) like Incremental Smoothing and Mapping using the Bayes tree (ISAM2) has been very successful and garnered much attention. Variable ordering, a well-known technique in linear algebra is employed for solving the factor graph. Our primary contribution in this work is to reuse the variable ordering of the graphs being combined to find the ordering of the fused graph. In the case of mapping, multiple robots provide a great advantage over single robot by providing a faster map coverage and better estimation quality. This coupled with an inevitable increase in the number of robots around us produce a demand for faster algorithms. For example, a city full of self-driving cars could pool their observation measurements rapidly to plan a traffic free navigation. By reusing the variable ordering of the parent graphs we were able to produce an order-of-magnitude difference in the time required for solving the fused graph. We also provide a formal verification to show that the proposed strategy does not violate any of the relevant standards. A common problem in multi-robot SLAM is relative pose graph initialization to produce a globally consistent map. The other contribution addresses this by minimizing a specially formulated error function as a part of solving the factor graph. The performance is illustrated on a publicly available SuiteSparse dataset and the multi-robot AP Hill dataset."

O projeto ISAM apresenta uma plataforma para o desenvolvimento e a execução de aplicações pervasivas. O ambiente de execução proposto na arquitetura ISAM, denominado ISAMpe (ISAM pervasive environment), foi concebido para ser implantado em escala global, com elevado número de componentes. Esses componentes podem ser móveis ou fixos e podem apresentar limitações em seus recursos computacionais. Muitas das aplicações pervasivas que podem ser executadas no ISAMpe têm necessidade de um serviço de disseminação capaz de distribuir informações de um produtor para um grande número de consumidores. Esta dissertação apresenta um serviço de disseminação de informações para a arquitetura ISAM, denominado DIMI (Disseminador Multicast de Informações). O DIMI apresenta uma arquitetura de multicast no nível de aplicação. O DIMI propõe um algoritmo de formação da topologia de disseminação que tem o objetivo de alcançar maior escalabilidade pelo alívio de sobrecarga em participantes específicos do canal, durante os momentos em que houver um grande número de novos consumidores querendo iniciar o consumo simultaneamente. No seu ambiente-alvo, o ISAMpe, o DIMI também oferece suporte à desconexão planejada, permitindo que dispositivos computacionais com limitações de conectividade participem da disseminação, e ainda oferece suporte à mobilidade de usuários. A topologia de comunicação do DIMI adapta-se às condições da rede física subjacente a ela, de acordo com critérios específicos da aplicação que utilizar o serviço. Os resultados obtidos com a simulação de alguns aspectos do funcionamento do DIMI e com a execução do protótipo do mesmo validam os argumentos usados para justificar a necessidade e a forma de construção do serviço. / The ISAM project presents a platform to the development and to the execution of pervasive applications. The execution environment proposed by the ISAM architecture, named ISAMpe (ISAM pervasive environment) was conceived to be deployed on global scale, having a large number of components. These components may be mobile or static and may present computational resource limitations. Many of the pervasive applications that may be executed on the ISAMpe need a dissemination service capable of distribute information from one producer to many consumers. This dissertation presents a information dissemination service for the ISAM architecture, named DIMI (Multicast Information Disseminator - Disseminador Multicast de Informações). DIMI presents an application-level multicast architecture. DIMI proposes an algorithm to create the dissemination topology which objective is to achieve scalability through the relief of overload on specific participants of the channel, during the moments where many new consumers want to start consumption simultaneously. Inside its target-environment, DIMI also offer support to user mobility and to planned disconnection, allowing resource limited computational devices to be participants of the dissemination. DIMI's dissemination topology adapt itself to the conditions of fabric network, accordingly to applications' criteria. The results obtained with the simulation of some DIMI's characteristics and with prototipation validate the arguments used to justify the necessity and the way of construction of the service.

O projeto ISAM apresenta uma plataforma para o desenvolvimento e a execução de aplicações pervasivas. O ambiente de execução proposto na arquitetura ISAM, denominado ISAMpe (ISAM pervasive environment), foi concebido para ser implantado em escala global, com elevado número de componentes. Esses componentes podem ser móveis ou fixos e podem apresentar limitações em seus recursos computacionais. Muitas das aplicações pervasivas que podem ser executadas no ISAMpe têm necessidade de um serviço de disseminação capaz de distribuir informações de um produtor para um grande número de consumidores. Esta dissertação apresenta um serviço de disseminação de informações para a arquitetura ISAM, denominado DIMI (Disseminador Multicast de Informações). O DIMI apresenta uma arquitetura de multicast no nível de aplicação. O DIMI propõe um algoritmo de formação da topologia de disseminação que tem o objetivo de alcançar maior escalabilidade pelo alívio de sobrecarga em participantes específicos do canal, durante os momentos em que houver um grande número de novos consumidores querendo iniciar o consumo simultaneamente. No seu ambiente-alvo, o ISAMpe, o DIMI também oferece suporte à desconexão planejada, permitindo que dispositivos computacionais com limitações de conectividade participem da disseminação, e ainda oferece suporte à mobilidade de usuários. A topologia de comunicação do DIMI adapta-se às condições da rede física subjacente a ela, de acordo com critérios específicos da aplicação que utilizar o serviço. Os resultados obtidos com a simulação de alguns aspectos do funcionamento do DIMI e com a execução do protótipo do mesmo validam os argumentos usados para justificar a necessidade e a forma de construção do serviço. / The ISAM project presents a platform to the development and to the execution of pervasive applications. The execution environment proposed by the ISAM architecture, named ISAMpe (ISAM pervasive environment) was conceived to be deployed on global scale, having a large number of components. These components may be mobile or static and may present computational resource limitations. Many of the pervasive applications that may be executed on the ISAMpe need a dissemination service capable of distribute information from one producer to many consumers. This dissertation presents a information dissemination service for the ISAM architecture, named DIMI (Multicast Information Disseminator - Disseminador Multicast de Informações). DIMI presents an application-level multicast architecture. DIMI proposes an algorithm to create the dissemination topology which objective is to achieve scalability through the relief of overload on specific participants of the channel, during the moments where many new consumers want to start consumption simultaneously. Inside its target-environment, DIMI also offer support to user mobility and to planned disconnection, allowing resource limited computational devices to be participants of the dissemination. DIMI's dissemination topology adapt itself to the conditions of fabric network, accordingly to applications' criteria. The results obtained with the simulation of some DIMI's characteristics and with prototipation validate the arguments used to justify the necessity and the way of construction of the service.

O projeto ISAM apresenta uma plataforma para o desenvolvimento e a execução de aplicações pervasivas. O ambiente de execução proposto na arquitetura ISAM, denominado ISAMpe (ISAM pervasive environment), foi concebido para ser implantado em escala global, com elevado número de componentes. Esses componentes podem ser móveis ou fixos e podem apresentar limitações em seus recursos computacionais. Muitas das aplicações pervasivas que podem ser executadas no ISAMpe têm necessidade de um serviço de disseminação capaz de distribuir informações de um produtor para um grande número de consumidores. Esta dissertação apresenta um serviço de disseminação de informações para a arquitetura ISAM, denominado DIMI (Disseminador Multicast de Informações). O DIMI apresenta uma arquitetura de multicast no nível de aplicação. O DIMI propõe um algoritmo de formação da topologia de disseminação que tem o objetivo de alcançar maior escalabilidade pelo alívio de sobrecarga em participantes específicos do canal, durante os momentos em que houver um grande número de novos consumidores querendo iniciar o consumo simultaneamente. No seu ambiente-alvo, o ISAMpe, o DIMI também oferece suporte à desconexão planejada, permitindo que dispositivos computacionais com limitações de conectividade participem da disseminação, e ainda oferece suporte à mobilidade de usuários. A topologia de comunicação do DIMI adapta-se às condições da rede física subjacente a ela, de acordo com critérios específicos da aplicação que utilizar o serviço. Os resultados obtidos com a simulação de alguns aspectos do funcionamento do DIMI e com a execução do protótipo do mesmo validam os argumentos usados para justificar a necessidade e a forma de construção do serviço. / The ISAM project presents a platform to the development and to the execution of pervasive applications. The execution environment proposed by the ISAM architecture, named ISAMpe (ISAM pervasive environment) was conceived to be deployed on global scale, having a large number of components. These components may be mobile or static and may present computational resource limitations. Many of the pervasive applications that may be executed on the ISAMpe need a dissemination service capable of distribute information from one producer to many consumers. This dissertation presents a information dissemination service for the ISAM architecture, named DIMI (Multicast Information Disseminator - Disseminador Multicast de Informações). DIMI presents an application-level multicast architecture. DIMI proposes an algorithm to create the dissemination topology which objective is to achieve scalability through the relief of overload on specific participants of the channel, during the moments where many new consumers want to start consumption simultaneously. Inside its target-environment, DIMI also offer support to user mobility and to planned disconnection, allowing resource limited computational devices to be participants of the dissemination. DIMI's dissemination topology adapt itself to the conditions of fabric network, accordingly to applications' criteria. The results obtained with the simulation of some DIMI's characteristics and with prototipation validate the arguments used to justify the necessity and the way of construction of the service.

After decades of development, optical fiber technology has reached a high degree of sophistication and maturity, and currently serves as the backbone of today''s internet. Despite its technical versatility and capability, current silica fiber technology still has a significant flaw: since silica fibers only possess very weak second order nonlinearity, it has been impossible to develop a large number of important nonlinear optical devices and instruments, such as optical parametric amplifiers (OPA) and optical parametric oscillators (OPO). In this thesis,we show how to overcome this intrinsic limitation, and introduce second order nonlinearity into silica fiber devices. / Master of Science

This dissertation is about fabrication and functionalization of metal nanoparticles for use in plasmonic and nonlinear optical (NLO) applications. In the first two chapters, I describe a series of experiments, where I combined silver nanoparticles fabricated by nanosphere lithography with ionic self-assembled multilayer (ISAM) films, tuning the geometry of the particles to make their plasmonic resonances overlap with the frequency of optical excitation. The designed hybrid metallic/organic nanostructures exhibited large enhancements of the efficiency of second harmonic generation (SHG) compared to conventional ISAM films, causing a modified film with just 3 bilayers to be optically equivalent to a conventional 700-1000 bilayer film. SHG responses from Ag nanoparticle-decorated hybrid-covalent ISAM (HCISAM) films were investigated as the next logical step towards high-Ï ²⁺ ISAM films. I found that the plasmonic enhancement primarily stems from interface SHG. Interface effects were characterized by direct comparison of SHG signals from PAH/PCBS ISAM films and PAH/PB HCISAM films. Though interface &chi²⁺ is substantially smaller in PAH/PCBS than in PAH/PB, plasmonically enhanced PAH/PCBS films exhibit stronger NLO response. I propose that the structure of PAH/PB film makes its interface more susceptible to disruptions in the nanoparticle deposition process, which explains our observations. During the fabrication of monolayer crystals for nanosphere lithography, I developed a variation of the technique of convective self-assembly, where the drying meniscus is restricted by a straight-edge located approximately 100 μM above the substrate adjacent to the drying zone. This technique can yield colloidal crystals at roughly twice the growth rate compared to the standard technique. I attribute this to different evaporation rates in the thin wet films in the two cases. I also found that the crystal growth rate depends strongly on the ambient relative humidity. Finally, dithiocarbamate (DTC)-grafted polymers were synthesized and employed to functionalize surfaces of Au nanopartciles. PAH-DTC shows greater stability in different environments than PEI-DTC. I also investigated the stability of PAH-DTC coated particles in suspensions with UV-Vis spectroscopy and autotitration. The covalently bonded PAH-DTC enhances the colloidal stability of the Au nanoparticles and enables subsequent ISAM film deposition onto the particles. / Ph. D.

The purpose of this thesis is to make a broadband antireflection coating configuration known as a quarter-wave stack consisting of one layer of titania and of one layer of silica nanoparticles. We utilize much that is already known about silica nanoparticle deposition. The first objective of this thesis is deposition and characterization of titania nanoparticle films deposited on glass microscope slides by a technique known as Ionic Self-Assembled Multilayers or ISAM deposition. This technique takes advantage of the electrostatic attraction between oppositely charged materials and ideally results in a uniform nanoparticle film whose thickness and optical properties can be tightly controlled. Deposition of a quarter-wave stack based on ISAM deposition of silica and titania nanoparticles is significantly simpler and less expensive than alternative deposition methods. Initial attempts to deposit titania films were unsuccessful because of excess diffuse scattering due to inhomogeneities in the film. In order to reduce diffuse scattering, two approaches were considered. The first approach was to improve the deposition process itself by experimenting with different values of deposition parameters such as solution pH and solution molarity. The other approach focused on removing the large nanoparticle aggregates from the colloidal solutions of titania nanoparticles that were suspected to be responsible for rough film surfaces resulting in diffuse scattering. This approach was successful. In addition, evidence suggested that surface roughness contributed more to diffuse scattering than the bulk of the films. After minimizing diffuse scattering from titania nanoparticle films, we used known results from research on silica nanoparticle films to deposit quarter-wave stacks consisting of one layer of titania nanoparticles with high refractive index and one layer of silica nanoparticles with low refractive index. This contrast in refractive indices is a desirable characteristic of quarter-wave stacks. The thicknesses and refractive indices of the two layers in the quarter-wave stacks were measured by ellipsometry and compared to the nominal thicknesses of these layers. Finally, the reflectance was derived from a model of the quarter-wave stack and was compared to the measured reflectance. It was found that construction of a quarter-wave stack by ISAM is possible but that it will be necessary to acquire data from more experiments. / Ph. D.

This thesis presents the characterization of the optical and mechanical properties of silica nanoparticle films fabricated by ionic self-assembly, also known as layer-by-layer (LbL) deposition. Utilizing electrostatic attraction of oppositely-charged materials permits uniform and rapid growth of the constituents onto planar and curved surfaces. In this work, silica nanoparticles are adsorbed onto glass and polycarbonate substrates, as well as micron-scale glass fibers, with the purpose of improving the optical quality of the respective media. Several methods are presented to improve the adhesion and cohesion of silica nanoparticle films on glass substrates. In the first method, the substrate and nanoparticle surfaces are coated with materials containing sulfonate end groups. Next, a photo-reactive polycation known as diazo-resin (DAR) is used in ISAM deposition with the modified silica nanoparticles. Subsequent exposure to UV converts the ionic bonds between the DAR and sulfonate groups into covalent ones. The second method to improve the mechanical strength is to heat the ISAM silica nanoparticle film at a high enough temperature (500 °C) to remove the polymer and partially fuse the nanoparticles. This technique is known as calcination and is shown to significantly improve the mechanical robustness of the film without compromising the optical properties. The final method involves the deposition of precursor and capping polymer layers around bulk silica nanoparticle films with both bilayer and quadlayer designs. The addition of these polymer layers improves the surface contact between adjacent nanoparticles but reduces the film porosity and consequently the optical transparency. Currently the calcination technique is the only one that significantly improves the film adhesion and cohesion, but suggestions are offered to potentially improve the performance of films made by the other two methods. An alternative way to functionalize polycarbonate substrates for silica nanoparticle ISAM deposition is also presented. The molecular structure of polycarbonate at the surface can be modified by exposing it to deep UV (λ = 185, 254 nm). By doing so, the surface becomes populated with carboxylate species, and thus permits ISAM deposition of poly(allylamine hydrochloride) (PAH) and silica nanoparticles. A variety of spectroscopic methods show that the molecular structure is changed by this procedure, and SEM shows that UV treatment improves the uniformity of ISAM films on polycarbonate. Finally, PAH/silica nanoparticle ISAM films are deposited onto glass fibers. The fibers are used for mechanical reinforcement of polymer composite optical media. The role of the nanoparticle film on the fibers is to reduce light scattering at the interfaces of materials with different thermo-optic coefficients, in other words, transmittance losses associated with changes in temperature. Fiber bundles coated with silica nanoparticles suffer from unacceptable levels of aggregation, and hence do not currently improve the transmittance over the temperature spectrum. Some evidence is presented, however, to suggest that the transparency can be improved if fiber aggregation during ISAM deposition can be avoided. / Ph. D.

In this thesis, we demonstrate, theoretically, that, by depositing a regular fused-silica fiber with optical nonlinear molecules, strong and thermodynamically stable SHG can be obtained. Our experiments also provide strong evidence for the theory. Start from the basic Maxwell equation, we derive the SHG efficiency that the excited power translates into the SHG signal. According to the SHG efficiency equation, a small radius and a long length will help to result in a high SHG efficiency, which also increases with the excited power. We fabricate silica fiber tapers with radius less than 5 μm through either wet etching or heating while stretching. Through improving the stretching setup, and adroitly manipulating both the stretching rate and the heating temperature, we are able to control the taper loss less than 1 dB. Then we dip taper part into cationic solution and anionic solution alternatively to have ISAM/CHISAM film on it. By improving the surface quality of film around a silica fiber taper, we are able to control film loss of PAH/PR film to less than 2 dB for 5 bilayers. We set up a SHG measurement stage for a nonlinear fiber, and develop a measurement method during the experiments. We have shown that by depositing (PAH/PB)10 films around a fiber taper with a diameter around 5 µm, we can obtain high SHG signal. The ratio of the obtained SHG signal to the excitation power for such a nonlinear fiber is more than 10 times of that of a 125 µm single mode fiber with the same length. Our experiment result provides strong evidence that centrosymmetric material can be used as SHG material. / Master of Science