Neste trabalho foi estudada a atividade eletrocatalítica dos eletrocatalisadores nanoestruturados de Ru, Ir, Hf ou La suportados em carbono Printex 6L frente à Reação de Redução de Oxigênio (RRO) em meio ácido. Inicialmente analisou-se a influência do Método de Impregnação e dos Precursores Poliméricos (MPP), também conhecido como Pechini para os eletrocatalisadores RuO2/C e IrO2/C. Ficou evidente neste estudo, que os materiais obtidos pelo MPP apresentaram uma maior eficiência de corrente para a eletrogeração de H2O2 quando comparado ao método da Impregnação. Na etapa seguinte, os eletrocatalisadores HfO2/C e LaONO3/C foram preparados apenas pelo MPP. As propriedades estruturais, morfológicas e de superfície foram investigadas por meio das técnicas de caracterização DRX, FRX, MET, XPS e TG. De acordo com os dados de DRX e MET, verificou-se que o método de incorporação do metal no carbono Printex 6L favoreceu a formação dos óxidos nanoestruturados. Ademais, foi verificado que os eletrocatalisadores obtidos pelo método de Pechini apresentam menores tamanho de cristalitos (1 a 5 nm), melhor distribuição dos óxidos sobre a matriz de carbono (menos aglomerados) e menores tamanhos de partículas. O comportamento eletroquímico dos eletrocatalisadores foi avaliado através das voltametrias lineares (curvas de polarização) obtidas pelo eletrodo de disco anel rotatório (RRDE). Os resultados obtidos pelas voltametrias lineares, cálculos de eficiência de corrente de H2O2 (H2O2 %), número total de elétrons trocados (nt) e de Koutecký-Levich mostraram que a incorporação dos eletrocatalisadores (Ru e Ir) no carbono Printex 6L obtidos por ambos os métodos de síntese influenciaram negativamente na eletrogeração de H2O2. Neste caso, os eletrocatalisadores de Ru e Ir apresentaram uma tendência ao mecanismo via 4 elétrons, ou seja, geração de H2O como produto final da RRO. Os resultados mostraram ainda que os eletrocatalisadores contendo maiores teores de Hf, apresentaram maiores eficiência de corrente para H2O2 quando comparado ao carbono Printex 6L, uma vez que o catalisador contendo 15 % de Hf apresentou valores de eficiência de corrente de H2O2 próximos a 80 % e número de elétrons de 2,4. Além disso, foi observado também um deslocamento no potencial de aproximadamente 200 mV para valores mais positivos, o que significa um menor consumo energético em termos de eletrogeração de H2O2. Para os eletrocatalisadores à base de La, a amostra contendo 7% apresentou uma melhor eficiência de corrente de H2O2, com valores próximos a 87% e número de elétrons de 2,3, além de um deslocamento do potencial de aproximadamente 250 mV para valores mais positivos. Pode-se inferir então, que os eletrocatalisadores de Hf e La obtidos pelo método de Pechini são promissores para utilização em Eletrodos de Difusão Gasosa (EDG) visando a eletrogeração in situ de H2O2, visto que apresentam uma tendência a mecanismo via 2 elétrons. / In the present work, the electrocatalytic activity of nanostructured electrocatalysts based on Ru, Ir, Hf or La supported in Printex L6 front of Oxygen Reduction Reaction (ORR) in an acid medium were studied. Initially, the influence of impregnation methods and polymeric precursors (MPP), also known as Pechini for the electrocatalysts RuO2/C and IrO2/C, was analyzed. It was evidenced in this study, that the materials obtained by MPP presented bigger efficiency for H2O2 electrogeneration when compared to the impregnation method. In the following stage, the electrocatalysts HfO2/C and LaONO3/C were prepared only by MPP. The structural properties and surface morphology were investigated by means of the characterization techniques DRX, FRX, TEM, XPS and TG. According to the XRD and TEM data, it was found that the method of metal incorporation in Printex 6L carbon promoted the formation of nanostructured oxides. Moreover, it was verified that the electrocatalysts obtained by Pechini\'s method presented smaller crystallite size (1 to 5 nm), better distribution of the oxides on the carbon matrix (fewer clusters) and smaller particle sizes. The electrochemical behavior of the electrocatalysts were evaluated by linear voltammetry (polarization curves) obtained by rotating ring-disk electrode (RRDE). The results obtained by linear voltammetry, calculations of current efficiency of H2O2 (H2O2 %), total number of exchanged electrons (nt) and of Koutecký-Levich showed that the incorporation of the electrocatalysts (Ru and Ir) in Printex 6L carbon obtained by both methods of synthesis influenced negatively on the electrogeneration of H2O2. In that case, the Ru and Ir electrocatalysts showed a tendency to a 4 electrons mechanism, that is, generation of H2O as final product of the ORR. The results also showed that the electrocatalysts containing higher Hf content, presented higher current efficiency for H2O2 when compared to carbon Printex L6, since that the catalyst containing 15% of Hf presented values of current efficiency for H2O2 around 80% and number of electrons of 2.4. Furthermore, a potential displacement for positive values of approximately 200 mV was also observed which means lower energy consumption in terms of H2O2 electrogeneration. For the La based electrocatalysts, the sample containing 7% showed better current efficiency for H2O2, with values near 87% and number of electrons of 2.3, besides a potential displacement of approximately 250 mV for more values positive. It can be inferred that the Hf and La electrocatalysts obtained by Pechini\'s method are promising for use in Gas Diffusion Electrodes (GDE) aiming in situ electrogeneration of H2O2, since they exhibit a tendency to a mechanism via 2 electrons.

<p>Many materials exhibit interesting and novel properties when prepared as thin films. Thin film metal oxides have had an impact on the technological progress of the microelectronics mainly due to their electrical and optical properties. Since the future goes towards the nanometre scale there is an increasing demand for thin film deposition processes that can produce high quality metal oxide films in this scale with high accuracy.</p><p>This thesis describes atomic layer deposition of Ta₂O₅, HfO₂ and SnO₂ thin films and chemical vapour deposition of SnO₂ thin films. The films have been deposited by employing metal iodides and oxygen as precursors. All these processes have been characterised with regards to important processing parameters. The films themselves have been characterised by standard thin film analysing techniques such as x-ray diffraction, scanning electron microscopy, atomic force microscopy and transmission electron microscopy. The chemical and physical properties have been coupled to critical deposition parameters. Furthermore, additional data in the form of electrical and gas sensing properties important to future applications in the field of microelectronics have been examined.</p><p>The results from the investigated processes have shown the power of the metal iodide based atomic layer deposition (ALD) and chemical vapour deposition (CVD) processes in producing high quality metal oxide thin films. Generally no precursor contaminations have been observed. In contrast to metal chloride based processes the metal iodide processes produces films with a higher degree of crystalline quality when it comes to phase purity, roughness and epitaxy. The use of oxygen as oxidising precursor allowed depositions at higher temperatures than normally employed in water based ALD processes and hence a higher growth rate for epitaxial growth was possible.</p>

Many materials exhibit interesting and novel properties when prepared as thin films. Thin film metal oxides have had an impact on the technological progress of the microelectronics mainly due to their electrical and optical properties. Since the future goes towards the nanometre scale there is an increasing demand for thin film deposition processes that can produce high quality metal oxide films in this scale with high accuracy. This thesis describes atomic layer deposition of Ta2O5, HfO2 and SnO2 thin films and chemical vapour deposition of SnO2 thin films. The films have been deposited by employing metal iodides and oxygen as precursors. All these processes have been characterised with regards to important processing parameters. The films themselves have been characterised by standard thin film analysing techniques such as x-ray diffraction, scanning electron microscopy, atomic force microscopy and transmission electron microscopy. The chemical and physical properties have been coupled to critical deposition parameters. Furthermore, additional data in the form of electrical and gas sensing properties important to future applications in the field of microelectronics have been examined. The results from the investigated processes have shown the power of the metal iodide based atomic layer deposition (ALD) and chemical vapour deposition (CVD) processes in producing high quality metal oxide thin films. Generally no precursor contaminations have been observed. In contrast to metal chloride based processes the metal iodide processes produces films with a higher degree of crystalline quality when it comes to phase purity, roughness and epitaxy. The use of oxygen as oxidising precursor allowed depositions at higher temperatures than normally employed in water based ALD processes and hence a higher growth rate for epitaxial growth was possible.

Since metal-oxide-semiconductor (MOS) devices have been adopted into integrated circuits, the endless demands for higher performance and lower power consumption have been a primary challenge and a technology-driver in the semiconductor electronics. The invention of complementary MOS (CMOS) technology in the 1980s, and the introduction of voltage and physical dimension scaling in the 1990s would be good examples to keep up with the everlasting demands. In the 2000s, technology continuously evolves and seeks for more power efficiency ways such as high-k dielectrics, metal gate electrodes, strained substrates, and high mobility channel materials. As a gate dielectric, silicon dioxide (SiO₂), most widely used in CMOS integrated circuits, has many prominent advantages, including a high quality interface (e.g. Dit ~ low 1010 cm-2eV-1), a good thermal stability in contact with silicon (Si), a large energy bandgap and the large energy band offsets in reference to Si, and a high quality dielectric itself. As the thickness of SiO₂ keeps shrinking, however, SiO₂ is facing its physical limitations from the viewpoint of gate dielectric leakage currents and reliability requirements. High-k dielectric materials have attracted extensive attention in the last decade due to their great potential for maintaining further down-scaling in equivalent oxide thickness (EOT) and a low dielectric leakage current. HfO₂ has been considered as one of the most promising candidates because of a high dielectric constant (k ~ 20-25), a large energy band gap (~ 6 eV) and the large band offsets (> 1.5 eV), and a good thermal stability. To enhance carrier mobility, strained substrates and high mobility channel materials have attracted a great deal of attention, thus III-V compound semiconductor substrates have emerged as one of possible candidates, in spite of several technical barriers, being believed as barriers so far. The absence of high quality and thermodynamically stable native oxide, like SiO₂ on Si, has been one such hurdle to implement MOS systems on III-V substrates. However, recently, there have been a number of remarkable improvements on MOS applications on them, inspiring more vigorous research activities. In this research, HfO2-based MOS capacitors and metal-oxidesemiconductor field effect transistors (MOSFETs) with a thin germanium (Ge) interfacial passivation layer (IPL) on III-V compound substrates were investigated. It was found that a thin Ge IPL could effectively passivate the surface of III-V substrate, consequently providing a high quality interface and an excellent gate oxide scalability. N-channel MOSFETs on GaAs, InGaAs, and InP substrates were successfully demonstrated and a minimum EOT of ~ 9 Å from MOS capacitors was achieved. This research has begun with GaAs substrate, and then expanded to InGaAs, InP, InAs, and InSb substrates, which eventually helped to understand the role of a Ge IPL and to guide future research direction. Overall, MOS devices on III-V substrates with an HfO₂ gate dielectric and a Ge IPL have demonstrated feasibility and potential for further investigations. / text

Made available in DSpace on 2014-10-09T12:43:31Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:05Z (GMT). No. of bitstreams: 1 06635.pdf: 4560564 bytes, checksum: 677cab6b14a66c0989ef5859a83679e3 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

O Granito Desemborque, um corpo de forma, aproximadamente, circular, situado no sul do Estado de São Paulo, tem área aflorante de 50 km2 e é representado por um biotita sienogranito. O caráter peraluminoso com teores significativos de K2O e Na2O, juntamente com o baixo conteúdo de CaO, altas razões Fe/Mg, elevados valores de SiO2 e de elementos traços como Zr, Nb e Y, atestam a afinidade alcalina do granito que pode ser classificado como do tipo A. Os teores de Y refletem a presença de fases acessórias como parisita de Ce, itrofluorita e monazita. Columbita, zircão rico em háfnio e cassiterita presentes na associação de minerais acessórios do Granito Desemborque foram analisados semiquantitativamente (teores em peso) por MEV-EDS. Com isso foi possível discriminar duas fases evolutivas para a geração de alguns dos minerais de metais raros associados ao corpo; uma francamente magmática (com subfases granítica e pegmatítica) e uma fase hidrotermal. A columbita (teor médio de Nb2O5 de 66,2% e 6,5% de Ta2O5) é nitidamente gerada na fase magmática sendo que na subfase granítica ela tem presença ubíqua e caráter disseminado. O zircão, por sua vez, ocorre nas duas subfases magmática, sendo que na subfase granítica ele teria um caráter mais tardio. O teor médio das análises foi de 9,3% de HfO2, classificando-o como um zircão rico em háfnio. Na fase hidrotermal, é que se desenrolariam os processos de enriquecimento em Hf desse mineral. A cassiterita, os minerais de REE e boa parte dos minerais radioativos têm a sua formação restrita a fase hidrotermal. Dentre as classificações propostas para granitos mineralizados, o Granito Desemborque se aproxima do tipo peralcalino mineralizado a metais raros com tendência a formar depósitos ou ocorrências de Nb e ETR. Os senões seriam o fato desse corpo não ser peralcalino (ele é peraluminosso) e dos potenciais minerais de Y e ETR só terem sido registrados como inclusões minerais hospedadas nos grãos de cassiterita (ítriocolumbita) e de zircão (xenotímio). A falta de concentrações minerais econômicas de Nb-Hf-Sn associadas ao Granito Desemborque pode ser imputada ao caráter anídrico do magma (tipo-A) e a falta ou limitação do fraturamento hidráulico. A ausência de concentrações minerais econômicas em virtude da remoção erosiva da zona de cúpula não se encontra de acordo com os resultados prospectivos encontrados, pois, a presença da cromita nas amostras de leito ativo coletadas nas drenagens estabelecidas bem no cerne do corpo granítico indica a preservação de restos de pendentes de teto da rocha encaixante (ortognaisses com boudins de rochas ultrabásicas). / The Desemborque Granite, a body almost of circular shape, placed in the southernmost part of São Paulo State, has an area of ca. 50 km2. and it is represented by a sienogranite biotite. Its peraluminous features with significant contents of K2O and Na2O, together with low CaO contents, high Fe/Mg ratios, elevated values of SiO2 and trace elements as Zr, Nb and Y, assure the granite alcaline affinity that can be classified as type A. The Y numbers reflect the presence of acessory phases as parasite de Ce, yttrofluorite and monazite. Columbite, zircon rich in hafnium and cassiterite presented in the association of accessory minerals of the Granite Desemborque were semiquantitatively analysed(values in weight) by MEV-EDS. Because of this it was possible to detail the two evolutional phases for the generation of some minerals of rare metals associated to the body; one fairly magmatic (with granitic sub-phases and pegmatitic) and an hidrotermal phase. Columbite (Nb2O5 mean value 66,2% and 6,5% Ta2O5) is clearly generated in magmatic phase and in the granitric sub-phase it has ubiquitous presence and disseminated character. Zircon, in its turn, occurs in the two magmatic sub-phases, and in the granitic sub-phase it would have a later character. The mean value of the analysis was of 9,3% for HfO2, classifying it as a zircon rich in hafnium. In the hidrotermal phase, the enrichment proccesses are developed in Hf of this mineral. Cassiterite, the REE minerals and a large number of radiactive mineral have their formation restricted to the hidrotermal phase. Amongst the proposed classification for the mineralized granites, the Granite Desemborque has an peralkalkine mineralized approach to rare metals with a wide tendency to create deposits or Nb and REE occurences. The opposition could be the fact that this body is not peralkaline (it is peraluminous) and the Y and REE mineral potentials only have been recorded in the hosted mineral inclusions in the cassiterite grains (yttrocolumbite) and of zircon (xenotímio). The lack of profitable Nb-Hf-Sn mineral concentrations associated to the Granite Desemborque can be magma anhydrous character (type-A) and the lack or limitation of the hydraulic fracturing. The absence of profitable mineral concentrations because of the erosive removal of the apical zone is not in agreement with the prospective results found, once the presence of chromite in the samples of the active stream bed collected at the draining which is established exactly in the basis of the granite body indicates the preservation of remaints roof pendant the wall rocks (ortognaisses with boudins of ultrabasic rocks).

Made available in DSpace on 2014-10-09T12:26:40Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:23Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

O Granito Desemborque, um corpo de forma, aproximadamente, circular, situado no sul do Estado de São Paulo, tem área aflorante de 50 km2 e é representado por um biotita sienogranito. O caráter peraluminoso com teores significativos de K2O e Na2O, juntamente com o baixo conteúdo de CaO, altas razões Fe/Mg, elevados valores de SiO2 e de elementos traços como Zr, Nb e Y, atestam a afinidade alcalina do granito que pode ser classificado como do tipo A. Os teores de Y refletem a presença de fases acessórias como parisita de Ce, itrofluorita e monazita. Columbita, zircão rico em háfnio e cassiterita presentes na associação de minerais acessórios do Granito Desemborque foram analisados semiquantitativamente (teores em peso) por MEV-EDS. Com isso foi possível discriminar duas fases evolutivas para a geração de alguns dos minerais de metais raros associados ao corpo; uma francamente magmática (com subfases granítica e pegmatítica) e uma fase hidrotermal. A columbita (teor médio de Nb2O5 de 66,2% e 6,5% de Ta2O5) é nitidamente gerada na fase magmática sendo que na subfase granítica ela tem presença ubíqua e caráter disseminado. O zircão, por sua vez, ocorre nas duas subfases magmática, sendo que na subfase granítica ele teria um caráter mais tardio. O teor médio das análises foi de 9,3% de HfO2, classificando-o como um zircão rico em háfnio. Na fase hidrotermal, é que se desenrolariam os processos de enriquecimento em Hf desse mineral. A cassiterita, os minerais de REE e boa parte dos minerais radioativos têm a sua formação restrita a fase hidrotermal. Dentre as classificações propostas para granitos mineralizados, o Granito Desemborque se aproxima do tipo peralcalino mineralizado a metais raros com tendência a formar depósitos ou ocorrências de Nb e ETR. Os senões seriam o fato desse corpo não ser peralcalino (ele é peraluminosso) e dos potenciais minerais de Y e ETR só terem sido registrados como inclusões minerais hospedadas nos grãos de cassiterita (ítriocolumbita) e de zircão (xenotímio). A falta de concentrações minerais econômicas de Nb-Hf-Sn associadas ao Granito Desemborque pode ser imputada ao caráter anídrico do magma (tipo-A) e a falta ou limitação do fraturamento hidráulico. A ausência de concentrações minerais econômicas em virtude da remoção erosiva da zona de cúpula não se encontra de acordo com os resultados prospectivos encontrados, pois, a presença da cromita nas amostras de leito ativo coletadas nas drenagens estabelecidas bem no cerne do corpo granítico indica a preservação de restos de pendentes de teto da rocha encaixante (ortognaisses com boudins de rochas ultrabásicas). / The Desemborque Granite, a body almost of circular shape, placed in the southernmost part of São Paulo State, has an area of ca. 50 km2. and it is represented by a sienogranite biotite. Its peraluminous features with significant contents of K2O and Na2O, together with low CaO contents, high Fe/Mg ratios, elevated values of SiO2 and trace elements as Zr, Nb and Y, assure the granite alcaline affinity that can be classified as type A. The Y numbers reflect the presence of acessory phases as parasite de Ce, yttrofluorite and monazite. Columbite, zircon rich in hafnium and cassiterite presented in the association of accessory minerals of the Granite Desemborque were semiquantitatively analysed(values in weight) by MEV-EDS. Because of this it was possible to detail the two evolutional phases for the generation of some minerals of rare metals associated to the body; one fairly magmatic (with granitic sub-phases and pegmatitic) and an hidrotermal phase. Columbite (Nb2O5 mean value 66,2% and 6,5% Ta2O5) is clearly generated in magmatic phase and in the granitric sub-phase it has ubiquitous presence and disseminated character. Zircon, in its turn, occurs in the two magmatic sub-phases, and in the granitic sub-phase it would have a later character. The mean value of the analysis was of 9,3% for HfO2, classifying it as a zircon rich in hafnium. In the hidrotermal phase, the enrichment proccesses are developed in Hf of this mineral. Cassiterite, the REE minerals and a large number of radiactive mineral have their formation restricted to the hidrotermal phase. Amongst the proposed classification for the mineralized granites, the Granite Desemborque has an peralkalkine mineralized approach to rare metals with a wide tendency to create deposits or Nb and REE occurences. The opposition could be the fact that this body is not peralkaline (it is peraluminous) and the Y and REE mineral potentials only have been recorded in the hosted mineral inclusions in the cassiterite grains (yttrocolumbite) and of zircon (xenotímio). The lack of profitable Nb-Hf-Sn mineral concentrations associated to the Granite Desemborque can be magma anhydrous character (type-A) and the lack or limitation of the hydraulic fracturing. The absence of profitable mineral concentrations because of the erosive removal of the apical zone is not in agreement with the prospective results found, once the presence of chromite in the samples of the active stream bed collected at the draining which is established exactly in the basis of the granite body indicates the preservation of remaints roof pendant the wall rocks (ortognaisses with boudins of ultrabasic rocks).

Made available in DSpace on 2014-10-09T12:43:31Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:05Z (GMT). No. of bitstreams: 1 06635.pdf: 4560564 bytes, checksum: 677cab6b14a66c0989ef5859a83679e3 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:26:40Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:23Z (GMT). No. of bitstreams: 0 / O presente trabalho estudou os efeitos das intera»c~oes hiper¯nas em dois sistemas de ¶oxidos: RCoO3 (R = Gd e Tb) com estrutura perovskita e ¯lmes ¯nos monocristalinos de HfO2 por meio da t¶ecnica de Correla»c~ao Angular Gama-Gama Perturbada (CAP), com o objetivo de fazer um estudo sistem¶atico do comportamento da varia»c~ao do gradiente de campo el¶etrico em fun»c~ao da temperatura. Para realiza»c~ao das medidas de intera»c~oes de quadrupolo el¶etrico utilizamos como de pontas de prova os n¶ucleos 111In ¡!111 Cd e o 181Hf ¡!181 Ta. As amostras de perovskitas foram confeccionadas por meio de um processo qu¶³mico denominado Sol-Gel e as an¶alises foram realizadas com aux¶³lio de difra»c~ao de raios-X. As pontas de prova foram inseridas nas solu»c~oes qu¶³micas durante o preparo das amostras. Os ¯lmes ¯nos foram fornecidos pelo Laborat¶orio de Intera»c~oes Hiper¯nas da Universidade de Lisboa e a ponta de prova de 181Hf foi ativada por meio da irradia»c~ao do ¯lme ¯no no reator IEA-R1 do IPEN no tempo adequado a espessura do ¯lme. As medidas foram realizadas na faixa de temperatura de 10 - 1560 K. Os resultados das medidas das amostras de perovskita indicam uma depend^encia do GCE com o s¶³tio de ocupa»c~ao dos ¶atomos da ponta de prova e uma varia»c~ao do GCE com a temperatura, que pode ser explicada por transi»c~oes de spins no ¶atomo de Co. As medidas do GCE dos ¯lmes ¯nos com mesma espessura apresentam uma segunda fra»c~ao, al¶em daquela correspondente a freqÄu^encia da HfO2 em amostras de bulk. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP