Orientador: Paulo Noronha Lisboa Filho / Banca: Margarida Juri Saeki / Banca: Valmor Roberto Mastelaro / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Resumo: Este trabalho teve como objetivos a preparação e caracterização de filmes finos de YBa2Cu3O.7-x e La0.7Ca0.3MnO3 depositados sobre substratos de níquel metálico, silício, e substratos cerâmicos de MgO, SrTiO.3. As análises realizadas tiveram como objetivos o estudo da formação da fase, e a determinação do comportamento de condução elétrica e das propriedades magnéticas dos filmes finos. Nas deposições realizadas sobre substratos de níquel foi utilizada uma camada intermediária de Y.2O.3, para posterior deposição de YBa.2Cu.3O.7-x. As soluções precursoras dos filmes foram obtidas através do método dos precursores poliméricos, com a inclusão do ácido etilenodiaminotetraacético (EDTA) como agente complexante. As deposições ocorreram através da técnica Spin-Coating. As análises realizadas através da Espectroscopia de Fotoelétrons de Raios X (XPS) e Difração de Raios X (XRD) auxiliaram, na identificação dos elementos químicos presentes nos filmes finos, e a verificação da formação das fases cristalográficas desejadas. Estas técnicas permitiram comprovar a eficácia da camada intermediária (buffer layer) de Y.2O.3 utilizada para a deposição de YBa.2Cu.3O.7-x sobre substratos de níquel metálico, e comprovar a necessidade de uma camada buffer layer para a obtenção de filmes de YBa.2Cu.3O.7-x depositado sobre substrato de silício. Assim como na deposição realizada sobre substrato de níquel, foi verificada também a boa formação das fases desejadas sobre os substratos cerâmicos. As análises de condução elétrica e das propriedades magnéticas demonstraram a característica supercondutora dos filmes de YBa.2Cu.3.O.7-x depositados sobre substratos de níquel metálico, MgO e SrTiOI.3, e ...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This paper aimed at preparing and characterizing YBa2Cu3O.7-x e La0.7Ca0.3MnO3 and thin films, deposited on metallic nickel substrates, silicon and MgO, SrTiO.3 and LaAIO.3 ceramic substrates. The analyses performed had as objectives to study the phase formation and to determine the electric conduction behavior and the magnetic properties of the thin films. In the depositions perfomed on nickel substrates, a YBa.2Cu.3O.7-x deposition. The precursory solutions of the films were obtained by means of the polymeric precursor method, with the inclusion of the ethylenediaminotetra acetic acid (EDTA), as complexant agent. The depositions occurred through the Spin-coating technique. The analyses performed by means of the X-ray Photoelectron Spectroscopy (XPS) and X-ray Diffraction (XRD) aided in the identification of the chemical elements present in the thin films and in the verification of the formation of the desired crystallographic phases. Such techniques allowed for confirming the Y.2O.3 buffer layer efficacy, utilized to the YBa.2Cu.3O.7-x deposition on metallic nickel substrates, and for confirming the need of a buffer layer in order to obtain the YBa.2Cu.3O.7-x films deposited on the silicon substrate. As in the deposition performed on the nickel substrate, it was also verified the good formation of the desired phases on the ceramic substrates. The analyses on electrical conduction and magnetic properties demonstrated the superconducting characteristic of the YBa.2Cu.3O.7-x films deposited on metallic nickel substrates, MgO and SrTiO.3, as well as the magnetic characteristic of the La.0.7Ca.0.3MNO.3 film deposited on the silicon substrate. The analyses performed by means of Scanning Electron Microscopy (SEM) showed a better ...(Complete abstract, click electronic address below) / Mestre

>Magister Scientiae - MSc / The efficiency of organic photovoltaics is influenced by the structure of the polymer, the morphology of the film, the interfaces between the layers, the choice of electron acceptor material and the ratio between the electron acceptor material and the polymer. In this project, we have used regioregular poly (3-hexylthiophene) (rr-P3HT) as the electron donor material and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), a derivative of the C60 fullerene, as the acceptor material. Different weight-ratios of rr-P3HT to PCBM were prepared by stirring for several hours in a chloroform solution and subsequently spin coated onto crystalline silicon and transparent conductive oxide/glass substrates. The effect of the PCBM concentration on the photo-induced optical emission and absorption properties of rr-P3HT was investigated by photoluminescence and ultraviolet-visible spectroscopy, respectively. Changes in the structural properties, as a function of the weight-ratio, were probed by high-resolution transmission electron microscopy, x-ray diffraction, Fourier transform infrared spectroscopy and Raman spectroscopy. Results show that the structural integrity and crystallinity of rr-P3HT is compromised with the addition of excessive amounts of PCBM, which has a negative impact on the optical absorption of rr-P3HT and the photo-induced charge transfer mechanism between the rr-P3HT and PCBM. This work illustrates that blending rr-P3HT with an equal weight of PCBM results in an optimum configuration for improved performance in organic photovoltaic devices.

Made available in DSpace on 2016-06-02T20:34:21Z (GMT). No. of bitstreams: 1 3252.pdf: 3233070 bytes, checksum: ee2927e22c3078fa25c271cf7d859fbf (MD5) Previous issue date: 2010-07-28 / Financiadora de Estudos e Projetos / The incorporation of conducting polymer into a conventional polymer matrix has received considerable attention in the last decade because of the possibility of combining the good processability and mechanical performance of the conventional polymer with the electrical optical properties of conducting polymer. Among conducting polymers, polyaniline (PANI) and its derivatives has been extensively used because of the low cost of raw material, ease of synthesis and environmental stability. The main objective of this study was to develop a sensor for electronic tongue, from thin films of blends of polyurethane with POMA on interdigitated electrodes produced by spin-coating technique, under optimized conditions, and check the electrical behavior of the sensors in states doped. Films PUR mixture with POMA, although they may have less sensitivity to the substances found in the analyte than the nano-structured films, they may have better adherence and therefore be used to analyze substances with which the nano-structured films would not be possible. Films mixture of polyurethane derived from castor oil (PUR) and POMA were obtained by the casting (free standing) and also on interdigitated electrodes by the method of spin coating. The films were characterized using the techniques of UV-Vis-Nir, thermo-dynamic-mechanical analysis (DMTA), thermogravimetric analysis (TGA), stress-strain and optical microscopy. The values of modulus of elasticity of the PUR solvent chloroform (PUR-Clo) for the mixture of PUR/POMA (m/m) 50/50 had values of 0.3 GPa and 4.1 GPa, respectively. With the incorporation of 10% of POMA in the PUR glass transition temperature (Tg) of the films increased from 67 to 137oC, respectively. For the analysis done by DMA, the films with 30, 40 and 50% of POMA in PUR, confirmed the presence of crosslinking between the polymers, Mc, values of 195, 322 and 517 mol/m3, respectively. The films doped with NH4OH and HCl have better response capacitive and resistive to various analytes analyzed in the frequency range 1-105 Hz Thus, the sensors doped and dedoped can be used as an identifier of fingerprint detection of substances in different concentrations. / A mistura de dois ou mais polímeros é uma alternativa para se obter um novo material que apresente propriedades desejáveis não encontradas nos componentes individuais. No caso da mistura de polímeros condutores com polímeros isolantes convencionais, tem-se como resultado, em geral, um terceiro material que apresenta boas propriedades mecânicas e alta condutividade elétrica que potencializam aplicações como sensores entre outras. O objetivo principal deste trabalho foi de desenvolver um sensor para língua eletrônica, a partir de filmes finos de mistura de poliuretano com POMA, sobre eletrodos interdigitados produzido pela técnica de spin-coating, sob condições otimizadas, e verificar o comportamento elétrico dos sensores e também a caracterização mecânica e térmica dos filmes auto-sustentáveis. Os filmes da mistura de Poliuretano derivada do óleo de mamona (PUR) e POMA foram obtidos pelo método casting (filmes auto-sustentáveis) e também sobre eletrodos interdigitados pelo método de spin coating . Os filmes foram caracterizados usando as técnicas de Uv-Vs-Nir, análise termo-dinâmicomecanica (DMTA), termogravimétrica (TGA), tensão deformação e microscopia óptica. Os valores de modulo de elasticidade do PUR com solvente clorofórmio (PUR-Clo) em relação à mistura de PUR/POMA 50/50 (m/m) apresentaram valores de 0,3 GPa e 4,1 GPa, respectivamente. Com a incorporação de 10% de POMA no PUR a temperatura de transição vítrea (Tg), dos filmes, aumentou de 67oC para 137oC, respectivamente. Pela analises realizadas através de DMA, os filmes com 30, 40 e 50% de POMA no PUR, confirmaram a presença de ligações cruzadas entre os polímeros, Mc, valores de 195, 322 e 517 mol/m3, respectivamente. Os filmes dopados com NH4OH e HCl apresentam melhores resposta capacitivas e resistivas para vários analitos analisados, na faixa de freqüência de 1 a 105 Hz. Assim, os sensores dopados e desdopados podem ser usados como um identificador de impressão digital na detecção de substâncias em diferentes concentrações.

>Magister Scientiae - MSc / In a quest for low operational and maintenance cost solar cell devices, organic photovoltaics remain a potential source of energy worthy to be explored. In order to generate cost- effective electricity from solar energy, either the efficiency of the solar cells must be improved or alternatively the manufacturing cost must be lowered. The power conversion efficiency (PCE) of organic photovoltaics is influenced by the choice of electron acceptor material, the structure of the polymer, the morphology of the film, the interfaces between the layers and the ratio between the electron acceptor material and the polymer. Nevertheless, efficiency is still limited compared to conventional silicon based PV cells due to low mobility of charge carriers with a short exciton diffusion length in the active layer. Currently, hybrid solar cells have been considered as one of the most promising concepts to address the limited efficiency of organic solar cells. Therefore in this thesis ZnO nanoparticles were synthesized using hydrothermal assisted method. These nanoparticles were incorporated in the poly (3-hexylthiophene) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM), and used as additional acceptors of electrons released from the polymer donor material, with the anticipation to increase the electron mobility, and ultimately the PCE. The thermo-gravimetric analyses revealed improved thermal stability of P3HT upon incorporating ZnO in the polymer matrix. X-ray diffraction analyses revealed that the diffraction peaks shift to higher angles when incorporating the ZnO in the P3HT:PCBM surface and this is consistent with the Raman observation. The photovoltaic properties demonstrated that the addition of ZnO nanoparticles in P3HT:PCBM bulk-heterojunction increases PCE from a baseline of ∼1.0 % in the P3HT:PCBM system to 1.7% in the P3HT:PCBM:ZnO ternary system. The enhanced PCE was due to improved absorption as compared to its counterparts. Upon increasing the addition of ZnO nanoparticles in the P3HT:PCBM matrix, the PCE decreases, due to a large phase separation between the polymer, PCBM and ZnO induced by ZnO agglomerations which resulted in increased surface roughness of the active layer. These findings signify that incorporation of ZnO nanostructures in the P3HT:PCBM polymer matrix facilitates the electron transport in the photoactive layer which results to improved efficiency.

For its inherent advantages, such as lightweight, low cost, flexibility, and opportunity to cover large surface areas, organic solar cells have attracted more and more attention in both academia and industry. However, the efficiency of organic solar cell is still much lower than silicon solar cells, but steadily rising as it now stands above 8%. The architecture of bulk heterojunction solar cells can improve the performance of organic solar cell a lot, but these improvements are highly dependent on the morphology of photoactive layer. Therefore, by controlling the morphology of photoactive layer, most commonly composed of a P3HT donor polymer and PCBM small molecule, the performance of organic solar cells could be optimized. The use of solvent additives in the solution formulation is particularly interesting, because it is a low cost method of controlling the phase separation of the photoactive layer and possibly removing the need for subsequent thermal and solvent vapor annealing. However, the role of the solvent additive remains not well understood and much debate remains on the mechanisms by which it impacts phase separation. In the first part of this thesis, we investigate the role of the solvent additive on the individual components (solvent, donor and acceptor) of the solution and the photoactive layer both in the bulk solution, during solution-processing and in the post-processing solid state of the film. In the second part of this thesis, we investigate the role of the additive on the blended solution state and resulting thin film phase separation. Finally, we propose a new method of controlling phase separation based on the insight into the role of the solvent additive. In the first part, we used an additive [octandiethiol (OT)] in the solvent to help the aggregation of P3HT in the solution. From the UV-vis experiments, the crystallinity of P3HT in the solutions increased while it decreased in thin films with steady increase of additive concentration. This method could be used for one step, annealing-free fabrication of organic solar cell with high performance. The solution can potentially be used to prepare ink for the large scale roll-to-roll ink-jet printing of P3HT thin films. Secondly, from the experiments it is found that differences in the evaporation rate and solubility of the components of the photoactive layer may be part of the reason for morphological changes. With lower evaporation rate than the host solvent, the additive concentration in the solution keeps increasing with time during the final stages of spin coating. In addition, the phase separation is increased with the increase of additive concentration, as demonstrated by AFM and TEM. By controlling the additive concentration, it is possible to control the phase separation of photoactive layer in pristine device. It is also found that the additive can change the wetting ability of the solvent to produce films with high surface coverage. With this information in hand, we modified the solution process of BHJ layers. A layer of crystals was deposited from the OT-containing solution by postponing the start of the spin coating for several minutes (delay time) after the solution is dropped on the surface of substrate. We found this to be a very effective method of increasing the phase separation and crystallinity of the photoactive materials. This effect was not possible when using oDCB solvent without any additive.

This work deals with the optimization of the preparation process of WO3 photoanodes nad their characterization. For compositions were prepared, which were applied to a substrate via spin-coating process and subsequently annealed at 450 °C. The length of milling of precursor particles contained in the coating formulations determined properties of deposited layers. were examined for. The additivity of the individual compositions was also observed. The structure of the layers was observed by optical microscopy and scanning electron microscopy (SEM), their composition by the X-ray diffraction (XRD) and their thickness and surface roughness was defined by contact profilometry. Photoelectrochemical properties of the prepared layers were also investigated by linear voltametry and chronoamperometry.

Using the Navier-Stokes equations along with a continuity equation, a one-dimensional model is developed to describe the spin coating process of thin polymeric films. The resulting model is a system of a parabolic partial differential equation coupled with an integral equation as well as with an ordinary differential equation describing the motion of a moving boundary. Viscosity and diffusivity are allowed to be varied in the model. To be able to perform the finite element approximation of the model equations, the moving boundary is fixed. Then the finite element method is applied along with the so called Method of Lines resulting in a semi-discrete problem, a large system of ordinary differential equations which is then solved with MATLAB. We present an existence and uniqueness result what concerns the semi-discrete solutions. Finally, we illustrate numerically the behavior of the solutions to our model.

>Magister Scientiae - MSc / Environmentally friendly photovoltaic devices make use of solar radiation as the energy source to generate electricity. Organic solar cells (OSCs) have been making headway in the last decade due to their cost-effectiveness and potential application in flexible devices. One of the disadvantages of OSCs is the short lifetime of the charge carriers, where the various interfaces that are present in the material play a significant role. In the inverted organic solar cell (IOSC), electrons are injected into the transparent conducting oxide, whereby the electrode alignment is reversed compared to the conventional structure. Nanosized zinc oxide (ZnO) thin-films with nanoridges/ripples embedded on the surface of the thin-film can be used as an electron transport/hole-blocking layers in inverted organic solar cells to enhance light-capturing by the active layer of the solar cell.

Metal-Organic Frameworks (MOFs) are an important class of materials that are gaining increasing relevance for many fields including energy storage, CO2 capture, photovoltaics, and catalysis. MOF mediated synthesis (MOFMS) is the decomposition of a MOF to form an amorphous carbon material decorated with metal nanoparticles. MOF thin films are an area where MOFMS has not been thoroughly explored, yet they are likely to be industrially relevant due to their potential application as highly dispersed, sinter resistant supported catalysts. In this work, we have developed a method for the growth of copper- and zinc-based MOF thin films on silicon- and aluminum- based wafers. A series of decomposition processes have allowed us to determine which variables can be used to design the final nanoparticle decorated product. These variables include oxygen/nitrogen ratios, the impact of water in atmospheric decomposition, substrate composition, and reduction under hydrogen. A high degree of control over the final thin film product is achieved, with the ability to make a carbon supported CuO structure with features between 1-5 nm, or CuO nanoparticles ranging from 10-500 nm, as well as finely tuned carbon/Cu ratios. Partially reduced Cu nanoparticles were obtained and used in the dehydrogenation of ethanol and methanol. Finally, alloyed nanoparticles were obtained through the growth and decomposition of Cu/Zn mixed-metal MOFs. Understanding the growth and decomposition variables as applied to supported MOF-thin films will enable development of next generation nanomaterials for use in catalysis.

Im Rahmen dieser Arbeit wurde ein Niedertemperatur Sol-Gel Spin-Coating Verfahren entwickelt, mit dem sich Metalloxide und -fluoride in Form von Nanometer-dicken Schichten abscheiden lassen. Ziel dieses Verfahrens ist die Herstellung von anti- (AR) und hoch reflektierenden (HR) Schichtsystemen, die aus einem alternierenden Aufbau von niedrig brechenden und hoch brechenden Materialien bestehen. Zur Darstellung der Metallfluoride wurde dabei eine neuartige nichtwässrige Sol-Gel Synthese ausgehend von Metallalkoxiden und in Alkoholen einkondensiertem Fluorwasserstoff angewendet. Die abgeschiedenen Schichten, die bei 100 °C getrocknet wurden, sind mit REM, TEM und AFM auf ihre morphologische Struktur, mit EDX und XPS auf ihre chemische Zusammensetzung und mit Ellipsometrie und UV-vis Transmissionsspektroskopie auf ihre optischen Eigenschaften hin untersucht worden. Mit diesem Verfahren gelang die Präparation von homogenen MgF2- und TiO2-Schichten mit geringen Rauheiten (Ra < 2,0 nm) auf Si- und SiO2-Substraten. Die MgF2-Schichten haben einen Brechungsindex von n500 = 1,36. Die TiO2-Schichten weisen einen Brechungsindex von n500 = 2,05 auf. Die Dicken der MgF2- und TiO2-Schichten sind zwischen 25 nm und 500 nm einstellbar. Durch einen alternierenden Aufbau von MgF2- und TiO2-Schichten gelang außerdem erstmalig die Herstellung von Metallfluorid- und Metalloxid-basierten Schichtsystemen über einen Niedertemperatur Sol-Gel Prozess. Mit Hilfe der bestimmten optischen Eigenschaften der MgF2- und TiO2-Einzelschichten wurden einfache AR und HR Designs entwickelt und aufgebaut. Die Transmissionsspektren der Designs und der jeweiligen Schichtsysteme zeigten dabei gute Übereinstimmungen, gleiches galt für die mit Hilfe der Spektralellipsometrie aufgenommenen Reflexionsspektren. In dieser Arbeit konnte erstmals gezeigt werden, dass sich das Niedertemperatur Sol-Gel Verfahren prinzipiell zur Herstellung von einfachen AR und HR Schichtsystemen eignet. / This work deals with the development of a low temperature sol-gel spincoating process for thin films with thicknesses in the nanometer range based on metal oxides and metal fluorides. Optical films such as anti-reflective (AR) or high reflective coatings are of much interest and consist of alternating dielectric layers of low and high refractive index materials. Regarding the general procedure for the metal fluorides a novel nonaqueous sol-gel synthesis starting from metal alkoxides and alcohol-dissolved HF was used. The coatings were dried and calcined at 100 °C. The morphology of these films was characterised with REM, TEM and AFM. EDX and XPS were used to indentify the chemical composition and ellipsometry and UV-vis spectroscopy to determine the optical properties of the films. This new process allows the preparation of homogeneous magnesium fluoride and titanium dioxide layers with low roughness (Ra < 2.0 nm) on Si and SiO2 substrates. The thicknesses of the MgF2 and TiO2 single layers were adjustable between 25 nm and 500 nm depending on the number of coating steps and on the concentration of the used sols. The MgF2 layers had a refractive index of n500 = 1.36 and the TiO2 layers a refraction index of n500 = 2.05. For the first time, an alternating metal fluoride and oxide multilayer system was produced with a low temperature sol-gel method (consisting of MgF2 and TiO2). Based on the determined optical constants of the MgF2 and TiO2 single layers, AR and HR multilayer systems were calculated and fabricated. The transmission spectra of the designs and the corresponding multilayer were in good agreement. Similar results were obtained with the reflection spectra determined with spectral ellipsometry. The presented investigations were able to show that the developed low temperature sol-gel process using the spin-coating technique is suitable for the preparation of simple AR and HR multilayer systems.