Nesse trabalho foram fabricados filmes finos de TiO2 por RF magnetron sputtering reativo sobre substrato de silício (1 0 0). A pressão parcial do oxigênio na câmara foi variada de 5 a 100% em relação ao argônio. Após a deposição os filmes foram submetidos a tratamento térmico em atmosfera de oxigênio. A estequiometria dos filmes e o perfil de profundidade foram obtidos por RBS. A estrutura cristalina foi obtida por XRD. As propriedades ópticas foram obtidas por interferometria e reflectância e as elétricas por meio das curvas C-V. Os valores de espessura dos filmes sem tratamento térmico aumentaram aproximadamente 41% com o aumento do oxigênio na câmara de deposição. Essa variação está ligada ao aumento da eficiência do sputtering do alvo. Os índices de refração dos filmes sem tratamento térmico se mantiveram dentro de um intervalo de aproximadamente 2,3 a 2,4. A diminuição do band gap com o tratamento térmico é consequência da mudança de fase cristalográfica de anatase para rutila. A estequiometria TiOx dos filmes antes do tratamento térmico apresentaram valores de x entre 2,0 e 2,4. A espessura em TFU dos filmes aumentou com o percentual de oxigênio na câmara. As amostras que receberam tratamento térmico apresentaram difusão de titânio na interface do substrato e incorporação de oxigênio no filme. Os valores da constante dielétrica aumentaram com o percentual de oxigênio na câmara, em contraposição com o efeito do tratamento térmico que diminuiu o valor. Todos os resultados observados são coerentes do ponto de vista da mudança de fase anatase rutila e aumento do percentual de oxigênio na câmara. / In this work thin films of TiO2 were produced by reactive RF magnetron sputtering on silicon substrate (1 0 0). The oxygen partial pressure in the chamber was varied from 5 to 100% in relation to argon. After deposition the films were submitted to thermal treatment under an oxygen atmosphere. The stoichiometry of the films and the depth profile were obtained by RBS. The crystal structure was obtained by XRD. Its optical properties were obtained by interferometry and reflectance and the electrical were obtained by means of the C-V curves. The thickness values of films without heat treatment increased approximately 41% with the increase of oxygen in the deposition chamber. This variation is linked to the increased sputtering efficiency of the target. The refractive indexes of films without heat treatment remained within a range of about 2.3 to 2.4. The decrease of the band gap with the heat treatment is a consequence of the change of crystallographic phase from anatase to rutile. The TiOx stoichiometry of the films before the heat treatment showed values of x between 2.0 and 2.4. The TFU thickness of the films increased with the percentage of oxygen in the chamber. The samples that received heat treatment shows diffusion of titanium at the interface of the substrate and incorporation of oxygen in the film. The values of the dielectric constant increased with the percentage of oxygen in the chamber, as opposed to the effect of the thermal treatment that decreased the value. All the results observed are consistent from the point of view of the anatase - rutile phase transition and the increase in the oxygen percentage in the chamber.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-05-16T17:11:07Z No. of bitstreams: 1 ChristianCarvalho.pdf: 1874919 bytes, checksum: 3c4ecd041d9c80194ae2c47a229bbd6a (MD5) / Made available in DSpace on 2017-05-16T17:11:07Z (GMT). No. of bitstreams: 1 ChristianCarvalho.pdf: 1874919 bytes, checksum: 3c4ecd041d9c80194ae2c47a229bbd6a (MD5) Previous issue date: 2016-03-31 / Fundação de Amparo à Pesquisa e ao Desenvolvimento Científico e Tecnológico do Maranhão (FAPEMA) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPQ) / The use of biodiesel/diesel mixtures out of the quality standards specified by the National Agency of Petroleum and Natural Gas and Biofuels - ANP can be harmful to the environment and automotive engines. Therefore, it is important to develop methodologies capable of certifying the commercial quality of such products. In such context, this project aims to design a low-cost sensor to the quantification of the biodiesel content in biodiesel / diesel pseudo-binary blends based on the dielectric constant as a response. Thus, pseudo-binary samples were prepared using soybean or babassu methyl biodiesel with commercial diesel. The dielectric measurements were performed using a LCR meter operating in parallel circuit. In this way, a voltage of 1.0 V, frequency ranging from 100 Hz to 2000 Hz and a pitch of 100 Hz were employed. The dielectric profile of diesel and biodiesel showed remarkable variations in the frequency range of 100-300 Hz and less intense changes in under 400 and 2000 Hz, which confirms greater system stability in this measurement range. The results obtained by ANOVA of pure soybean biodiesel, pure babassu biodiesel and diesel oil showed that there was no significant difference between data treatment at the 95% significance level, once the Fcalculate was lower than the Fcritical. The frequency of 1000 Hz was adopted in biodiesel analysis of content in diesel, as it was verified that the system had a higher stability at this frequency. The correspondent values of dielectric constant demonstrate regularity and stability as well as a precision between the values found. Observing the values of the dielectric constants as a function of the percentage of biodiesel in the diesel, it was possible to plot the correlation curve for a linear model. Finally, according to the Kruskal-Wallis test reinforces the thesis that measuring dielectric constants (K) can be used to determine the concentration of biodiesel in mineral diesel. / A utilização de misturas biodiesel/diesel fora dos padrões especificados pela Agência Nacional de Petróleo e Gás Natural e Biocombustíveis – ANP podem ser prejudiciais ao meio-ambiente e causar prejuízos aos donos de veículos automotivos. Neste sentido, torna-se necessário o desenvolvimento de novas metodologias capazes de certificar a qualidade destes produtos no Brasil. O presente trabalho teve por objetivo desenvolver um sensor de baixo custo para determinar o teor de biodiesel em misturas pseudo-binárias biodiesel/diesel, utilizando constante dielétrica como resposta. Para tanto, foram preparadas misturas utilizando biodieseis metílicos de soja e/ou babaçu e óleo diesel A comercial. As medidas dielétricas foram realizadas em um medidor LCR configurado para funcionar com o circuito em paralelo. Desta forma, foram empregadas tensão de 1,0 V, frequência de 100 Hz - 2000 Hz e um passo de 100 Hz. O perfil dielétrico do óleo diesel e dos biodieseis demonstrou variações acentuadas no intervalo de frequência de 100 - 300 Hz e alterações de menor intensidade entre as frequências de 400 a 2000 Hz, confirmando maior estabilidade do sistema nessa faixa. Os resultados obtidos por ANOVA do biodiesel de soja puro, biodiesel de babaçu puro e o óleo diesel, demostraram que não há diferença significativa entre os tratamentos ao nível de significância de 95%, visto que o Fcalculado foi menor que o Fcrítico. A frequência de 1000 Hz foi adotada nas análises do teor de biodiesel no diesel, pois verificou-se maior estabilidade do sistema nessa frequência. Os valores de constante dielétrica em questão demonstram regularidade e estabilidade, além de uma precisão entre os valores encontrados. Observando os valores das constantes dielétricas em função da porcentagem de biodiesel no diesel, foi possível traçar a curva de correlação para um modelo linear. Por fim, o teste de Kruskal-Wallis demonstrou que a tese de que as medidas constantes dielétricas (𝐾) podem vir a ser utilizadas para determinar a concentração de biodiesel no diesel mineral.

The properties of composite materials in which spherical inclusions are embedded in a matrix of some kind, have been studied for many decades and many analytical models have been developed which measure these properties. There has been a steady progression in the complexity of models over the years, providing greater insight into the nature of these materials and improving the accuracy in the measurement of their properties. Some of the properties with which this thesis is concerned are, the elastic, thermal and electrical properties of such composites. The size of the spherical inclusion which acts as the reinforcing phase, has a major effect on the overall properties of composite materials. Once an inclusion is embedded into a matrix, a third region of different properties between the inclusion and matrix is known to develop which is called the interphase. It is well known in the composite community that the smaller the inclusion is, the larger the interphase region which develops around it. Therefore, with the introduction of nanoparticles as the preferred reinforcing phase for some composites, the interphase has a major effect on its properties. It is the aim of this thesis to consider the role of the interphase on the properties of composites by modeling it as an inhomogeneous region. There is much scientific evidence to support the fact that the interphase has an inhomogeneous nature and many papers throughout the thesis are cited which highlight this. By modeling the inhomogeneous properties by arbitrary mathematical functions, results are obtained for the various properties in terms of these general functions. Some specific profiles for the inhomogeneous region are considered for each property in order to demonstrate and test the models against some established results.

<p>Due to the constantly decreasing dimensions of electronic devices, the conventional dielectric material in transistors and capacitors, SiO₂, has to be replaced by a material with higher dielectric constant. Some of the most promising candidates are tantalum oxide,Ta₂O₅, zirconium oxide, ZrO₂ and hafnium oxide, HfO₂.</p><p>This thesis describes new chemical vapour deposition (CVD) and atomic layer deposition (ALD) processes for deposition of Ta₂O₅, ZrO₂ and HfO₂ using the metal iodides as starting materials. The layer-by-layer growth in ALD was also studied in real time with a quartz crystal microbalance (QCM) to examine the process characteristics and to find suitable parameters for film deposition.</p><p>All the processes presented here produced high-purity films at low deposition temperatures. It was also found that films deposited on Pt substrates generally crystallise at lower temperature, or with lower thickness, than on silicon and single-crystalline oxide substrates. Films grown on MgO(001) and α-Al₂O₃(001) substrates were strongly textured or epitaxial. For example, monoclinic HfO₂ deposited on MgO(001) were epitaxial for deposition temperatures of 400-500 C in ALD and 500-600 C in CVD. Electrical characterisation showed that the crystallinity of the films had a strong effect on the dielectric constant, except in cases of very thin films, where the dielectric constant was more dependent on layer thickness.</p>

Due to the constantly decreasing dimensions of electronic devices, the conventional dielectric material in transistors and capacitors, SiO2, has to be replaced by a material with higher dielectric constant. Some of the most promising candidates are tantalum oxide,Ta2O5, zirconium oxide, ZrO2 and hafnium oxide, HfO2. This thesis describes new chemical vapour deposition (CVD) and atomic layer deposition (ALD) processes for deposition of Ta2O5, ZrO2 and HfO2 using the metal iodides as starting materials. The layer-by-layer growth in ALD was also studied in real time with a quartz crystal microbalance (QCM) to examine the process characteristics and to find suitable parameters for film deposition. All the processes presented here produced high-purity films at low deposition temperatures. It was also found that films deposited on Pt substrates generally crystallise at lower temperature, or with lower thickness, than on silicon and single-crystalline oxide substrates. Films grown on MgO(001) and α-Al2O3(001) substrates were strongly textured or epitaxial. For example, monoclinic HfO2 deposited on MgO(001) were epitaxial for deposition temperatures of 400-500 C in ALD and 500-600 C in CVD. Electrical characterisation showed that the crystallinity of the films had a strong effect on the dielectric constant, except in cases of very thin films, where the dielectric constant was more dependent on layer thickness.

The objective of my thesis was to develop novel techniques and methods to probe the dielectric properties of biomembranes in air and their natural environment - liquid solution. The dielectric constant ε(r) of biomembranes is a parameter especially important in cell electrophysiology as it ultimately determines the ion membrane permeability, the membrane potential formation or the action potential propagation velocity, among others. However, no technique is able to provide this quantity with the required nanoscale spatial resolution and in electrolyte solution. AFM is an extremely versatile tool to investigate electric properties at the nanoscale, and hence constitutes a good candidate technique to approach the quantification of the nanoscale dielectric properties of biomembranes. Although a few AFM techniques exist, capable of investigating polarization properties, it remains difficult to extract quantitative values of εr from the measurements, especially in liquid environment. One reason for this is on the instrumental side, since for studies at the nanoscale very small quantities have to be measured, that can be easily overwhelmed by electronic noise as it maybe for example the case in current sensing based techniques. Electrostatic Force sensing techniques may in principle have an advantage here, since the used cantilevers for force detection are extremely sensitive and naturally, undesired nonlocal electrical signals from the cantilever are suppressed. Another important aspect is attributed to a lack of sufficiently precise quantitative models to relate measured force with the dielectric constant value of the sample. Indeed, for measurements on insulating substrates like mica or glass that are sometimes required for biological samples, still no quantitative model is available. Moreover, successful measurements of dielectric properties in liquid media, that is fundamental for the functionality of some biological samples, has not been shown until now. As consequence of the existing limitations for quantitative dielectric imaging the objectives of this work were to extend the quantitative capabilities of Electrostatic Force Microscopy to image the dielectric constant of biomembranes with nanoscale spatial resolution. In particular, the three objectives I addressed in the work are: 1. To evaluate the possibility to perform quantitative dielectric measurement on biomembranes on metallic substrates and in air with Electrostatic Force Microscopy that may offer higher precision with respect to current sensing techniques. 2. To extend the applicability of quantitative dielectric measurement to the case of thick insulating substrates in order to facilitate its use with biomembranes that cannot be prepared on metallic substrates. 3. To develop a setup for dielectric imaging in liquid environment based either on current detection or on the principles of electrostatic force microscopy. Finally to perform nanoscale dielectric measurements on bio-membranes in their natural liquid environment. How each of these objectives could be reached is detailed in my thesis. / El objetivo de mi tesis era desarrollar nuevas técnicas y métodos para medir las propiedades dieléctricas de biomembranas en aire y en su medio natural, es decir, en solución líquida. La constante dieléctrica (εr) de las biomembramas es un parámetro especialmente importante en la electrofisiología celular, ya que fundamentalmente determina la permeabilidad iónica de la membrana, la formación del potencial de membrana o la velocidad de propagación del potencial de acción, entre otros. El AFM es una herramienta extremadamente versátil para investigar propiedades eléctricas a nanoescala, y por ello constituye una buena técnica candidata para la cuantificación de las propiedades dieléctricas de las biomembranas a nanoescala. Aunque existen algunas técnicas basadas en el AFM capaces de investigar las propiedades de polarización, continúa siendo difícil extraer valores cuantitativos de εr de las medidas, especialmente en medio líquido. Una de las razones radica en la parte instrumental, ya que para los estudios en la nanoescala tienen que medirse cantidades muy pequeñas, y este proceso puede verse entorpecido por ruido electrónico como puede ser el caso, por ejemplo, en las técnicas basadas en la detección de corriente eléctrica. En principio, las técnicas de detección de fuerza electroestática disponen aquí de una ventaja, ya que las sondas utilizadas para la detección de la fuerza son extremadamente sensibles y naturalmente se suprimen señales eléctricas no locales y no deseadas. Otro aspecto importante se atribuye a la falta de modelos cuantitativos suficientemente precisos para relacionar la fuerza medida con el valor de la constante dieléctrica de la muestra. En realidad, para realizar medidas en sustratos aislantes como son la mica o el vidrio, que a veces son necesarios para muestras biológicas, todavía no se dispone de ningún modelo cuantitativo. Por otra parte, hasta ahora no se han publicado medidas de propiedades dieléctricas en medio líquido, que para algunas muestras biológicas es fundamental para mantener la funcionalidad. Como consecuencia de las limitaciones existentes de las medidas dieléctricas, el objetivo de este trabajo fue extender las capacidades cuantitativas de la Microscopía de Fuerzas Eletroestáticas para hacer imágenes dieléctricas de biomembranas con resolución espacial a nanoescala en substratos conductores, aislantes y en medio líquido.

Supercapacitors are well known for their improvised power density compared to batteries. Ongoing research is mainly focused on improving the energy density of supercapacitors by using different electrode material nanocomposites. The recent research has revealed that graphene (G)-polyaniline (PANI) nanocomposite could be a promising material for supercapacitor applications. The supercapacitor is also associated with self-leakage current regardless of any electrode material. The main objectives of the project are to: (i) synthesize highly fabricate supercapacitor based of G-PANI electrode; (ii) improve the energy density of supercapacitor by applying ultrathin monolayer/monolayers film electrode surface. It is crucial to either improve or retain the effective capacitance of the dielectric film. The dielectric material chosen is polyvinylidene fluoride (PVDF) due to its dielectric constant and electrochemical properties. Langmuir-Schaefer (LS) technique is used to deposit the PVDF film onto the substrate. The optical properties of electrode materials were measured by UV-vis spectrophotometer. The surface morphology of the fabricated electrode material has been investigated using scanning electron microscopic (SEM) and atomic force microscopic (AFM) studies. The supercapacitor with and without dielectric layer have been studied using cyclic voltammetry, charging and discharging, and electrochemical impedance techniques, respectively. The specific capacitance has been found to increase by application of one monolayer of PVDF film of G-PANI electrode. However, the LS film of PVDF does not show the minimization of leakage current but revealed an increase in the specific capacitance due to enhancement in surface area associated with the electrode besides PVDF is also an electrochemical active material. The electrochemical investigation of various layers of PVDF on G-PANI in symmetric and asymmetric supercapacitor configuration has been presented in thesis. The future scope of the project could be designing the electrode with various number of layers of dielectric material that could reduce the leakage current, and retaining the specific capacitance of G-PANI nanocomposite electrodes.

Inadequate compaction of a soil subgrade can lead to detrimental outcomes that are not only costly but dangerous to the general public. To avoid this, quality control (QC) devices such as the nuclear density gauge (NDG) are currently being used to monitor the compaction and moisture content of soil subgrades. However, regulatory concerns associated with the NDG have encouraged federal and state agencies, as well as the heavy civil construction industry to consider non-nuclear devices for QC testing of compacted soils. One such non-nuclear device is the Soil Density Gauge (SDG), which utilizes electromagnetic wave propagation to obtain soil properties such as wet unit weight and moisture content. This research shows that through using soil-specific trend lines, the SDG has the capability of obtaining an equivalent NDG wet unit weight. Alongside the SDG, two dielectric moisture probes were also evaluated and through a calibration process on compacted soils, a general moisture content trend line was developed. This general moisture content trend line related outputted volumetric moisture contents from the moisture probes to gravimetric moisture contents. Field data were then plotted along with the general moisture content trend line to show that these devices have the potential of predicting gravimetric moisture contents. By combining the results of the SDG and moisture probe analyses, graphs were then developed that relate SDG wet unit weights to NDG dry unit weights using soil and moisture-specific trend lines.

Le développement des mémoires dynamiques (DRAM) à haute performance basées sur la structure métal-isolateur-métal (MIM) nécessite de remplacer la couche de dioxyde de silicium par des matériaux diélectriques à haute permittivité diélectrique. L'utilisation de ces isolants dits high-k permet de réduire la taille du dispositif DRAM tout en conservant une densité de capacité élevée et un faible courant de fuite pour diminuer la fréquence de rafraichissement. Parmi les nombreux matériaux high k, le dioxyde de titane (TiO2) est l'un des candidats les plus prometteurs en raison de sa constant diélectrique relativement élevée pouvant atteindre 170 dans le TiO2 cristallisé en phase rutile. De plus, il est possible d’obtenir cette phase à basse température par le procédé ALD (< 250 °C) si le dépôt est réalisé sur un substrat RuO2 (phase rutile) grâce à une très faible différence de paramètres de maille entre les deux matériaux. L'objectif principal de cette thèse est d'étudier les mécanismes des réactions chimiques qui se produisant à l'interface RuO2/TiO2 lors du dépôt et leur influence sur les propriétés structurales et diélectriques du film TiO2, en particulier l'influence des espèces oxydantes, le plasma O2 et le H2O. L’influence des électrodes supérieure et inferieures sur les propriétés électriques et structurales de TiO2 a également été étudiée. Ensuite, la constante diélectrique, la conductivité ac et la tangente de perte des structures MIM à base d’oxyde de titane dopé aluminium ont été étudiés dans une gamme de fréquences large bande, de 1 Hz à 2 GHz. Enfin, la réalisation des MIM tridimensionnelles (3D) utilisant un substrat de silicium structuré en réseaux des trous coniques denses a été démontrée. Les structures MIM 3D réalisées ont permis d’augmenter sensiblement la densité de capacité tout en gardant de bonnes performances en termes de courant de fuite. / The development of high performance dynamic random access memory (DRAM) based on metal-insulator-metal (MIM) structure made it necessary to replace the conventional silicon dioxide layer by dielectric materials with high dielectric constants. The use of these so-called high-k insulators allows aggressive scaling of DRAM devices while keeping high capacitance density and, more importantly, low leakage current. Among the numerous high k dielectrics, titanium dioxide (TiO2) is one of the most attractive candidate due to its rather high dielectric constant (k). Rutile TiO2 is the interesting phase due to its high dielectric constant and the possibility to deposit this phase at low temperature by ALD (< 250 °C) by using RuO2 substrate thanks to a very small lattice mismatch between the two materials. The main objective of this thesis is to investigate the surface chemical reactions mechanisms at the RuO2/TiO2 interface and their influence on the ALD TiO2 film properties, especially the influence of oxidizing species, namely, H2O or O2 plasma. The influence of bottom and top electrode on electrical and structural proprieties of TiO2 MIM structure was also studied. Then, the dielectric constant, the ac conductivity and the loss tangent of aluminum doped titanium oxide are measured through a wide band frequency range, from 1 Hz to 2 GHz. Finally, the feasibility of three-dimensional (3D) MIM structures was studied by using dense array of truncated conical holes etched in a silicon substrate. The 3D MIM capacitors showed a large increase in the capacitance density while retaining very good electrical properties especially a leakage current comparable to planar MIM devices.

Doctor of Philosophy / Department of Chemistry / Daniel A. Higgins / This dissertation describes the application of wide-field single-molecule fluorescence microscopy techniques to investigations of DNA-surface interactions on chemically graded organosilane surfaces. The adsorption and desorption behaviors of double-stranded (ds) plasmid DNA along the amino-trimethoxysilane and octyl-trichlorosilane gradients were explored as a function of solution pH, solution ionic strength and surface properties. The results provide an improved fundamental understanding of DNA interactions with different surfaces and are certain to aid in the development and advancement of DNA-based biological and biomedical devices. Three distinct experiments were performed in completion of the work for this dissertation. In the first study, total internal reflection fluorescence (TIRF) microscopy was employed to study DNA interactions with aminosilane gradient surfaces under relatively acidic and basic environments. Electrical potentials were applied to assist DNA adsorption and desorption. The single-molecule data clearly showed that DNA capture and release was achieved on the monolayer and submonolayer coated regions of the aminosilane gradient surface under relatively basic pH conditions, with the help of an electrical potential. Meanwhile, DNA adsorption was found to be quasi-reversible on the multilayers at the high aminosilane end of the gradient in the relatively acidic solution. The results of these studies demonstrate the importance of manipulating the electrostatic interactions of DNA with charged surfaces in order to achieve DNA capture and release. The fundamental knowledge of the DNA-surface interactions gained in these studies will be helpful in diverse fields ranging from the layer-by-layer assembly of polyelectrolyte-based thin films to the selective electronic sensing of charged biomolecules. In the second study, the local dielectric properties of the least polar environments in dsDNA were assessed by using the solvatochromic dye, nile red, as a polarity-sensitive probe. TIRF spectroscopic imaging methods were employed in these studies. Although the dielectric constant within the least polar regions of dsDNA was previously predicted by theoretical and computational methods, no experimental measurements of its value had been reported to date. The results provide important knowledge of the factors governing the polarity of DNA microenvironments to which intercalators bind, and provide vital experimental support for the values determined in computational studies. In the third study, TIRF microscopy and single molecule tracking methods were employed to study DNA interactions with an opposed two-component C8-silane and aminosilane gradient surface as a function of solution pH. The mobility of surface-adsorbed DNA molecules was explored and quantified in these studies. The preliminary results further demonstrated the importance of electrostatic interactions over hydrophobic interactions in governing the adsorption of DNA to surfaces. The mobility of surface-adsorbed DNA was found to be largely independent of position along the two-component gradient. These studies were originally undertaken as a route to observation of cooperative effects that are believed to govern DNA-surface binding. Unfortunately, no clear evidence of cooperative effects was observed at the mixed regions of the two-component gradient surface.