In this work, we performed an experimental analysis using a two-dimensional semiconducting transition metal dichalcogenide (TMD), specifically tungsten diselenide (WSe2), for gas sensor applications. Our method entailed building a chemically liquid exfoliated WSe2 gas sensing device with gold (Au) electrodes to measure its reaction and sensitivity to environmental gasses such as CO2 and N2. The 2D thin film was created through a solution processing method and electrically coupled in a two-terminal configuration; photonic curing system along with the hot plate annealing process was used on the thin film for rapid annealing, enhancing particle connectivity, stable crystal structure, and increasing overall electrical conductivity. The inkjet printing technology is used to explore the potential of the 2D thin film fabrication process that defines a well-controlled and scalable additive manufacturing process at the nano level that makes it possible to develop next-generation flexible devices. The additive nano-manufacturing process allowed us to establish the film's structure and chemical properties before measuring the electrical characteristics of the films when exposed to CO2 and N2 gases at room temperature. To explore and validate the sensitivity to human interaction with the gas-sensing device, we carried out further experiments with direct exposure to human breath in an open environmental space which shows a promising landmark for developing a next-generation flexible breath-sensing device.

Die Kombination aus anorganischen Nanopartikeln und Mikrogelen in einem hybriden System erlaubt die Herstellung von Materialien mit vielseitigen neuen Eigenschaften. Im Idealfall weisen solche hybriden Materialien neben den Eigenschaften von beiden indivduellen Systemen zusätzlich synergetische Effekte auf, welche aus den Interaktionen zwischen dem anorganischen Nanopartikel und dem Mikrogel resultieren. Im ersten Teil dieser Arbeit wird eine neuartige und eingängige Methode zur Herstellung von Cu2O@PNIPAM Kern-Schale Nanoreaktoren präsentiert. Die PNIPAM Schale schützt dabei die Cu2O Nanopartikel effektiv vor Oxidation. Die Cu2O@PNIPAM wurden als Photokatalysator zum Abbau von Methylorange unter sichtbarem Licht eingesetzt. Im Vergleich zu den reinen Cu2O Nanopartikeln konnte eine signifikante Steigerung der katalytischen Aktivität festgestellt werden. Desweiteren kann die photokatalytische Aktivität mittels Temperatur durch die thermosensitive PNIPAM Schale abgestimmt werden. Verhältnismäßig geringe Konzentrationen einer Cu2O@PNIPAM wässrigen Lösung (1,5 Gew%) können direkt als neuartige Tinte genutzt werden. Keine zusätzlichen Additive oder organische Lösungsmittel sind für die Strahldruckprozesse vonnöten. Gedruckte Bauelemente bestehend aus den Cu2O@PNIPAM wurden als Gas Sensoren eingesetzt und zeigten eine geringere Nachweisgrenze für NO2 als die reinen Cu2O Nanowürfel. Im zweiten Teil der Arbeit wurden katalytisch aktive Au Nanopartikel an copolymerisierten α –Cyclodextrin (α-CD) Einheiten in einem Poly(N-vinylcaprolactan) (PVCL) Mikrogel immobilisiert. Diese hybriden Partikel sind sehr aktive Katalysatoren für die Reduktion von aromatischen Nitroverbindungen. Die Reduktion von 4-Nitrophenol (Nip) und 2,6-Dimethyl-4-nitrophenol (DMNip) wurden als Modellreaktionen ausgewählt. Durch selektive Bindungseingenschaften der Nitroverbindungen an die α-CD Einheiten konnten verschiedene katalytische Aktivitäten für Nip and DMNip festgestellt werden. / The combination of inorganic nanoparticles and organic microgels in one hybrid system allows for the preparation of new materials with multifunctional properties. Ideally, such hybrid materials reflect both the properties of its individual components and synergetic effects due to the interaction between inorganic nanoparticles and microgels. In the first part of this thesis, the fabrication of Cu2O@Poly(N-isopropylacrylamide) (PNIPAM) core-shell nanoreactors has been presented. It was found that the PNIPAM shell effectively protects the Cu2O nanocubes from oxidation. The core-shell microgels have been used as photocatalyst for the decomposition of methyl orange and a significant enhancement in the catalytic activity has been observed compared with the bare Cu2O nanocubes. Most importantly, the photocatalytic activity of the core-shell nanoreactors can be further tuned by the thermosensitive PNIPAM shell. The aqueous solution of Cu2O@PNIPAM core-shell nanoparticles with quite low solid content (1.5wt. %) can be also directly used as a novel ink material for the inkjet printing without adding any other surfactants and organic solvents. The gas sensor device printed by core-shell nanoparticles is more sensitive to NO2 than that made from the bare Cu2O nanocubes. In the second part, a kind of hybrid microgel has been fabricated by immobilization of catalytically active Au nanoparticles in the α-cyclodextrin (α-CD) modified poly(N-vinylcaprolactam) (PVCL) microgels without addition of reducing agent and surfactant. The hybrid microgels can work efficiently as catalyst for the reduction of aromatic nitro-compounds by using the reduction of 4-nitrophenol (Nip) and 2,6-dimethyl-4-nitrophenol (DMNip) as model reactions. Due to the selective binding property of α-CDs to nitro compounds, the synthesized hybrid microgels show different catalytic activity for the target compounds, 4-nitrophenol (Nip) and 2,6-dimethyl-4-nitrophenol (DMNip), during the catalytic reactions.

In this research a state-of-the-art micro-thermal conductivity detector is developed based on MEMS technology. Its efficient design include a miniaturized 100×2 µm bridge from doped polysilicon, suspended 10 µm away from the single crystalline silicon substrate through a thermally grown silicon dioxide sacrificial layer. The microbridge is covered by 200 nm silicon nitride layer to provide more life time. Analytical models were developed that describe the relationship between the sensor response and ambient gas material properties. To obtain local temperature distribution and accurate predictions of the sensor response, a computational three dimensional simulation based on real geometry and minimal simplifications was prepared. It was able to handle steady-state and transient state, include multiple physics such as flow, heat transfer, electrical current and thermal stresses. Two new methods of measurement for micro TCD were developed; a time resolved method based on transient response of the detector to a step current pulse was introduced that correlates time constant of the response to the concentration of gas mixture. The other method is based on AC excitation of the micro detector; the amplitude and phase of the third harmonic of the resulting output signal is related to gas composition. Finally, the developed micro-sensor was packaged and tested in a GC system and was compared against conventional and complex FID for the detection of a mixture of VOCs. Moreover compact electronics and telemetry modules were developed that allow for highly portable applications including microGC utilization in the field.

La qualité de l’air extérieur (QAE) a fait l’objet d’une législation dès 1996 avec la loi LAURE. Depuis 2008, la directive européenne 2008/50/CE a instauré des obligations de mesure et de seuils à ne pas dépasser pour certains polluants à l’échelle européenne. Selon de nombreuses données toxicologiques et épidémiologiques, la pollution de l’air est à l’origine d’insuffisances respiratoires, d’asthme, de maladies cardiovasculaires et de cancers.Les composés organiques volatils (COV) et notamment le benzène, le toluène, l’ethylbenzène et les xylènes (les composés BTEX) sont des polluants avérés et participent grandement à la dégradation de la qualité de l’air intérieur et extérieur. Ce travail de thèse a concerné la réalisation d’un multicapteur de gaz à base d’oxyde métallique pour la détection de traces de BTEX dans le cadre du projet SMARTY (SMart AiR qualiTY). Un système de caractérisation électrique complet a été conçu et mise au point pour la détection de très faibles concentrations de BTEX (le ppb). Après une étude bibliographique, plusieurs matériaux ont été sélectionnés (WO3, ZnO, SnO2). Les caractérisations électriques des couches sensibles sélectionnées ont été effectuées sous air sec et sous différents taux d’humidité en présence de BTEX et de gaz interférents (NO2, CO2). Le WO3 a montré les meilleures performances en présence d’humidité et a été choisi pour le transfert de technologie qui accompagne les nouveaux transducteurs brevetés AMU. Le multicapteur à base de WO3 a montré une détection limite de 1 ppb sous 50% d’humidité relative et a permis de détecter et de quantifier de manière efficace les BTEX. / Outdoor air quality is subjected to the law LAURE since 1996. In 2008, the european directive 2008/50/EC introduced measurement requirements and thresholds that should not be exceeded for certain pollutants on a european scale. According to several toxicological and epidemiological studies, air pollution causes respiratory failure, asthma, cardiovascular diseases and cancers. In Europe, air pollution is responsible for more than 300 000 early deaths a year.Volatile organic compounds (VOCs), particularly benzene, toluene, ethylbenzene and xylenes (BTEX compounds) are proven pollutants and play a major role in the degradation of indoor and outdoor air quality. This thesis is dedicated to the development of a metal oxide based multi-gas sensor for the detection of traces of BTEX within the framework of the SMARTY project (SMart AiR qualiTY). A complete electrical characterization system was designed and implemented for the detection of sub-ppm concentrations of BTEX.Based on the state-of-art, several materials were selected (WO3, ZnO, SnO2). The electrical characterizations of the selected sensitive layers were carried out under dry air and under different humidity levels in the presence of BTEX and interfering gases (NO2, CO2). Tungsten oxide (WO3) exhibits the best performance in the presence of moisture and is chosen for the technology transfer that accompanies the new patented AMU transducers. The WO3-based multi-sensor has a lower limit of detection (LOD) of 1 ppb at 50% relative humidity and effectively detects and quantifies BTEX.

O desenvolvimento de novos materiais que possam ser aplicados como sensores resistivos de gás torna-se mais importante a cada dia devido sua importância no monitoramento ambiental, controle de emissão industrial e aplicações médicas. Desta forma, esforços têm sido realizados a fim de desenvolver dispositivos funcionais que apresentem uma alta sensibilidade, seletividade e baixo consumo de energia operando em temperaturas próximas a temperatura ambiente. O composto ZnO nanoestruturado puro e/ou dopado exibindo diferentes morfologias têm sido apontado como um candidato promissor na detecção de diferentes tipos de gases devido suas propriedades eletrônicas e da alta razão superfície/volume que facilitam a adsorção de espécies gasosas sobre sua superfície. Adicionalmente, diferentes estudos tem mostrado que o desempenho de sensores resistivos pode ser melhorado através da inserção de dopantes na rede ou na superfície do material sensor. Motivados por essas considerações, neste trabalho, filmes finos e espessos de composição ZnO e Zn1-xCoxO nanoestruturados obtidos através dos métodos dos precursores poliméricos, RF sputtering e tratamento hidrotermal foram avaliados visando sua aplicação como sensor dos gases O3, NO2 e CO. O estudo das propriedades estruturais de longo alcance investigadas através da técnica de difração de raios X mostrou que a adição de cobalto causa uma diminuição da intensidade dos picos de difração. Medidas do espectro de absorção de raios-X indicaram que nas amostras obtidas pelo método dos precursores poliméricos e RF sputtering, respectivamente, os átomos de Co assumem predominantemente o estado de valência 2+ e 3 +. A composição química da superfície das amostras foi analisada através da técnica de espectroscopia de fotoelétrons de raios X (XPS) enquanto as propriedades microestruturais foram avaliadas por microscopia eletrônica de varredura (MEV) e microscopia de força atômica (AFM). Medidas da resistência elétrica das amostras foram utilizadas para avaliar as propriedades sensoras das amostras, como a sensibilidade, a seletividade, o tempo de resposta e de recuperação quando expostos a diferentes concentrações dos gases O3, CO e NO2. As medidas de resistência elétrica quando os filmes foram expostos as estes gases mostrou que as três metodologias de síntese foram eficientes na obtenção de amostras que apresentam um grande potencial para serem aplicadas como sensores de gás. Entretanto, a amostra obtida por RF-sputtering apresentou as melhores propriedades de detecção ao gás ozônio com, valor de resposta quarenta (40) vezes maior, que foi atribuído a sua alta rugosidade e as características microestruturais apresentadas por essa amostra. As amostras Zn1-xCoxO obtidas pelo método dos precursores poliméricos exibiram uma maior sensibilidade ao ozônio e uma menor temperatura de trabalho em relação a amostra ZnO, preparada por esse mesmo método. Além disso, a adição de cobalto contribuiu para a seletividade do composto. A melhora das propriedades sensoras foram atribuídas a uma melhor atividade catalítica causada pelos íons Co e a presença de defeitos na superfie do material, que favoreceu a adsorção das moléculas de oxigênio na superfície da amostra / The development of new materials to be applied as gas resistive sensors has become increasingly important regarding environmental monitoring, industrial emission control and medical applications. Pure or doped ZnO nanostructured compounds that exhibit different morphologies have been identified as promising candidates for the detection of different types of toxic gases due to their electronic properties and high surface/volume ratio, which facilitates the adsorption of gaseous species on their surface. Studies have shown the performance of resistive sensors can be improved by the doping or presence of defects in the network or at the surface of the sensor material. The present doctoral thesis addresses the evaluation of ZnO and Zn1-xCoxO nanostructured films obtained by the polymeric precursor method, RF sputtering deposition and hydrothermal treatment and their application as O3, NO2 and CO gas sensors. Their long-range order structure investigated by the X-ray diffraction technique showed the addition of cobalt decreases the intensity of diffraction peaks. Measurements of X-ray absorption spectra at Co K-edge indicated Co atoms in the samples obtained by the RF sputtering technique and polymeric precursor method predominantly assume the 2+ and 3+ oxidation state. Measurements of electrical resistance were used in the evaluation of ZnO and Zn1-xCoxO nanostructured films sensing properties such as sensitivity, selectivity, response and recovery times under different concentrations of O3, CO and NO2 gases. The electrical resistance of the films exposed to those gases showed the three methodologies of synthesis effectively obtained samples to be applied as gas sensors. However, the sample obtained by the RF-sputtering deposition technique exhibited the best detection properties towards ozone gas and a forty-time higher response value, attributed to greater roughness and microstructural features. Zn1-xCoxO samples obtained by the polymeric precursor method exhibited higher sensitivity and a lower working temperature in relation to ozone gas. Such characteristics were attributed to a better catalytic activity promoted by the addition of Co ions and the presence of defects on the surface of the material, which favors the adsorption of oxygen molecules on the sample surface.

O presente trabalho envolve a síntese e caracterização de um polímero da família dos poli(p-fenilenovinileno)s (PPV), aplicável em camadas ativas de dispositivos como narizes eletrônicos, muito utilizados em várias áreas, como medicina, meio ambiente e indústria alimentícia. O trabalho visou também ao desenvolvimento de um nariz eletrônico, abrangendo o processo de preparação, o que incluiu a confecção dos eletrodos dos sensores de gases, o estudo referente ao equipamento de aquisição de dados e à comunicação com o microcomputador. Visou-se à otimização do equipamento que já vem sendo utilizado em medidas para várias detecções, estudando-se fatores como frequência da corrente alternada empregada, forma de onda (senoidal, quadrada e triangular), temperatura da amostra e distância entre os dígitos nos eletrodos. Verificou-se a possibilidade da utilização de nariz eletrônico na área de alimentos, estudando-se a identificação de méis de abelha de floradas diferentes e a detecção de fungos em laranjas pós-colheita. / The present thesis involves the synthesis and characterization of a polymer of the poly(p-phenylenevinylene) (PPV) family, applicable as active layer of devices such as gas sensors and electronic noses, which are instruments widely used in several areas, including medicine, environmental sciences and food industry. This work also aimed the full development of an electronic nose, from the making of the electrodes and sensors to the study of the data acquisition and its communication with a personal computer. In order to optimize the equipment, the influence of several factors such as frequency of the applied alternating current, its waveform (sine, square and triangle), temperature of the sample, and spacing between the digits of the electrodes were investigated. Finally, the equipment was used for the identification of honeys from different blossoms and for the detection of fungi in post-harvest oranges.

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 Pm3̄m 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 Pm3̄m 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.

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 Pm3̄m 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 Pm3̄m 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.

Observando o atual interesse em polímeros organometálicos para diversas aplicações, foi feita a síntese de uma série de polímeros conjugados contendo ferroceno na cadeia principal visando à investigação de suas propriedades, em especial fenômenos magnetorresistivos, magneto-ópticos e de óxido-redução. Os polímeros preparados pelo método de McMurry foram os seguintes: PFV: poli(1,1\'-ferrocenilenovinileno) e PFV-DOPPV-M: poli[1,1\'-ferrocenilenovinileno-alt-(2,5-di-n-octilóxi)-1,4-fenilenovinileno]. Outros dois polímeros foram preparados utilizando o método de polimerização de Wittig, o PFV-DOPPV-W: poli[1,1\'-ferrocenilenovinileno-alt-(2,5-di-n-octilóxi)-1,4-fenilenovinileno] e o PFV-DMPPV: poli[1,1\'-ferrocenileno-vinileno-alt-(2,5-dimetóxi)-1,4-fenilenovinileno]. A síntese de polímeros contendo segmentos π-conjugados equenos e bem definidos separados por segmentos não-conjugados é uma das melhores stratégias para a obtenção de polímeros emissores de luz azul. Com base nesse argumento foi feita a síntese de uma série de polímeros contendo um derivado metoxilado de bisfenol-A (BPA) na cadeia principal, alternando-se com unidades de PPV ou PFV que apresentam segmentos conjugados bem definidos. Os polímeros preparados foram os seguintes: BPA-DOPPV:poli[2,2-bis(4-metoxifenil)-propano-alt-2,5-(di-n-octilóxi)-1,4-divinilbenzeno]; BPA-PPV: poli[2,2-bis(4-metoxifenil)-propano-alt-1,4-ivinilbenzeno]; BPA-DMPPV: poli[2,2-bis(4-metoxifenil)-propano-alt-2,5-dimetóxi-1,4-ivinilbenzeno]; BPA-DBPPV: poli[2,2-bis(4-metoxifenil)-propano-alt-2,5-dibromo-1,4-divinilbenzeno] e BPA-PFV: poli[2,2-bis(4-metoxifenil)-propano-alt-1,1\'-divinil-ferroceno]. Todos os polímeros obtidos foram caracterizados por métodos espectroscópicos (UV-VIS, IR, RMN), análises térmicas, SEC, entre outras. Algumas aplicações foram estudadas para esses polímeros, tais como a construção de um eletrodo de ORP modificado, a produção de diodos orgânicos emissores de luz (OLEDs) e a determinação da resposta \"olfativa\" de sensores de gases. / Owing to the current interest in organometallic polymers and their applications, a group of conducting polymers containing ferrocene in the main chain was synthesized aiming the study of their magnetoresistive, magneto-optic and redox properties. The following polymers were prepared via McMurry method: poly(1,1\'-ferrocenylenevinylene) (PFV) and poly[1,1\'-ferrocenylenevinylene-alt-(2,5-di-n-octiloxy)-1,4-phenylenevinylene] (PFV-DOPPV-M). Two other polymers were synthesized via Wittig method: poly[1,1\'-ferrocenylenevinylene-alt-(2,5-di-n-octiloxy)-1,4-phenylenevinylene] (PFV-DOPPV-W) and poly[1,1\'-ferrocenylene-vinylene-alt-(2,5-dimethoxy)-1,4-phenylenevinylene] (PFV-DMPPV). The synthesis of polymers with well-defined small π-conjugated segments separated by non-conjugated segments is one of the best strategies to obtain blue light emitting polymers. Based on this statement the synthesis of several polymers formed by methoxylated bisphenol-A (BPA) alternated with PPV or PFV units was performed. The prepared polymers were the following: poly[2,2-bis(4-methoxyphenyl)-propane-alt-2,5-(di-n-octiloxy)-1,4-divinylbenzene] (BPA-DOPPV), poly [2,2-bis(4-methoxyphenyl)-propane-alt-1,4-divinylbenzene] (BPA-PPV), poly[2,2-bis(4-methoxyphenyl)-propane-alt-2,5-dimethoxy-1,4-divinylbenzene] (BPA-DMPPV), poly[2,2-bis(4-methoxyphenyl)-propane-alt-2,5-dibromo-1,4-divinylbenzene] (BPA-DBPPV) and poly[2,2-bis(4-methoxyphenyl)-propane-alt-1,1\'-divinylferrocene] (BPA-PFV). All the synthesized polymers were characterized by spectroscopic methods (UV/VIS, IR, NMR), thermal analysis, SEC, among others. Some applications to these polymers were studied: a modified ORP electrode, organic light emitting devices (OLEDs) and gas sensors.

With the rapid progress of nanotechnologies, there are two developing trends for the next generation of sensors: miniaturization and multi-functionality. Device miniaturization requires less power consumption, or even self-powered system. Multi-functional devices are usually based on multi-property coupling effects. Piezoelectric semiconductors have been considered to be potential candidates for self-powered/multi-functional devices due to their piezotronic coupling effect. In this dissertation, ZnO and CdSe nanowire arrays have been synthesized as the piezoelectric semiconductor materials to develop the following self-powered/multi-functional sensors: (1) self-powered gas sensors of ZnO/SnO2, ZnO/In2O3, ZnO/WO3 and CdSe nanowire arrays have been assembled. All these gas sensors are capable of detecting oxidizing gas and reducing gas without any external power supply owing to piezotronic effect which can convert mechanical energies to electrical energy to power the sensors; (2) a self-powered ZnO/ZnSe core/shell nanowire array photodetector has been fabricated. This photodetector is able to detect the entire range of the visible spectrum as well as UV light because of its type II heterostructure. The absolute sensitivity and the percentage change in responsivity of the photodetector were significantly enhanced resulting from the piezo-phototronic effect. The photodetector also exhibited self-powered photodetection behavior; (3) three dimensional nanowire arrays, such as ZnO and ZnO/Co3O4, have been synthesized to investigate piezo-magnetotronic and piezo-photo-magnetotronic effects. Under magnetic field, the magnetic-induced current of ZnO nanowire array decreased as magnetic field increased, and the current difference was magnified by one order of magnitude caused by piezo-magnetotronic effect through applying a stress. In contrast, under UV light illumination, the current response increased with an increment of magnetic field. The current difference was enhanced by at least two orders of magnitude attributed to piezo-photo-magnetotronic effect. Furthermore, ZnO/Co3O4 core/shell structure was employed to further improve the magnetic-induced current difference. This phenomenon projects a potential for multi-functional piezo-magnetotronic and piezo-photo-magnetotronic device development.