Depuis la révolution industrielle les niveaux des concentrations atmosphériques des gaz à effet de serre ne cessent d’augmenter provocant ainsi une accélération du réchauffement climatique. Les composés organiques volatils (COVs) contribuent non seulement à cet effet de serre mais aussi à la pollution environnementale qui a un impact négatif sur toutes les espèces vivantes de la planète. Par exemple, au cours de l’année 2012, la pollution de l'air a été à l’origine 7 millions de décès, selon l'Organisation mondiale de la santé (OMS) [1]. Très récemment, une étude médicale de la commission Lancet sur la pollution et la santé a révélé qu'en 2015 un décès sur six était lié à la pollution de l'air et de l'eau, 6,5 millions de décès dans le monde chaque année sont liés à la pollution de l'air intérieur et extérieur [2]. En effet, les COVs, très volatils et utilisés comme solvants par exemple, peuvent être indirectement à l’origine de toux, d’inconfort thoracique, de gêne douloureuse, d’essoufflement respiratoire, d’irritation nasale ou oculaire ou encore de la gorge. Ils peuvent aussi être directement toxiques ou explosifs ou encore perturbateurs de la réponse immunitaire. De plus certains d’entre eux sont classés CMR (cancérogène, mutagène et reprotoxique). Dans ces conditions une meilleure connaissance des effets liés à l’exposition aux COVs sur la santé et l’environnement est vraiment nécessaire. Cette connaissance passe également par la détection et la quantification des concentrations de COVs afin de proposer un meilleur aménagement des environnements et d'alerter les individus concernés en temps réel sur les dangers encourus. La plupart des plateformes déjà existantes ou commercialisées sont soient trop coûteuses, soient très consommatrices d'énergie, soient fonctionnelles à des températures élevées, soient instables pour la détection en temps réel ou à long terme ce qui limite la prolifération des sites de mesures. Ainsi, cette thèse s’inscrit dans le domaine des capteurs de gaz dédiés pour la détection de la pollution dans l’air. Elle porte sur le développement d’une plateforme de détection, de suivi et de quantification des composés organiques volatils (COVs) en temps réel, utilisant un capteur de gaz différentiel flexible et imprimé basé sur des transducteurs micro-ondes et des matériaux carbonés polymères composites comme couches sensibles. Le dispositif proposé vise à fournir des informations directement exploitables pour constituer à terme une plateforme de faible coût embarquée, dédiée à l’internet des objets pour faciliter la prolifération des sites de détection et de contrôle en réalisant des réseaux de capteurs communicants sans fil fonctionnant en environnements variés. / Since the Industrial Revolution, the levels of atmospheric concentrations of greenhouse gases have been increasing, causing an acceleration of global warming. Volatile organic compounds (VOCs) contribute not only to this greenhouse effect, but also to environmental pollution, which has a negative impact on all living species on the planet. For example, in the year 2012, air pollution caused 7 million deaths, according to the World Health Organization (WHO) [1]. In addition, a very recent medical study by the Lancet Commission on Pollution and Health found that one in six deaths in 2015 was related to air and water pollution [2]. Also, indoor and outdoor air pollution is linked to 6.5 million deaths worldwide each year. VOCs can indirectly cause cough, chest discomfort, painful discomfort, shortness of breath, as well as nasal, ocular or throat irritation. They can also be directly toxic or explosive or disruptive of the immune response. In addition, some of them are classified as CMR (carcinogenic, mutagenic and reprotoxic). They are very volatile and often used as solvents for example. In these conditions, a better understanding of the health and environmental effects of exposure to VOCs is necessary. Such knowledge also involves the detection and quantification of VOC concentrations in order to propose a better management of the environments and to alert people in real time of the dangers incurred. Most of the existing or commercially available platforms are either too expensive, energy intensive, high temperature functional, unstable for real-time or long-term detection, which limits the proliferation of measurement sites. This thesis is in the field of dedicated gas sensors for the detection of pollution in the air. It deals with the development of a platform for the detection, monitoring and quantification of volatile organic compounds (VOCs) in real time, using a flexible and printed differential gas sensor based on microwave transducers and composite polymeric carbon materials as sensitive layers. The proposed device aims at providing directly exploitable information such as a low-cost embedded platform dedicated to the Internet of things and which offers increasing possibilities for the proliferation of detection and control sites by realizing networks of wireless communicating sensors operating in various environments.

No description available.

I takt med att tekniken för mikroelektromekaniska system utvecklas uppkommer det nya områden för tillämpning. Ett område är inom gassensorer där icke-dispersiv infraröd strålning används genom att mäta absorptionen hos olika gaser för att bestämma mängden av en specifik gas i luften. I detta projekt var målet att använda en vågledare med en infraröd lysdiod på ena sidan och en fotodetektor på andra sidan där vågledaren har som uppgift att utsätta ljuset för maximal mängd koldioxid innandet träffar fotodetektorn. Motiveringen för valet av koldioxid var att det är en gas som har stor påverkan på både klimat och arbetsmiljö. Metoden som ansågs vara bäst för placeringen av tidigare nämnda komponenter var att använda programmerbara rörelseenheter som kallas hexapod som består av sex ben som möjliggör tredimensionella rörelser och rotationer kring varje axel i det kartesiska koordinatsystemet. Experiment där elektromagnetiska störningar från lysdioden undersöktes vilket visade att det förekom elektromagnetisk störning samt att lysdioden påverkade fotodetektorn genom spridning trots att lysdiod och fotodetektor inte var vända mot varandra. / As the technology for microelectromechanical systems develops, new areas of application are emerging. One area is within gas sensors where non-dispersive infrared radiation is used by measuring the absorption of various gases to determine the concentration of a specific gas in the air. In this project, the goal was to use a waveguide with an infrared LED on one side and a photodetector on the other side where the waveguide has the task of exposing the light to the maximum amount of carbon dioxide before it hits the photodetector. The reason for the choice of carbon dioxide was that it is a gas that has a great impact on both the climate and the working environment. The method that was considered to be best for the placement of the aforementioned components was to use programmable motion units called hexapods which consist of six struts that enable three-dimensional movements and rotations around each axis of the Cartesian coordinate system. Experiments in which the electromagnetic interference from the LED were investigated showed that there was electromagnetic interference and that the LED affected the photodetector by scattering, even though the LED and photodetector were not facing each other.

The technology evolution and complexity of new circuit applications involve emerging reliability problems and even more sensitivity of integrated circuits (ICs) to electrostatic discharge (ESD)-induced damage. Regardless of the aggressive evolution in downscaling and subsequent improvement in applications' performance, ICs still should comply with minimum standards of ESD robustness in order to be commercially viable. Although the topic of ESD has received attention industry-wide, the design of robust protection structures and circuits remains challenging because ESD failure mechanisms continue to become more acute and design windows less flexible. The sensitivity of smaller devices, along with a limited understanding of the ESD phenomena and the resulting empirical approach to solving the problem have yielded time consuming, costly and unpredictable design procedures. As turnaround design cycles in new technologies continue to decrease, the traditional trial-and-error design strategy is no longer acceptable, and better analysis capabilities and a systematic design approach are essential to accomplish the increasingly difficult task of adequate ESD protection-circuit design. This dissertation presents a comprehensive design methodology for implementing custom on-chip ESD protection structures in different commercial technologies. First, the ESD topic in the semiconductor industry is revised, as well as ESD standards and commonly used schemes to provide ESD protection in ICs. The general ESD protection approaches are illustrated and discussed using different types of protection components and the concept of the ESD design window. The problem of implementing and assessing ESD protection structures is addressed next, starting from the general discussion of two design methods. The first ESD design method follows an experimental approach, in which design requirements are obtained via fabrication, testing and failure analysis. The second method consists of the technology computer aided design (TCAD)-assisted ESD protection design. This method incorporates numerical simulations in different stages of the ESD design process, and thus results in a more predictable and systematic ESD development strategy. Physical models considered in the device simulation are discussed and subsequently utilized in different ESD designs along this study. The implementation of new custom ESD protection devices and a further integration strategy based on the concept of the high-holding, low-voltage-trigger, silicon controlled rectifier (SCR) (HH-LVTSCR) is demonstrated for implementing ESD solutions in commercial low-voltage digital and mixed-signal applications developed using complementary metal oxide semiconductor (CMOS) and bipolar CMOS (BiCMOS) technologies. This ESD protection concept proposed in this study is also successfully incorporated for implementing a tailored ESD protection solution for an emerging CMOS-based embedded MicroElectroMechanical (MEMS) sensor system-on-a-chip (SoC) technology. Circuit applications that are required to operate at relatively large input/output (I/O) voltage, above/below the VDD/VSS core circuit power supply, introduce further complications in the development and integration of ESD protection solutions. In these applications, the I/O operating voltage can extend over one order of magnitude larger than the safe operating voltage established in advanced technologies, while the IC is also required to comply with stringent ESD robustness requirements. A practical TCAD methodology based on a process- and device- simulation is demonstrated for assessment of the device physics, and subsequent design and implementation of custom P1N1-P2N2 and coupled P1N1-P2N2//N2P3-N3P1 silicon controlled rectifier (SCR)-type devices for ESD protection in different circuit applications, including those applications operating at I/O voltage considerably above/below the VDD/VSS. Results from the TCAD simulations are compared with measurements and used for developing technology- and circuit-adapted protection structures, capable of blocking large voltages and providing versatile dual-polarity symmetric/asymmetric S-type current-voltage characteristics for high ESD protection. The design guidelines introduced in this dissertation are used to optimize and extend the ESD protection capability in existing CMOS/BiCMOS technologies, by implementing smaller and more robust single- or dual-polarity ESD protection structures within the flexibility provided in the specific fabrication process. The ESD design methodologies and characteristics of the developed protection devices are demonstrated via ESD measurements obtained from fabricated stand-alone devices and on-chip ESD protections. The superior ESD protection performance of the devices developed in this study is also successfully verified in IC applications where the standard ESD protection approaches are not suitable to meet the stringent area constraint and performance requirement.

Dans un monde de plus en plus pollué par l'activité industrielle, la détection des espèces gazeuses nocives dans l'atmosphère est d'une importance essentielle. Le marché des capteurs de gaz est déjà bien développé, avec la présence de diverses technologies et principes de détection, chacune présentant des avantages et des inconvénients intrinsèques. Dans le cadre de cette thèse, un alliage entre deux ou plusieurs technologies de détection typiquement utilisées de façon autonome a été visée, afin d'améliorer les performances globales des systèmes capteurs ainsi formées. A ce fin, nous avons conçu et étudié des dispositifs capteurs basées sur la transduction optique, couplée à un matériau sensible au gaz cible à détecter. Plus précisément, nous avons intégré pour la première fois un matériau catalyseur pouvant accélérer le taux d'oxydation des espèces chimiques (tel le monoxyde de carbone ou l'hydrogène) avec une architecture optique capable d'absorber la chaleur cédée lors de cette oxydation. L'augmentation de température occasionnée est traduite en une variation d'intensité lumineuse constituante le signal de sortie du capteur. Les travaux effectués sur les mesures de la dispersion thermique et chromatique de l'indice de réfraction des matériaux constituant le transducteur optique par des techniques d'optique guidé, ellipsométrie et des techniques photométriques sont présentés. Le sondage par moyen optique des propriétés électriques des matériaux semiconducteurs a également été étudié, y compris les variations de ces propriétés en présence des gaz oxydants, réducteurs et combustibles. / In a world suffering from increasing air pollution due to spiraling industrial activity, the detection of toxic gasses in the atmosphere is of paramount importance. The gas detector market is already well developed, and features a wide variety of detection technologies and techniques, each presenting its own set of intrinsic advantages and drawbacks. In this thesis, a combination of two or more technologies typically used independently has been studied in order to improve the global performances of gas detection systems. To this length, we have conceived and studied detector architectures based upon optical transduction systems, coupled with a material presenting a specific sensitivity to the target gas. More precisely, we have for the first time integrated a catalyst designed to accelerate the oxidation rate of chemical species (such as carbon monoxide or hydrogen) with an optical component capable of absorbing the heat generated by the oxidation reaction. The associated increase in temperature is translated to a variation of the optical intensity comprising the exit signal of the detector. The work carried out measuring the chromatic and temperature dispersion of the refractive index of the materials comprising the optical transduction component by guided mode techniques, ellipsometry and photometric techniques is presented. The optical probing of the electrical properties of semiconductor materials has also been studied, including the variations of these properties following interactions with oxidizing, reducing, or combustible gasses.

EN Heme containing gas sensor proteins play important role in bacterial physiology in regulating many processes such as cell differentiation, virulence, biofilm formation or intercellular communication. For their structure, typical modular architecture is characteristic where various sensor domains (usually at the N-terminus) regulate the activity of the catalytic or functional domains (usually at the C-terminus). In this dissertation thesis, we focused on three representatives from the group of oxygen sensing proteins, namely histidine kinase AfGcHK, diguanylate cyclase YddV, phosphodiesterase EcDOS and also on protein RR, which is the interaction partner of AfGcHK. The main aim of the thesis was to study intra-protein/inter-domain signal transduction in two representatives of heme sensor proteins with a globin fold of the sensor domain (AfGcHK, YddV) and in one representative with PAS fold of the sensor domain (EcDOS). Another objective was to describe inter-protein signal transduction in the two component signaling system AfGcHK-RR and structurally characterize these two interacting partners. Emphasis was also placed on the study of the interaction between model sensor domains and different signaling molecules and also on function of individual amino acids involved in the binding of these...

A presente tese de doutorado deu início a uma nova linha de pesquisa no grupo de Síntese de Polímeros Condutores do IQ-USP, que consiste nos estudos relacionados a sensores de gases para equipamentos do tipo narizes eletrônicos, confeccionados com polímeros condutores. Para isso, foram sintetizados eletroquimicamente sete polímeros da família dos poli(p-fenileno vinileno)s, dos quais cinco inéditos, substituídos por grupos receptores e doadores de elétrons.Todos os polímeros, incluindo seus precursores, foram caracterizados espectroscopicamente (RMN de 1H, IV e UV-Vis). Estudos de análises térmicas (TG e DSC) e de cromatografia por exclusão de tamanho (SEC) foram realizados com os polímeros que possuíam grupos alifáticos de cadeias longas, tendo sido um desses polímeros usado na confecção de dispositivos metal/polímero/metal, cujas medidas de corrente vs. tensão permitiram determinar a mobilidade dos portadores de carga. Sensores de gases foram feitos com os polímeros sintetizados, mostrando boa seletividade quando testados com vapores de uma série de solventes orgânicos polares e apolares. / In this thesis we describe the electrosynthesis of seven difterent poly(p-phenilenevinylene)s, PPVs, bearing long and short, electron donating and withdrawing side groups. These polymers are aimed for our recent interest in gas sensors based on conducting polymers and their application in electronic noses. Five out of the seven polymers are novel materials, hence never described before. The polymers were characterized spectroscopically. Those with long side chain were also submitted to thermal analyses and size exclusion chromatography. Electrical measurements (I x V) in metal/polymer/metal sandwich devices led to the determination of the charge carrier mobility of one of the polymers. Gas sensors, having thin films of the synthesized polymers as active layers, have shown good selectivity towards several organic solvent vapors and water as well.

Les systèmes mobiles intelligents sont déjà dotés de plusieurs composants de type capteur comme les accéléromètres, les thermomètres et les détecteurs infrarouge. Cependant, jusqu’à aujourd’hui l’intégration de capteurs chimiques dans des systèmes compacts sur puce reste limitée pour des raisons de consommation d’énergie et dissipation de chaleur principalement. Le travail présenté dans cette thèse fut donc concentrée sur la démonstration de l’intégration 3D monolithique de SETs sur un substrat de technologie CMOS (Complementary Metal Oxide Semiconductor) pour la réalisation de la fonction capteurs de gaz très sensible et ultra basse consommation d’énergie. L’approche proposée consiste à l’intégration de SETs métalliques à double grilles dans l'unité de fabrication finale BEOL (Back-End-Of-Line) d'une technologie CMOS à l’aide du procédé nanodamascene. L'objectif principal de cette thèse de doctorat peut être divisé en 4 parties : (1) la modélisation et simulation de la réponse d’capteur de gaz à base de SET à double grilles ou d’un MOSFET FD-SOI, et l’estimation de la sensitivité ainsi que la puissance consommée; (2) la caractérisation de la sensitivité du Pt comme couche sensible pour la détection du H2 par la technique de mesure de charge de surface, et le développement du procédé de texturation de surface de la grille fonctionnalisée avec les réseaux de nanotubes de carbone; (3) le développement et l’optimisation du procédé de fabrication des SETs à double grilles dans l’entité BEOL d’un substrat CMOS; et (4) la fonctionnalisation d’un MOSFET FD-SOI avec du Pt pour réalise la fonction de capteur de H2. / The need of integration of new functionalities on mobile and autonomous electronic systems has to take into account all the problematic of heterogeneity together with energy consumption and thermal power dissipation. Therefore, the work presented in this thesis is focussed on the proof of concept of 3D monolithical integration of SETs on CMOS technology for high sensitivity and ultra-low power gas sensing functionality. The proposed approach is to integrate metallic double gate-single electron transistors (DG-SETs) in the Back-End-Of-Line (BEOL) of CMOS circuits (within the CMOS interconnect layers) using the nanodamascene process. The main objective of this Ph.D. thesis can be divided into 4 parts: (1) modelling and simulation of a DG-SET and an FD-SOI MOSFET based gas sensor response, and estimation of the sensitivity as well as the power consumption; (2) investigation of Pt sensitivity to hydrogen by surface charge measurement technique and development of the sensing electrode surface texturing process with CNT networks; (3) development and optimization of DG-SET integration process in the BEOL of a CMOS substrate, and (4) FD-SOI MOSFET functionalization with Pt for H2 sensing.

Les travaux portent sur les multiplexeurs optiques fonctionnant à mi-IR pour la source à large bande dans l'application de détection de gaz. Deux configurations ont été étudiées: réseau de guides d'onde (AWG) et réseau concave planaire (PCG). Premièrement, le principe du fonctionnement a été compris afin de développer une solution analytique pour le champ de sortie en utilisant une approximation gaussienne du champ et de l'optique de Fourier. Ensuite, un outil de simulation semi-analytique de la réponse spectrale pour les deux configurations de multiplexeur a été développé dans MATLAB. La distribution normale des erreurs de phase a été introduite dans le modèle semi-analytique AWG, ce qui nous a permis d'étudier la corrélation entre l'écart-type des erreurs de phase et le niveau de diaphonie de la réponse spectrale AWG. AWG à 5,65 μm a été fabriqué à partir de la technologie SiGe / Si à l'aide de l'outil MATLAB pour le calcul des paramètres de conception et de l'outil P.Labeye pour le calcul de la géométrie AWG. Les dispositifs avec des paramètres légèrement variables ont été caractérisés: AWG1 avec guides d'ondes de 4,6 μm et MMI de 9 μm; AWG2 avec guides d'ondes de 4,6 μm et MMI de 11 μm; AWG3 avec guides d'ondes de 4,8 μm et MMI de 9 μm. Des mesures des dispositifs sur la puce 36 (centre de la plaquette) et sur la puce 32 (côté de la plaquette) ont été effectuées et analysées. Les mesures de température de AWG2 et AWG3 (puce 32 et puce 36) aux points cinq points de température ont montré une dépendance linéaire du déplacement spectral avec la température qui a une bonne corrélation avec les prédictions de simulation. / The work focuses on optical multiplexers operating in mid-IR for broadband source in gas sensing application. Two configurations were studies – arrayed waveguide grating (AWG) and planar concave grating (PCG). First, principle of operation was understood in order to develop analytical solution for output field using Gaussian approximation of the field and Fourier Optics. Then, semi-analytical simulation tool of the spectral response for both multiplexer configurations was developed in MATLAB. Normal distribution of phase errors was introduced to semi-analytical AWG model, which allowed us to study the correlation between standard deviation of phase errors and the level of crosstalk of AWG spectral response. AWG at 5.65 µm was fabricated based on SiGe/Si technology using the MATLAB tool for design parameters calculation and P.Labeye’s tool for AWG geometry calculation. Devices with slightly varying parameters were characterized: AWG1 with 4.6 µm waveguides and 9µm MMI; AWG2 with 4.6 µm waveguides and 11µm MMI; AWG3 with 4.8 µm waveguides and 9µm MMI. Measurements of devices on chip 36 (center of the wafer) and chip 32 (side of the wafer) were performed and analyzed. Temperature measurements of AWG2 and AWG3 (chip 32 and chip 36) at points five temperature points showed linear dependence of spectral shift with the temperature which has a good correlation with simulation predictions.

A presente tese de doutorado deu início a uma nova linha de pesquisa no grupo de Síntese de Polímeros Condutores do IQ-USP, que consiste nos estudos relacionados a sensores de gases para equipamentos do tipo narizes eletrônicos, confeccionados com polímeros condutores. Para isso, foram sintetizados eletroquimicamente sete polímeros da família dos poli(p-fenileno vinileno)s, dos quais cinco inéditos, substituídos por grupos receptores e doadores de elétrons.Todos os polímeros, incluindo seus precursores, foram caracterizados espectroscopicamente (RMN de 1H, IV e UV-Vis). Estudos de análises térmicas (TG e DSC) e de cromatografia por exclusão de tamanho (SEC) foram realizados com os polímeros que possuíam grupos alifáticos de cadeias longas, tendo sido um desses polímeros usado na confecção de dispositivos metal/polímero/metal, cujas medidas de corrente vs. tensão permitiram determinar a mobilidade dos portadores de carga. Sensores de gases foram feitos com os polímeros sintetizados, mostrando boa seletividade quando testados com vapores de uma série de solventes orgânicos polares e apolares. / In this thesis we describe the electrosynthesis of seven difterent poly(p-phenilenevinylene)s, PPVs, bearing long and short, electron donating and withdrawing side groups. These polymers are aimed for our recent interest in gas sensors based on conducting polymers and their application in electronic noses. Five out of the seven polymers are novel materials, hence never described before. The polymers were characterized spectroscopically. Those with long side chain were also submitted to thermal analyses and size exclusion chromatography. Electrical measurements (I x V) in metal/polymer/metal sandwich devices led to the determination of the charge carrier mobility of one of the polymers. Gas sensors, having thin films of the synthesized polymers as active layers, have shown good selectivity towards several organic solvent vapors and water as well.