Simulação de transporte eletrônico em dispositivos unimoleculares baseados em indicadores de pH

Nas últimas décadas, diversos pesquisadores têm tentado empregar moléculas em dispositivos eletrônicos de nanoescala. Por este motivo, diferentes parâmetros eletro/ópticos, que regem o transporte eletrônico em moléculas orgânicas, precisam ser analisados. Neste trabalho foi desenvolvido um estudo de transporte de carga para o composto Vermelho de Propila, popularmente utilizado como indicador de pH. A motivação para estudá-lo resulta de sua estrutura constituída por subunidades doadora-aceitadora, acopladas via grupo azo (N=N), uma característica bem conhecida em retificadores moleculares. A metodologia utilizada para tratar o sistema em equilíbrio é baseada em métodos de Mecânica Molecular e Hartree-Fock. Sendo que, para simular o sistema em não-equilíbrio, foi empregado o formalismo de Landauer-Büttiker. Através desses métodos, as curvas características do sistema molecular foram traçadas e comparadas. O resultado da comparação permitiu explicar os fenômenos que regem o transporte eletrônico na nanoestrutura. Além disso, foram analisados os efeitos de contatos metálicos, ligados a molécula na presença de campo elétrico externo.

Estudo da orientação dipolar fotoassistida de grupos azobenzênicos em filmes finos através de medidas da atividade eletro-óptica

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Síntese e caracterização de monômeros azo-carbonatos para a preparação de poli(azo-carbonato)s e poli)azo-uretana)s

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Dynamical speckles patterns of action potential transmission effects in squid giant axon membrane.

Undoubtedly the most important result of the investigations in physiology and biophysics was the discovery of the electrochemical mechanism of propagation of the action potential in nerves that was made by Hodgkin and Huxley during the first half of the past century. Since some decades ago diverse experiments about the electro optical properties of the axon membrane there was published using the most diverse optical experimental ‘procedures POT 6-10’. In this paper some results of a dynamical speckle technique applied for obtaining microscopic images of a section of a squid giant axon membrane during the activation by electrical impulses and his digital process are presented.

Advanced Numerical Simulation of Silicon-Based Solar Cells

Photovoltaic (PV) conversion is the direct production of electrical energy from sun without involving the emission of polluting substances. In order to be competitive with other energy sources, cost of the PV technology must be reduced ensuring adequate conversion efficiencies. These goals have motivated the interest of researchers in investigating advanced designs of crystalline silicon solar (c-Si) cells. Since lowering the cost of PV devices involves the reduction of the volume of semiconductor, an effective light trapping strategy aimed at increasing the photon absorption is required. Modeling of solar cells by electro-optical numerical simulation is helpful to predict the performance of future generations devices exhibiting advanced light-trapping schemes and to provide new and more specific guidelines to industry. The approaches to optical simulation commonly adopted for c-Si solar cells may lead to inaccurate results in case of thin film and nano-stuctured solar cells. On the other hand, rigorous solvers of Maxwell equations are really cpu- and memory-intensive. Recently, in optical simulation of solar cells, the RCWA method has gained relevance, providing a good trade-off between accuracy and computational resources requirement. This thesis is a contribution to the numerical simulation of advanced silicon solar cells by means of a state-of-the-art numerical 2-D/3-D device simulator, that has been successfully applied to the simulation of selective emitter and the rear point contact solar cells, for which the multi-dimensionality of the transport model is required in order to properly account for all physical competing mechanisms. In the second part of the thesis, the optical problems is discussed. Two novel and computationally efficient RCWA implementations for 2-D simulation domains as well as a third RCWA for 3-D structures based on an eigenvalues calculation approach have been presented. The proposed simulators have been validated in terms of accuracy, numerical convergence, computation time and correctness of results.

Hyperbranched polyether polyols as building blocks for complex macromolecular architectures

The present thesis deals with the development of new branched polymer architectures containing hyperbranched polyglycerol. Materials investigated include hyperbranched oligomers, hyperbranched polyglycerols containing functional initiator-cores at the focal point, well-defined linear-hyperbranched block copolymers and also negatively charged hyperbranched polyelectrolytes.rnHyperbranched oligoglycerols (DPn = 7 and 14) have been synthesized for the first time. The materials show narrow polydispersity (Mw/Mn ca. 1.45) and a very low content in cyclic homopolymers. 13C NMR evidences the dendritic structure of the oligomers and the DB could be calculated (44% and 52%). These new oligoglycerols were compared with the industrial products obtained by polycondensation which exhibit narrow polydispersity (Mw/Mn<1.3) butrnmultimodal distribution in SEC. Detailed 13C NMR and Maldi-ToF studies reveal the presence of branched units and cyclic compounds. In comparison, the hyperbranched oligoglycerols comprise a very low proportion of cyclic homopolymer which render them very interesting materials for biomedical applications for example.rnThe site isolation of the core moiety in dendritic structure offers intriguing potential with respect to peculiar electro-optical properties. Various initiator-cores (n-alkyl amines, UVabsorbing amines and benzophenone) for the ROMBP of glycidol have been tested. The bisglycidolized amine initiator-cores show the best control over the molecular weight and the molecular weight distribution. The photochemical analyses of the naphthalene containingrnhyperbranched polyglycerols show a slight red shift, a pronounced hypochromic effect (decrease of the intensity of the band) compared with the parent model compound and the formation of a relative compact structure. The benzophenone containing polymers adopt an open structure in polar solvents. The fluorescence measurements show a clear “dendritic effect” on the fluorescence intensities and the quantum yield of the encapsulated benzophenone.rnA convenient 3-step strategy has been developed for the preparation of well-defined amphiphilic, linear-hyperbranched block copolymers via hypergrafting. The procedure represents a combination of carbanionic polymerization with the alkoxide-based, controlled ring-opening multibranching polymerization of glycidol. Materials consisting of a polystyrene linear block and a hyperbranched polyglycerol block exhibit narrow polydispersity (1.01-1.02rnfor 5.4% to 27% wt. PG and 1.74 for 52% wt. PG) with a high grafting efficiency. The strategy was also extended to materials with a linear polyisoprene block.rnDetailed investigations of the solution properties of the block copolymers with linear polystyrene blocks show that block copolymer micelles are stabilized by the highly branched block. The morphology of the aggregates is depending on the solvent: in chloroform monodisperse spherical shape aggregates and in toluene ellipsoidal aggregates are formed. On graphite these aggregates show interesting features, giving promising potential applications with respect to the presence of a very dense, functional and stable hyperbranched block.rnThe bulk morphology of the linear-hyperbranched block copolymers has been investigated. The materials with a linear polyisoprene block only behave like complex liquids due to the low Tg and the disordered nature of both components. For the materials with polystyrene, only the sample with 27% wt. hyperbranched polyglycerol forms some domains showing lamellae.rnThe preparation of hyperbranched polyelectrolytes was achieved by post-modification of the hydroxyl groups via Michael addition of acrylonitrile, followed by hydrolysis. In aqueous solution materials form large aggregates with size depending on the pH value. After deposition on mica the structures observed by AFM show the coexistence of aggregates andrnunimers. For the low molecular weight sample (PG 520 g·mol-1) extended and highly ordered terrace structures were observed. Materials were also successfully employed for the fabrication of composite organic-inorganic multilayer thin films, using electrostatic layer-bylayer self-assembly coupled with chemical vapor deposition.

Design and Prototyping High Endurance Multi-Rotor

The topic of this thesis fo cus on the preliminary design and the p erformance analysis of a multirotor platform. A multirotor is an electrically p owered Vertical Take Off (VTOL) machine with more than two rotors that lift and control the platform. Multirotor are agile, compact and robust, making them ideally suited for b oth indo or and outdo or application especially to carry-on several sensors like electro optical multisp ectral sensor or gas sensor. The main disadvantage is the limited endurance due to heavy Li-Po batteries and high disk loading through the use of different small prop ellers. At the same time, the design of the multirotor do es not follow any engineering principle but it follow the ideas of amateurs’ builder. An adaptation of the classic airplane design theory for the preliminary design is implemented to fill the gap and detailed study of the endurance is p erformed to define the right way to make this kind of VTOL platforms.

Efficiency limits for silicon/perovskite tandem solar cells: a theoretical model

The primary goal of this work is related to the extension of an analytic electro-optical model. It will be used to describe single-junction crystalline silicon solar cells and a silicon/perovskite tandem solar cell in the presence of light-trapping in order to calculate efficiency limits for such a device. In particular, our tandem system is composed by crystalline silicon and a perovskite structure material: metilammoniumleadtriiodide (MALI). Perovskite are among the most convenient materials for photovoltaics thanks to their reduced cost and increasing efficiencies. Solar cell efficiencies of devices using these materials increased from 3.8% in 2009 to a certified 20.1% in 2014 making this the fastest-advancing solar technology to date. Moreover, texturization increases the amount of light which can be absorbed through an active layer. Using Green’s formalism it is possible to calculate the photogeneration rate of a single-layer structure with Lambertian light trapping analytically. In this work we go further: we study the optical coupling between the two cells in our tandem system in order to calculate the photogeneration rate of the whole structure. We also model the electronic part of such a device by considering the perovskite top cell as an ideal diode and solving the drift-diffusion equation with appropriate boundary conditions for the silicon bottom cell. We have a four terminal structure, so our tandem system is totally unconstrained. Then we calculate the efficiency limits of our tandem including several recombination mechanisms such as Auger, SRH and surface recombination. We focus also on the dependence of the results on the band gap of the perovskite and we calculare an optimal band gap to optimize the tandem efficiency. The whole work has been continuously supported by a numerical validation of out analytic model against Silvaco ATLAS which solves drift-diffusion equations using a finite elements method. Our goal is to develop a simpler and cheaper, but accurate model to study such devices.

Metal-oxide film and photonic structures for integrated device applications

The application of photonic crystal technology on metal-oxide film is a very promising field for future optical telecommunication systems. Band gap and polarization effects in lithium niobate (LiNbO3) photonic crystals and bismuth-substituted iron garnets (BiYIG) photonic crystals are investigated in this work reported here. The design and fabrication process are similar for these two materials while the applications are different, involving Bragg filtering in lithium niobate and polarization rotation in nonreciprocal iron garnets. The research of photonic structures in LiNbO3 is of high interest for integrated device application due to its remarkable electro-optical characteristics. This work investigated the photonic band gap in high quality LiNbO3 single crystalline thin film by ion implantation to realize high efficiency narrow bandwidth filters. LiNbO3 thin film detachment by bonding is also demonstrated for optical device integration. One-dimensional Bragg BiYIG waveguides in gyrotropic system are found to have multiple stopbands and evince enhancement of polarization rotation efficiency. Previous photon trapping theory cannot explain the phenomena because of the presence of linear birefringence. This work is aimed at investigating the mechanism with the support of experiments. The results we obtained show that selective suppression of Bloch states in gyrotropic bandgaps is the key mechanism for the observed phenomena. Finally, the research of ferroelectric single crystal PMN-PT with ultra high piezoelectric coefficient as a biosensor is also reported. This work presents an investigation and results on higher sensitivity effects than conventional materials such as quartz and lithium niobate.

Advances in the modeling, characterization and reliability of concentrator multijunction solar cells

Los sistemas de concentración fotovoltaica (CPV) parecen ser una de las vías más prometedoras para generar electricidad a gran escala a precios competitivos. La investigación actual se centra en aumentar la eficiencia y la concentración de los sistemas para abaratar costes. Al mismo tiempo se investiga sobre la fiabilidad de los diferentes componentes que integran un sistema de concentración, ya que para que los sistemas de concentración sean competitivos es necesario que tengan una fiabilidad al menos similar a los sistemas basados en células de silicio. En la presente tesis doctoral se ha llevado a cabo el estudio de aspectos avanzados de células solares multi-unión diseñadas para trabajar a concentraciones ultra-altas. Para ello, se ha desarrollado un modelo circuital tridimensional distribuido con el que simular el comportamiento de las células solares triple-unión bajo distintas condiciones de funcionamiento, así mismo se ha realizado una caracterización avanzada de este tipo de células para comprender mejor su modo de operación y así poder contribuir a mejorar su eficiencia. Finalmente, se han llevado a cabo ensayos de vida acelerados en células multiunión comerciales para conocer la fiabilidad de este tipo de células solares. Para la simulación de células solares triple-unión se ha desarrollado en la presente tesis doctoral un modelo circuital tridimensinal distribuido el cuál integra una descripción completa de la unión túnel. De este modo, con el modelo desarrollado, hemos podido simular perfiles de luz sobre la célula solar que hacen que la densidad de corriente fotogenerada sea mayor a la densidad de corriente pico de la unión túnel. El modelo desarrollado también contempla la distribución lateral de corriente en las capas semiconductoras que componen y rodean la unión túnel. Por tanto, se ha podido simular y analizar el efecto que tiene sobre el funcionamiento de la célula solar que los concentradores ópticos produzcan perfiles de luz desuniformes, tanto en nivel de irradiancia como en el contenido espectral de la luz (aberración cromática). Con el objetivo de determinar cuáles son los mecanismos de recombinación que están limitando el funcionamiento de cada subcélula que integra una triple-unión, y así intentar reducirlos, se ha llevado a cabo la caracterización eléctrica de células solares monouni ón idénticas a las subcelulas de una triple-unión. También se ha determinado la curva corriente-tensión en oscuridad de las subcélulas de GaInP y GaAs de una célula dobleunión mediante la utilización de un teorema de reciprocidad electro-óptico. Finalmente, se ha analizado el impacto de los diferentes mecanismos de recombinación en el funcionamiento de la célula solar triple-unión en concentración. Por último, para determinar la fiabilidad de este tipo de células, se ha llevado a cabo un ensayo de vida acelerada en temperatura en células solares triple-unión comerciales. En la presente tesis doctoral se describe el diseño del ensayo, el progreso del mismo y los datos obtenidos tras el análisis de los resultados preliminares. Abstract Concentrator photovoltaic systems (CPV) seem to be one of the most promising ways to generate electricity at competitive prices. Nowadays, the research is focused on increasing the efficiency and the concentration of the systems in order to reduce costs. At the same time, another important area of research is the study of the reliability of the different components which make up a CPV system. In fact, in order for a CPV to be cost-effective, it should have a warranty at least similar to that of the systems based on Si solar cells. In the present thesis, we will study in depth the behavior of multijunction solar cells under ultra-high concentration. With this purpose in mind, a three-dimensional circuital distributed model which is able to simulate the behavior of triple-junction solar cells under different working conditions has been developed. Also, an advanced characterization of these solar cells has been carried out in order to better understand their behavior and thus contribute to improving efficiency. Finally, accelerated life tests have been carried out on commercial lattice-matched triple-junction solar cells in order to determine their reliability. In order to simulate triple-junction solar cells, a 3D circuital distributed model which integrates a full description of the tunnel junction has been developed. We have analyzed the behavior of the multijunction solar cell under light profiles which cause the current density photo-generated in the solar cell to be higher than the tunnel junction’s peak current density. The advanced model developed also takes into account the lateral current spreading through the semiconductor layers which constitute and surround the tunnel junction. Therefore, the effects of non-uniform light profiles, in both irradiance and the spectral content produced by the concentrators on the solar cell, have been simulated and analyzed. In order to determine which recombination mechanisms are limiting the behavior of each subcell in a triple-junction stack, and to try to reduce them when possible, an electrical characterization of single-junction solar cells that resemble the subcells in a triplejunction stack has been carried out. Also, the dark I-V curves of the GaInP and GaAs subcells in a dual-junction solar cell have been determined by using an electro-optical reciprocity theorem. Finally, the impact of the different recombination mechanisms on the behavior of the triple-junction solar cell under concentration has been analyzed. In order to determine the reliability of these solar cells, a temperature accelerated life test has been carried out on commercial triple-junction solar cells. In the present thesis, the design and the evolution of the test, as well as the data obtained from the analysis of the preliminary results, are presented.

Nanoimprinted diffraction gratings for crystalline silicon solar cells: implementation, characterization and simulation

Light trapping is becoming of increasing importance in crystalline silicon solar cells as thinner wafers are used to reduce costs. In this work, we report on light trapping by rear-side diffraction gratings produced by nano-imprint lithography using interference lithography as the mastering technology. Gratings fabricated on crystalline silicon wafers are shown to provide significant absorption enhancements. Through a combination of optical measurement and simulation, it is shown that the crossed grating provides better absorption enhancement than the linear grating, and that the parasitic reflector absorption is reduced by planarizing the rear reflector, leading to an increase in the useful absorption in the silicon. Finally, electro-optical simulations are performed of solar cells employing the fabricated grating structures to estimate efficiency enhancement potential.

Laser pulse shaping with liquid crystals

A method of unpolarized laser pulses shaping is reported. The basis of the method is the use of an hybrid optical bistable device with nematic liquid-crystals, similar to the one previously reported by us. A sample of the input light constrols, by an asymmetrical electronic comparator, a 1 x 2 electro-optical total switch. The output pulses are reshaped and maintain the same polarization properties as the input light. From triangular input light signals, symmetriacl and asymmetrical output pulses have been obtained. The minimum pulse width achieved was 0.1 msec. A representation of the output versus input light signals gives an hysteresys cycle in the asymmetrical case.

Digital light beam deflector with liquid cristal (1980)

In this letter , we report a new method for óptical switching based on the electro-optical properties of liquid crystal materials and, in particular, of the nematic type. The basis of this new method is the use of twisted wedge structure that has not been reported before elsewhere. In the past several years , great efforts in integrated optics have been made to develop optical switching devices with fast speed by using electro-optic, acousto-optic or magneto -optic materials. A mechanically operated óptical switch made of grade-index rod 1enses and e1ectromagnets has been proposed too . Switches of this kind include one input and two output waveguides and, depending on the app1ied voltage, one incident light on the switch exits either in one or another of the two output waveguides.

The influence of antiferroelectric compounds on helical pitch of orthoconic W-1000 mixture

The influence of six antiferroelectric compounds on the helical pitch of mixture W-1000, which was reported as long pitch orthoconic antiferroelectric liquid crystalline mixture, was checked by spectrophotometry and polarimetry methods. The electro-optical properties for the mixture with the longest pitch were measured. An improvement in electro-optical response due to the long pitch is reported. The novelty in electro-optical properties is the good symmetry response.