Metal Organic Frameworks (MOFs) are a new class of nanoporous materials with high surface area, thermal/chemical stability and a taylorable pore size. These properties make MOFs ideal for storage and gas separation applications. Piezoresistive microcantilever sensors are microfabricated devices that are highly sensitive to surface strain due to doped single crystal silicon regions. Changes in resistance generated by surface strain can be measured with a high degree of accuracy using a Wheatstone bridge and basic instrumentation. This thesis will discuss the use of piezoresistive microcantilever sensors as a transduction mechanism for detection of volatile organic compounds (VOC's) using MOF coatings. It will be shown that by coating a microcantilever with MOFs it is possible to detect low levels of different VOC's (hundreds of parts per million). Excellent sensitivity and a simple transduction mechanism make these devices low power and highly compact. Such devices would be capable of detecting a plethora of different analytes at low concentrations. Devices were engineered for maximum response and microfabricated in the cleanroom with high yield. A custom setup for testing the devices was designed and machined. A number of MOFs were selected and tested, their response was recorded and analyzed. Twelve different analytes including eleven VOC's and water were used to characterize the MOFs. Microcantilever sensors were shown to be durable, reliable and stable in long term testing despite being subjected to many different analytes. MOF coatings proved flexible, durable, stable and reversible. This work will show a promising new technology for a next generation gas sensor.

Nanomaterials are the heart of nanoscience and nanotechnology. Research into nanostructures has been vastly expanding worldwide and their application spreading into numerous branches of science and technology. The incorporation of these materials in commercial products is revolutionising the current technological market. Nanomaterials have gained such enormous universal attention due to their unusual properties, arising from their size in comparison to their bulk counterparts. These nanosized structures have found applications in major devices currently under development including fuel cells, computer chips, memory devices, solar cells and sensors. Due to their aforementioned importance nanostructures of various materials and structures are being actively produced and investigated by numerous research groups around the world. In order to meet the market needs the commercialisation of nanomaterials requires nanomaterial fabrication mechanisms that will employ cheap, easy and low temperature fabrication methods combined with environmentally friendly technologies. This thesis investigates low temperature growth of various one-dimensional nanostructures for their potential application in chemical sensors. It proposes and demonstrates novel materials that can be applied as catalysts for nanomaterial growth. In the present work, zinc oxide (ZnO) and silicon (Si) based nanostructures have been fabricated using low temperature growth methods including hydrothermal growth for ZnO nanowires and plasma-enhanced chemical vapour deposition (PECVD) technique for Si nanostructures. The structural, optical and electrical properties of these materials have been investigated using various characterisation techniques. After optimising the growth of these nanostructures, gas and biosensors have been fabricated based on Si and ZnO nanostructures respectively in order to demonstrate their potential in chemical sensors. For the first time, in this thesis, a new group of materials have been investigated for the catalytic growth of Si nanostructures. Interesting growth observations have been made and theory of the growth mechanism proposed. The lowest growth temperature in the published literature is also demonstrated for the fabrication of Si nanowires via the PECVD technique. Systematic studies were carried out in order to optimise the growth conditions of ZnO and Si nanostructures for the production of uniformly shaped nanostructures with consistent distribution across the substrate. v The surface structure and distribution of the variously shaped nanostructures has been analysed via scanning electron microscopy. In addition, the crystallinity of these materials has been investigating using Raman and X-ray diffraction spectroscopies and transmission electron microscopy. In addition to the fabrication of these one-dimensional nanomaterials, their potential application in the chemical sensors has been tested via production of a glucose biosensor and an isopropyl alcohol vapour gas sensor based on ZnO and Si nanostructures respectively. The operation of the devices as sensors has been demonstrated and the mechanisms explored.

O objetivo deste trabalho foi contribuir para o desenvolvimento de um dispositivo elétrico baseado em moléculas organometálicas sobre substratos de silício poroso visando a sua aplicação no desenvolvimento de sensores de gás. Foi proposto um procedimento de deposição de monocamadas de moléculas de Ftalocianina sobre a superfície da estrutura de silício poroso aproveitando sua elevada superfície específica. As moléculas de Ftalocianina adsorvidas sobre o filme de silício poroso oxidado termicamente não apresentaram processos de reação química preservando suas características elétricas e ópticas. Foi fabricado um dispositivo com eletrodo de Ouro baseado no filme de moléculas de Ftalocianina depositado sobre silício poroso oxidado. A partir das curvas características I x V foi identificado o mecanismo de transporte de portadores através do filme de Ftalocianina e o tipo de junção na região de eletrodo-Ftalocinina. O mecanismo é baseado na corrente limitada por cargas armadilhadas nos níveis altamente localizados no interior da banda proibida entre os níveis HOMO e LUMO das moléculas de Ftalocianina. A resposta I x V do dispositivo mostrou-se sensível à exposição a gases orgânicos mostrando maior sensibilidade para o gás (Metanol) com maior constante dielétrica, sugerindo uma importante contribuição do efeito de blindagem sobre os níveis de armadilha, e como conseqüência a diminuição da profundidade destes níveis. / The aim of this work was to contribute for the development of an electrical device based on organometallic molecules onto porous silicon bulks for the application in the development of gas sensor devices. It was proposed a procedure of deposition of monolayer of Phthalocyanine molecules onto the surface of the porous silicon structure taking advantage of its high specific surface. The Phthalocyanine molecules adsorbed on the porous silicon film thermally oxidized did not show any chemical reaction process preserving their electrical and optical characteristics. A device was fabricated with Gold electrodes based on the Phthalocyanine molecules film deposited onto oxidized porous silicon. From the (I x V) characteristic curves, the carrier transport mechanism through the Phthalocyanine film and the junction type in the Phthalocyanine-electrode region were identified. The mechanism is based on the current limited by the trapped charges in the highly localized levels inside the band gap between the HOMO and LUMO levels of the Phthalocyanine molecules. The I x V response of the device showed to be sensitive to organic gases exposition showing higher sensibility to (Methanol) gas with higher dielectric constant, suggesting an important contribution of the shield effect on the trap levels and as a result decreasing the depth of these levels.

O presente trabalho consiste no desenvolvimento de uma nova técnica de identificação de materiais poliméricos por meio do uso de um nariz eletrônico. Narizes eletrônicos têm sido desenvolvidos para detecção automática e classificação de odores e gases. São instrumentos capazes de medir a concentração ou intensidade odorante de modo similar a um olfatômetro, mas sem as limitações inerentes ao uso de painel humano, o que é altamente desejável. O nariz eletrônico é composto por um sistema de sensores, no nosso caso, utilizamos um arranjo de quatro sensores, que foram confeccionados pela deposição de finos filmes de polímeros condutores dopados sobre a superfície de eletrodos interdigitados. Estes sensores foram conectados a condutivímetros acoplados a um computador de uso pessoal (PC) através de um conversor AD. O PC era dotado de softwares de aquisição e tratamento de dados. Amostras dos materiais a serem analisados foram aquecidas a 257°C e o arranjo de sensores foi exposto aos compostos voláteis produzidos durante esse aquecimento. Realizaram-se 30 ensaios formados por períodos de exposição (5 segundos; compostos voláteis) intercalados por períodos de recuperação (45 segundos; ar puro). Os dados obtidos foram tratados estatisticamente por Análises de Componentes Principais (PCA). Esse arranjo de sensores mostrou-se eficiente, sendo capaz de diferenciar nove tipos de materiais poliméricos testados. Apresentou 100% de acerto em 30 ensaios de classificação realizados. / This research consists in the development of a new technique capable of the identification of polymeric materials using an electronic nose. Electronic noses have been developed for automatic detection and classification of odors, vapors and gases. They are instruments capable of measuring the concentration or intensity of an odorant similarly to an olfactometer, but without the inherent limitations of the human panel, which is highly desired. The electronic nose is composed by a system of chemoresistive sensors, in this case, an array of four sensors was used, which were made through a deposition of thin films of doped conductive polymers, on the surface of interdigitated electrodes. These sensors were connected to conductivity meters coupled to a personal computer (PC) through AD converters. The PC had acquisition and data processing softwares installed on it. Thirty readings were made or each analyzed polymer consisting of alternated 5 seconds exposure periods and 45 seconds recovery periods. The collected data were statistically processed by Principal Component Analysis (PCA). This electronic nose was efficient, being able to identify nine types of polymeric materials through the analysis of the different volatile compounds released when these materials were heated to the heat of 257ºC. A 100% correct classification score was obtained in the 30 sets of analysis.

O objetivo deste trabalho foi contribuir para o desenvolvimento de um dispositivo elétrico baseado em moléculas organometálicas sobre substratos de silício poroso visando a sua aplicação no desenvolvimento de sensores de gás. Foi proposto um procedimento de deposição de monocamadas de moléculas de Ftalocianina sobre a superfície da estrutura de silício poroso aproveitando sua elevada superfície específica. As moléculas de Ftalocianina adsorvidas sobre o filme de silício poroso oxidado termicamente não apresentaram processos de reação química preservando suas características elétricas e ópticas. Foi fabricado um dispositivo com eletrodo de Ouro baseado no filme de moléculas de Ftalocianina depositado sobre silício poroso oxidado. A partir das curvas características I x V foi identificado o mecanismo de transporte de portadores através do filme de Ftalocianina e o tipo de junção na região de eletrodo-Ftalocinina. O mecanismo é baseado na corrente limitada por cargas armadilhadas nos níveis altamente localizados no interior da banda proibida entre os níveis HOMO e LUMO das moléculas de Ftalocianina. A resposta I x V do dispositivo mostrou-se sensível à exposição a gases orgânicos mostrando maior sensibilidade para o gás (Metanol) com maior constante dielétrica, sugerindo uma importante contribuição do efeito de blindagem sobre os níveis de armadilha, e como conseqüência a diminuição da profundidade destes níveis. / The aim of this work was to contribute for the development of an electrical device based on organometallic molecules onto porous silicon bulks for the application in the development of gas sensor devices. It was proposed a procedure of deposition of monolayer of Phthalocyanine molecules onto the surface of the porous silicon structure taking advantage of its high specific surface. The Phthalocyanine molecules adsorbed on the porous silicon film thermally oxidized did not show any chemical reaction process preserving their electrical and optical characteristics. A device was fabricated with Gold electrodes based on the Phthalocyanine molecules film deposited onto oxidized porous silicon. From the (I x V) characteristic curves, the carrier transport mechanism through the Phthalocyanine film and the junction type in the Phthalocyanine-electrode region were identified. The mechanism is based on the current limited by the trapped charges in the highly localized levels inside the band gap between the HOMO and LUMO levels of the Phthalocyanine molecules. The I x V response of the device showed to be sensitive to organic gases exposition showing higher sensibility to (Methanol) gas with higher dielectric constant, suggesting an important contribution of the shield effect on the trap levels and as a result decreasing the depth of these levels.

O presente trabalho consiste no desenvolvimento de uma nova técnica de identificação de materiais poliméricos por meio do uso de um nariz eletrônico. Narizes eletrônicos têm sido desenvolvidos para detecção automática e classificação de odores e gases. São instrumentos capazes de medir a concentração ou intensidade odorante de modo similar a um olfatômetro, mas sem as limitações inerentes ao uso de painel humano, o que é altamente desejável. O nariz eletrônico é composto por um sistema de sensores, no nosso caso, utilizamos um arranjo de quatro sensores, que foram confeccionados pela deposição de finos filmes de polímeros condutores dopados sobre a superfície de eletrodos interdigitados. Estes sensores foram conectados a condutivímetros acoplados a um computador de uso pessoal (PC) através de um conversor AD. O PC era dotado de softwares de aquisição e tratamento de dados. Amostras dos materiais a serem analisados foram aquecidas a 257°C e o arranjo de sensores foi exposto aos compostos voláteis produzidos durante esse aquecimento. Realizaram-se 30 ensaios formados por períodos de exposição (5 segundos; compostos voláteis) intercalados por períodos de recuperação (45 segundos; ar puro). Os dados obtidos foram tratados estatisticamente por Análises de Componentes Principais (PCA). Esse arranjo de sensores mostrou-se eficiente, sendo capaz de diferenciar nove tipos de materiais poliméricos testados. Apresentou 100% de acerto em 30 ensaios de classificação realizados. / This research consists in the development of a new technique capable of the identification of polymeric materials using an electronic nose. Electronic noses have been developed for automatic detection and classification of odors, vapors and gases. They are instruments capable of measuring the concentration or intensity of an odorant similarly to an olfactometer, but without the inherent limitations of the human panel, which is highly desired. The electronic nose is composed by a system of chemoresistive sensors, in this case, an array of four sensors was used, which were made through a deposition of thin films of doped conductive polymers, on the surface of interdigitated electrodes. These sensors were connected to conductivity meters coupled to a personal computer (PC) through AD converters. The PC had acquisition and data processing softwares installed on it. Thirty readings were made or each analyzed polymer consisting of alternated 5 seconds exposure periods and 45 seconds recovery periods. The collected data were statistically processed by Principal Component Analysis (PCA). This electronic nose was efficient, being able to identify nine types of polymeric materials through the analysis of the different volatile compounds released when these materials were heated to the heat of 257ºC. A 100% correct classification score was obtained in the 30 sets of analysis.

L'objectif de cette recherche est d’explorer de nouvelles voies dans le domaine de la détection de gaz en ajustant finement la nature chimique, la texture et la morphologie de la couche active pour concevoir de nouveaux capteurs de gaz sélectifs. Ainsi, l’obtention de matériau présentant une haute sélectivité vis-à-vis des gaz constitue un enjeu majeur dans le domaine des capteurs de gaz. Notre approche est basée sur la conception de précurseurs moléculaires uniques - les alcynylorganoétains - qui contiennent toutes les fonctionnalités requises pour obtenir des matériaux hybrides stables par le procédé sol-gel, ces matériaux permettant une détection sélective des gaz nocifs / toxiques. Puis, les propriétés de détection de gaz de ces matériaux ont été comparées à celles de nanoparticules de dioxyde d'étain (SnO2) synthétisées à pression autogène. Une série de matériaux fonctionnels à base d'organooxoétains a été déposé sous forme de films minces films par le procédé d’enduction centrifuge puis ces films ont été caractérisés par des mesures de XRD, FT-IR, RAMAN, AFM, SEM, TEM, sorption d’azote et TGA-DTA. Les études de détection de gaz montrent que l'un des oxydes d'organoétain hybride présente une réponse sélective de détection de gaz tels que le CO, H2, l'éthanol, l'acétone et le NO2, tandis que les nanoparticules SnO2 conduisent à une détection non sélective des m^mes gaz dans les mêmes conditions. Ainsi, la meilleure sélectivité vis-à-vis du CO (à 100 et 200 ppm), de H2 (à 100, 200 et 400 ppm) et de NO2 (à 1, 2, 4 et 8 ppm) a été obtenue à 100 ° C pour le matériau hybride organostannique tandis que ce matériau ne conduisait à aucune réponse avec l’éthanol et l’acétone. Par ailleurs, les films de SnO2 nanoparticulaire sont sensibles à tous les gaz testés à de faibles concentrations (CO: 10 ~ 100 ppm, NO2: 0,5 à 4 ppm, H2: 100 à 800 ppm, acétone: 25 à 200 ppm, éthanol : 10 ~ 100 ppm) sur une plage de température comprise entre 200 et 400 °C. En outre, la sélectivité des matériaux SnO2 vis-à-vis de NO2 (entre 0,5 à 4 ppm) peut être optimisée en contrôlent bien la température de détection. Enfin, les matériaux à base d’organoétains et de dioxyde d’étain présentent une capacité de détection de gaz très élevée à de faibles concentrations en gaz. Ces résultats ont permis de développer une classe de matériaux entièrement nouvelle pour la détection sélective de gaz ainsi offrent la possibilité d'intégrer une fonctionnalité organique dans les oxydes métalliques capables de détecter les gaz. / The ultimate objective of this research is to draw new prospects in the gas sensing field by finely tuning the chemical nature, the texture and the morphology of the active layer to develop new type selective gas sensors. High gas selectivity has been a challenging issue during the past decades in the gas sensing area. Our approach is based on the design of molecular single precursors – alkynylorganotins which contain suitable functionalities required to obtain stable hybrid materials by the sol-gel method exhibiting selective gas detection towards harmful/toxic gases. Their gas sensing properties have been compared with those of tin dioxide (SnO2) nanoparticles synthesized by the hydrothermal route. A series of functional organooxotin-based materials have been processed as films by the spin or drop coating method and characterized by XRD, FT-IR, RAMAN, AFM, SEM, TEM, N2 sorption and TGA-DTA measurements. Gas sensing studies show that one of the hybrid organotin oxides exhibits an outstanding selective gas sensing response towards various gases, such as CO, H2, ethanol, acetone and NO2 whereas SnO2 nanoparticles present non-selective gas sensing ability under the same experimental condition. Thus, the best gas selectivity toward CO (at 100 and 200 ppm), H2 (at 100, 200 and 400 ppm) and NO2 (at 1, 2, 4 and 8 ppm) was achieved at 100 °C for the hybrid organooxotin-based film, however, it showed no response to ethanol/acetone at the same working temperature. On the other hand, the nanoparticulate SnO2 films prepared are sensitive to all the gases tested at low concentrations (CO: 10~100 ppm; NO2: 0.5~4 ppm; H2: 100~800 ppm; acetone: 25~200 ppm; ethanol: 10~100 ppm) in an operating temperature range from 200 to 400 °C. Moreover, the selectivity of SnO2 materials towards NO2 (between 0.5 ~ 4 ppm) can be optimized by well-manipulating the sensing temperatures. Finally, both organooxotin-based and tin oxide-based materials display superior gas sensing ability at low gas concentrations which opens a fully new class of gas sensing materials as well as a new possibility to integrate organic functionality in gas sensing metal oxides.

<p>Tungsten trioxide is a material with a variety of application areas. For example, the material is used within thin film technologies as electrochromic material in smart windows, as electrochemically functional material in thermal control applications or as active layer in gas sensing application. Metal-oxide semiconductor gas sensors are of significant interest to detect toxic and hazardous gases. The use of small and cheep sensors is preferable since a large number of sensors easily can be placed at different sites to monitor the concentration of different species without involving huge investments.</p><p>In this work, WO₃ nanoparticle films were produced using an advanced gas deposition unit for gas sensing applications. The structure of the WO₃ nanoparticle films was determined using X-ray diffraction, neutron scattering, X-ray photoelectron spectroscopy, elastic recoil detection analysis and electron microscopy. The as deposited films consist of sub-stoichiometric WO₃ and exhibit a large degree of porosity, which together with the small particle size of about 5 nm results in a large surface area and therefore excellent prospects for gas sensor applications. </p><p>Investigations on the optical properties and temperature dependence of the resistance indicate hopping conduction in the WO₃ films. The bandgaps for tetragonal and monoclinic WO₃ were found to be direct, which is in accordance with band structure calculations.</p><p>Sensor properties were investigated using resistance measurements upon test gas exposures. The experiments were performed at fixed operating temperatures as well as on temperature modulated sensors. The films of WO₃ showed excellent sensitivity to H₂S gas and selectivity to other gases. The responses of temperature modulated sensors were further analyzed using mathematical transformations and pattern recognition methods whereby different gases could be distinguished.</p><p>We also present a sensing technique using conduction noise as a tool for detection of alcohol vapor. The relative change of the noise, due to the inserted alcohol, can be as large as two orders of magnitude. </p>

Tungsten trioxide is a material with a variety of application areas. For example, the material is used within thin film technologies as electrochromic material in smart windows, as electrochemically functional material in thermal control applications or as active layer in gas sensing application. Metal-oxide semiconductor gas sensors are of significant interest to detect toxic and hazardous gases. The use of small and cheep sensors is preferable since a large number of sensors easily can be placed at different sites to monitor the concentration of different species without involving huge investments. In this work, WO3 nanoparticle films were produced using an advanced gas deposition unit for gas sensing applications. The structure of the WO3 nanoparticle films was determined using X-ray diffraction, neutron scattering, X-ray photoelectron spectroscopy, elastic recoil detection analysis and electron microscopy. The as deposited films consist of sub-stoichiometric WO3 and exhibit a large degree of porosity, which together with the small particle size of about 5 nm results in a large surface area and therefore excellent prospects for gas sensor applications. Investigations on the optical properties and temperature dependence of the resistance indicate hopping conduction in the WO3 films. The bandgaps for tetragonal and monoclinic WO3 were found to be direct, which is in accordance with band structure calculations. Sensor properties were investigated using resistance measurements upon test gas exposures. The experiments were performed at fixed operating temperatures as well as on temperature modulated sensors. The films of WO3 showed excellent sensitivity to H2S gas and selectivity to other gases. The responses of temperature modulated sensors were further analyzed using mathematical transformations and pattern recognition methods whereby different gases could be distinguished. We also present a sensing technique using conduction noise as a tool for detection of alcohol vapor. The relative change of the noise, due to the inserted alcohol, can be as large as two orders of magnitude.

Semiconductor-based gas sensors have been used for a wide range of applications over the last few decades. In this thesis, sensing properties of pure ZnO and Ga doped ZnO are investigated. There are three types of tested gas species, H2, O2 and NO, and three test temperatures, 300oC, 400oC and 500oC. After measurements of response to exposure to H2 and O2, it is concluded that Ga doped ZnO and ZnO are both n-type metal oxides. In measurements of NO, two test conditions were considered, the case with background O2 (10%) in the gas flow and the case without background O2. NO can be oxidized to NO2 or reduced to N2 and O2. The resistance of Ga doped ZnO and ZnO sensors always decreases for all exposures to NO except for the case in which the Ga doped ZnO sensor was exposed to NO in a background of O2 at 500 oC. In this special case, the resistance of Ga doped ZnO actually increases during exposure to low concentrations of NO (&lt; 30 ppm). It is not clear whether the change in response direction is due to an n-p transition or different reactions between gas molecules and Ga doped ZnO. Work function measurements were therefore conducted to understand more about the electron transfer during gas exposure. The work function measurements suggest that there are probably several stages of interactions between gas molecules and Ga doped ZnO during each gas pulse exposure.