Porous metal oxides formed by supercritical carbon dioxide (SCCO2) treatments at low temperature were used for displays, solar cells, and light emitting diodes (LEDs) applications. The SCCO2 fluid, also known as green solvents, exhibits low viscosity, low surface tension and high diffusivity as gases, and high density and solubility same with liquids. In this thesis, we successfully fabricated porous antimony-doped tin oxide (ATO) and porous indium tin oxide (ITO) by the SCCO2 treatments. In addition, the treatment can also be used to improve the work function and surface energy of ITO anode of an organic LED (OLED). The performance of the OLEDs was drastically enhanced in comparison with that of the devices without any ITO surface treatments. First, the porous ATO films were formed by the SCCO2 treatment for absorption of silver molecules in silver electro deposition devices. The porosity, resistivity and average optical transmittance of the porous ATO film in visible wavelength were 43.1%, 3 £[-cm and 90.4%, respectively. For the silver electro deposition devices with the porous ATO film, the transmittance contrast ratio of larger than 12 in visible spectrum was obtained at an operating voltage of 1.5 V. Furthermore, for the 0.25 cm2 device, the switching time of 4.5 seconds was achieved by applying a square-wave voltage ranging from 1.5 to -0.2 V between the electrodes. On the other hand, the porous ITO with low refractive index was prepared by SCCO2/IPA treatment on gel-coated ITO thin films. The high refractive index of the ITO film was achieved by long-throw radio-frequency magnetron sputtering technique at room temperature. The index contrast (£Gn) was higher than 0.6 between porous ITO and sputtered ITO films. The large £Gn is useful for fabricating conductive anti-reflection (AR) and high reflection (HR) structures using the porous ITO on sputtered ITO bilayers. The weighted average reflectance and transmittance of 4.3% and 83.1% were achieved for the double-layer ITO AR electrode with a sheet resistance of 1.1 K£[/¡E. For HR structures, the reflectance and sheet resistance were 87.9% and 35 £[/¡E with 4 periods ITO bilayers. Finally, the SCCO2 treatments with strong oxidizer H2O2 were proposed to modify surface property of ITO anode of a fluorescent OLED. The highest work function and surface energy of 5.5 eV and 74.8 mJ/m2 was achieved by the SCCO2/H2O2 treatment. For the OLED with 15 min SCCO2 treatment at 4000 psi, the turn-on voltage and maximum power efficiency of 6.5 V and 1.94 lm/W were obtained. The power efficiency was 19.3% and 33.8% higher than those of the OLEDs with oxygen plasma treated and as-cleaned ITO anodes.

Current gas sensor technology, although meeting the minimum requirements in many instances, suffers for a number of limitations. Hence, there is currently a considerable volume of research being undertaken at many laboratories of different countries. In the past, all chemical sensors and catalyst were optimized empirically by a trial and error method. Today, however, systematic research and development is becoming increasingly important in order to improve sensors and to find new sensing principles. Obtaining a long term stable gas sensor with improved sensitivity, selectivity, and low cost for mass production passes through fundamental research and material characterization to build new chemically sensitive devices or to improve existing ones. The bottom line in the design and manufacture of modern gas sensors is the transfer from ceramic(of Figaro type) to thin film gas sensors(TFGs). This transfer provides new opportunities for further microminiaturization, power consumption and cost reduction of gas sensors. Therefore, at the present time, thin film gas sensors are the basis for the design of the modern gas sensitive multi-parameter microsensor systems. Applications of these systems include environment, security, home systems, smart buildings, transportation, discrete manufacturing, process industries and so on. Microelectromechanical systems(MEMS) based integrated gas sensors present several advantages for these applications such as ease of array fabrication, small size, and unique thermal manipulation capabilities. MEMS based gas sensors; which are usually produced using a standard CMOS(Complimentary Metal Oxide Semiconductor) process, have the additional advantages of being readily realized by commercial foundries and amenable to the inclusion of on-chip electronics. In order to speed up the design and optimization of such integrated sensors, microheater designs for gas sensor applications have been presented as first part of the present thesis. As heater design is the key part for a gas sensor operation. So 3D simulations have been used to optimize micro-heater geometry. The application of MEMS Design Tool(COVENTORWARE) has been presented to the design and analysis of micro-hotplate (MHP) structures. Coupled Electro-thermal analysis provided an estimation of thermal losses and temperature distribution on the hotplate for realistic geometrical and material parameters pertinent to fabrication technology. Five microheater designs have been proposed in terms of different sizes and shapes in order to optimize the microhotplate structure to be used for gas sensor operation for the specified range of temperature and power consumption. To produce a gas sensor, which is able to detect LPG leak, thin films of tin oxide have been developed. FR sputtering has been used to deposit gas sensitive tin oxide thin filmls under various deposition conditions. Four different values of pressure in the range from high pressure(5 X 10-2 mbar) to lower pressure (2 X 10-3 mbar), three RF power values 50, 75, 100 W and varied oxygen percentage in sputtering atmosphere (0-18%) have been used to optimize the material properties of tin oxide thin films to study the sensitivity towards LPG. All the samples have been analyzed using various macro and microscopic characterization techniques. Extensive studies have been done on the sensor response for the samples deposited under different conditions. Finally the sample film deposited at 5 x 10-3 mbar, with applied power of 75 W in the presence of 8% oxygen, showed maximum sensitivity towards LPG.

Today there is a great deal of interest in the development of gas sensors for applications like air pollution monitoring, indoor environment control, detection of harmful gases in mines etc. Based on different sensing principles, a large variety of sensors such as semiconductor gas sensors, thermoelectric gas sensors, optical sensors and thermal conductivity sensors have been developed. The present thesis reports a detailed account of a novel method followed for the design and development of a thermoelectric gas sensor for sensing of Volatile Organic Compounds. Thermoelectric effect is one of the highly reliable and important working principles that is widely being put into practical applications. The thermoelectric property of semiconducting tin oxide film has been utilized in the sensor that has been developed. The thermoelectric property of semiconducting tin oxide film has been utilized in the sensor. The deposition parameters for sputtering of tin oxide film have been optimized to obtain a high seebeck coefficient. A test set-up to characterize the deposited films for their thermoelectric property has been designed and developed. A novel method of increasing the seebeck coefficient of tin oxide films has been successfully implemented. Thin films of chromium, copper and silver were used for this purpose. Deposition of the semiconducting oxide on strips of metal films has led to a noticeable increase in the seebeck coefficient of the oxide film without significantly affecting its thermal conductivity. The next part of our work involved development of a gas sensor using this thermoelectric film. These sensors were further tested for their response to volatile organic compounds. The sensor showed significant sensitivity to the test gases at relatively low temperatures. In addition to this, the developed sensor is also selective to acetone gas.

Thin films are an enabling technology for a wide range of applications, from microprocessors to diffusion barriers. Nanolaminate thin films combine two (or more) materials in a layered structure to achieve performance that neither film could provide on its own. Atomic layer deposition (ALD) is a chemical vapor deposition technique in which film growth occurs through self limiting surface reactions. The atomic scale control of ALD is well suited for producing nanolaminate thin films. In this thesis, ALD of two nanolaminate systems will be investigated: Al₂O₃-Ta₂O₅ and ZnO-SnO₂. Al₂O₃ and Ta₂O₅ are high κ dielectrics that find application as gate oxides for field effect devices such as metal oxide semiconductor field effect transistors and thin film transistors. Al₂O₃-Ta₂O₅ nanolaminate films of a fixed composition and total thickness, but with varied laminate structures, were produced to explore the influence of layer thickness on dielectric behavior. Layer thickness was found to have little impact on the dielectric constant but a strong impact on the leakage current. Thick layered nanolaminates (with 2.5 to 10 nm layers) performed better than either pure material. Showing structure provides a means of tailoring nanolaminate properties. ZnSnO is an amorphous oxide semiconductor used to make transparent TFTs. Although ALD is naturally suited to the production of nanolaminates, the deposition of homogenous ternary compounds is still uncommon. For very thin depositions, nucleation behavior can dominate, resulting in ALD growth rates different than for thicker films. Initial work on ALD of the ZnO-SnO₂ system is presented, focusing on nucleation and growth of each material on the other. It was found that both ZnO and SnO₂ inhibit the growth of one another and a method was developed to characterize the average growth rate for few cycle depositions. / Graduation date: 2011

This thesis aims to provide insight into the fundamental electrochemical processes taking place when cycling SnO2 in lithium-ion batteries (LIBs). Special attention was paid to the partial reversibility of the tin oxide conversion reaction and how to enhance its reversibility. Another main effort was to pinpoint which limitations play a role in tin based electrodes besides the well-known volume change effect in order to develop new strategies for their improvement. In this aspect, Li+ mass transport within the electrode particles and the large first cycle charge transfer resistance were studied. Li+ diffusion was proven to be an important issue regarding the electrochemical cycling of SnO2. It was also shown that it is the Li+ transport inside the SnO2 particles which represents the largest limitation. In addition, the overlap between the potential regions of the tin oxide conversion and the alloying reaction was investigated with photoelectron spectroscopy (PES) to better understand if and how the reactions influence each other`s reversibility. The fundamental insights described above were subsequently used to develop strategies for the improvement of the performance and the cycle life for SnO2 electrodes in LIBs. For instance, elevated temperature cycling at 60 oC was employed to alleviate the Li+ diffusion limitation effects and, thus, significantly improved capacities could be obtained. Furthermore, an ionic liquid electrolyte was tested as an alternative electrolyte to cycle at higher temperatures than 60 oC which is the thermal stability limit for the conventional LP40 electrolyte. In addition, cycled SnO2 nanoparticles were characterized with transmission electron microscopy (TEM) to determine the effects of long term high temperature cycling. Also, the effect of vinylene carbonate (VC) as an electrolyte additive on the cycling behavior of SnO2 nanoparticles was studied in an effort to improve the capacity retention. In this context, a recently introduced intermittent current interruption (ICI) technique was employed to measure and compare the development of internal cell resistances with and without VC additive.

Chemisorption of an organic monolayer to tune the surface properties of a transparent conductive oxide (TCO) electrode can improve the performance of organic electronic devices that rely on efficient charge transfer between an organic active layer and a TCO contact. Here, a series of perylene diimides (PDIs) was synthesized and used to study relationships between monolayer structure/properties and electron transfer kinetics at PDI-modified indium-tin oxide (ITO) electrodes. In these PDI molecules, one of the imide substituents is a benzene ring bearing a phosphonic acid (PA) and the other is a bulky aryl group that is twisted out of the plane of the PDI core. The size of the bulky aryl group and the substitution of the benzene ring bearing the PA were both varied, which altered the extent of aggregation when these molecules were absorbed as monolayer films (MLs) on ITO, as revealed by both attenuated total reflectance (ATR) and total internal reflection fluorescence spectra. Polarized ATR measurements indicate that, in these MLs, the long axis of the PDI core is tilted at an angle of 33-42 degrees relative to the surface normal; the tilt angle increased as the degree of bulky substitution increased. Rate constants for electron transfer (k(s,opt)) between these redox-active modifiers and ITO were determined by potential-modulated ATR spectroscopy. As the degree of PDI aggregation was reduced, k(s,opt) declined, which is attributed to a reduction in the lateral electron self-exchange rate between adsorbed PDI molecules, as well as the heterogeneous conductivity of the ITO electrode surface. Photoelectrochemical measurements using a dissolved aluminum phthalocyanine as an electron donor showed that ITO modified with any of these PDIs is a more effective electron-collecting electrode than bare ITO.

O óxido de índio dopado com estanho é um semicondutor degenerado de alta transparência no espectro visível e alta condutância elétrica. Por suas propriedades, ele é utilizado como eletrodo transparente em diversas aplicações. Algumas destas aplicações exigem que os filmes sejam depositados sobre substratos poliméricos, que degradam em temperaturas acima de 100 °C. Por este motivo, métodos de deposição que utilizam baixas temperaturas são necessários. O objetivo deste trabalho é o desenvolvimento de técnicas de deposição de filmes de óxido de índio dopado com estanho, em baixas temperaturas (< 100 °C), pelo método de magnetron sputtering de rádio fequência. Filmes foram obtidos sobre substratos de silício, vidro e policarbonato, e suas propriedades físicas, elétricas, ópticas, químicas e estruturais foram analisadas por perfilometria, elipsometria, curvas corrente-tensão, prova de quatro pontas, medidas de efeito Hall, difratometria de raios-X e espectrofotometria. Filmes depositados sobre silício e vidro tiveram resistividade elétrica mínima da ordem de 10^-4 Ohm.cm, enquanto a resistividade do filme obtido sobre policarbonato foi da ordem de 10^-3 Ohm.cm. A transmitância óptica média no espectro visível das amostras variou de 66 a 87 %. Do ponto de vista estrutural, as amostras tenderam a apresentar fase amorfa e cristalina, com orientação preferencial ao longo da direção [100]. De modo geral, as amostras obtidas de 75 a 125 W tiveram as melhores propriedades para serem utilizadas em aplicações que exijam eletrodos transparentes, considerando aspectos elétricos e ópticos. / Indium-tin oxide is a degenerate semiconductor that shows high transmittance in the visible region of the spectrum and high electrical conductance. Because of its properties, this material is used as transparent electrode in a wide variety of applications. Some of these applications demand the indium-tin oxide layer to be deposited over polymer substrates, which degrade at temperatures above 100 °C. Because of this degradation problem, deposition methods at low temperatures are needed. The purpose of this work is the development of low temperature (< 100 °C) indium-tin oxide deposition processes by radio frequency magnetron sputtering method. Thin films were deposited over silicon, glass and polycarbonate substrates, and their physical, electrical, optical, chemical and structural properties were analyzed by surface high step meter, ellipsometry, current-voltage curves, four-point probe analysis, Hall effect measurements, X-ray diffractometry and spectrophotometry. Films deposited over silicon and glass substrates showed minimal electrical resistivity in the order of 10^-4 Ohm.cm, while the resistivity of the film obtained over polycarbonate was in the order of 10^-3 Ohm.cm. The average transmittance in the visible spectrum varied over the range 66 to 87 %. According to the structural study, the films present both amorphous and crystalline phases, with crystallites showing preferential orientation along the [100] direction. In general, films deposited with power varying over the range 75 to 125 W showed the best results to be applied as transparent electrodes, considering electrical and optical aspects.

O óxido de índio dopado com estanho é um semicondutor degenerado de alta transparência no espectro visível e alta condutância elétrica. Por suas propriedades, ele é utilizado como eletrodo transparente em diversas aplicações. Algumas destas aplicações exigem que os filmes sejam depositados sobre substratos poliméricos, que degradam em temperaturas acima de 100 °C. Por este motivo, métodos de deposição que utilizam baixas temperaturas são necessários. O objetivo deste trabalho é o desenvolvimento de técnicas de deposição de filmes de óxido de índio dopado com estanho, em baixas temperaturas (< 100 °C), pelo método de magnetron sputtering de rádio fequência. Filmes foram obtidos sobre substratos de silício, vidro e policarbonato, e suas propriedades físicas, elétricas, ópticas, químicas e estruturais foram analisadas por perfilometria, elipsometria, curvas corrente-tensão, prova de quatro pontas, medidas de efeito Hall, difratometria de raios-X e espectrofotometria. Filmes depositados sobre silício e vidro tiveram resistividade elétrica mínima da ordem de 10^-4 Ohm.cm, enquanto a resistividade do filme obtido sobre policarbonato foi da ordem de 10^-3 Ohm.cm. A transmitância óptica média no espectro visível das amostras variou de 66 a 87 %. Do ponto de vista estrutural, as amostras tenderam a apresentar fase amorfa e cristalina, com orientação preferencial ao longo da direção [100]. De modo geral, as amostras obtidas de 75 a 125 W tiveram as melhores propriedades para serem utilizadas em aplicações que exijam eletrodos transparentes, considerando aspectos elétricos e ópticos. / Indium-tin oxide is a degenerate semiconductor that shows high transmittance in the visible region of the spectrum and high electrical conductance. Because of its properties, this material is used as transparent electrode in a wide variety of applications. Some of these applications demand the indium-tin oxide layer to be deposited over polymer substrates, which degrade at temperatures above 100 °C. Because of this degradation problem, deposition methods at low temperatures are needed. The purpose of this work is the development of low temperature (< 100 °C) indium-tin oxide deposition processes by radio frequency magnetron sputtering method. Thin films were deposited over silicon, glass and polycarbonate substrates, and their physical, electrical, optical, chemical and structural properties were analyzed by surface high step meter, ellipsometry, current-voltage curves, four-point probe analysis, Hall effect measurements, X-ray diffractometry and spectrophotometry. Films deposited over silicon and glass substrates showed minimal electrical resistivity in the order of 10^-4 Ohm.cm, while the resistivity of the film obtained over polycarbonate was in the order of 10^-3 Ohm.cm. The average transmittance in the visible spectrum varied over the range 66 to 87 %. According to the structural study, the films present both amorphous and crystalline phases, with crystallites showing preferential orientation along the [100] direction. In general, films deposited with power varying over the range 75 to 125 W showed the best results to be applied as transparent electrodes, considering electrical and optical aspects.

O objetivo desta tese de doutorado foi estudar a influência da adição do íon estanho (Sn4+) à rede do composto SrTiO3 em substituição ao íon de titânio visando otimizar as propriedades elétricas desse composto e, como consequência, obter uma melhora de seu desempenho como um sensor de gás na forma de filmes finos. Para realizar a deposição destes filmes finos através dos métodos de Deposição por Feixe de Elétrons (EBD), alvos cerâmicos de composição SrTi1-xSnxO3 (STSO) com x = 0; 0,20; 0,40; 0,60; 0,80; 0,85; 0,90; 0,95; 1 foram obtidos através do método dos precursores poliméricos modificado. A sequência de formação de soluções sólidas foi determinada através do refinamento Rietveld das amostras STSO na forma de pó sinterizadas, obtidas através dos métodos dos precursores poliméricos e de reação de estado sólido, mostrando que a transição da fase cúbica Pm3&#772;m do composto SrTiO3 até a fase ortorrômbica Pnma do composto SrSnO3 não depende do método de síntese. As medidas de espectroscopia Raman e absorção de raios-X (XANES, na borda K do Ti) das amostras tanto na forma de pó, obtidas através do método dos precursores poliméricos e de reação de estado sólido, quanto na forma de filme fino obtidas por EBD revelaram a existência de uma desordem local na rede do composto SrTiO3 que diminui com o aumento da temperatura e com a diminuição da concentração de Sn. Os filmes finos STSO obtidos por EBD foram avaliados como sensores utilizando-se os gases O3 e NH3. Em medidas realizadas com o gás ozônio (O3), os resultados mostraram que os filmes finos de 100 nm de espessura apresentaram uma maior sensibilidade tendo a amostra com 60% de Sn com o melhor desempenho a 350°C para 0,15 ppm do gás. As análises de performance dos filmes STSO quanto a seletividade indicaram que não foram seletivos e que apresentaram uma maior resposta ao gás ozônio quando comparados ao gás NH3. / The objective of this work was to study the influence of the addition of tin ion (Sn4+) into the SrTiO3 compound lattice, to replace the titanium ion (Ti4+). The aim was to optimize the electrical properties of SrTiO3 compound and, as a consequence, to obtain an improvement of its performance as a gas sensor in the thin films samples. To perform the deposition of these thin films through Electron Beam Deposition (EBD), ceramic targets of composition SrTi1-xSnxO3 (STSO) with x = 0; 0.20; 0.40; 0.60; 0.80; 0.85; 0.90; 0.95; and 1 were obtained by the modified polymer precursor method. The solid solution formation sequence was determined by the Rietveld refinement of the STSO sintered powdered samples, obtained by both polymeric precursor and solid-state reaction methods, showing that the transition from the cubic Pm3&#772;m phase of the SrTiO3 compound to the orthorhombic Pnma phase of the SrSnO3 compound does not depend on the synthesis method. The measurements of Raman spectroscopy and absorption of X-rays (XANES, at Ti K-edge), of the powdered samples obtained by both synthesis methods and of the thin films obtained by EBD, revealed the existence of a local disorder in the SrTiO3 compound lattice which decreases with increasing of temperature and with decreasing of Sn concentration. The STSO thin films were evaluated as sensors using the O3 and NH3 gases. In measurements accomplished with the ozone gas (O3), the results showed that thin films of 100 nm thickness had a higher sensitivity. The sample having 60% of tin showed the best performance at 350°C for 0.15 ppm of ozone gas. The performance analysis related to the selectivity of the STSO films indicated they were not selective and that presented a higher response to the ozone gas when compared to the NH3 gas.

Made available in DSpace on 2017-07-21T20:42:37Z (GMT). No. of bitstreams: 1 Samara Schmidt.pdf: 2152425 bytes, checksum: fb332f072ac95b26d2a0afaf94d0a90a (MD5) Previous issue date: 2012-03-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work a Fe(III)-doped tin oxide (SnO2) system using chemical mixture of SnO2 and Iron(III) nitrate nonahydrate (Fe(NO3)3. 9H2O). This system was calcined at temperatures from 600 ºC to 1200 C. The as-calcined powders were characterized using several techniques: thermal analysis (DTA/TG) to identify the thermal stability;X-ray diffraction to identify the resulting phases; scanning electron microscopy and photocorrelation spectroscopy to study the material morphological structure. The usefulness of the ceramic pigment was evaluated testing the solubility of the oxide system in frit and its color stability. Also, using UV-visible diffuse reflectance spectroscopy, the CiELab* coordinates of the system were estimated. / Neste trabalho foi desenvolvido um sistema óxido de estanho (SnO2) dopado com óxido de ferro III (Fe2O3) através de mistura química de SnO2 e nitrato ferro III nonahidratado (Fe(NO3)3. 9H2O). Este sistema foi calcinado em intervalos de temperaturas que variaram de 600 a 1200 C. A caracterização do pó calcinado foi realizada a partir de várias técnicas, entre elas, a análise termogravimétrica e termodiferencial para identificação da estabilidade térmica, a técnica de difração de raios X para a identificação das fases resultantes, a técnica de microscopia eletrônica de varredura e espectroscopia de fotocorrelação para a compreenção da estrutura morfológica do material. Avaliou-se a eficácia do pigmento cerâmico através da solubilidade do sistema óxido com a frita bem como a estabildade da cor. Também, através da técnica de espectofotometria na região do UV-Vis, obteve-se as cores do sistema caracterizados nas coordenadas CIELab*.