Cette étude est dédiée à l’optimisation de capteurs chimiques de gaz de type résistifs à base de dioxyde d’étain (SnO2) pour l’application en ligne d’échappement automobile. Les capteurs sont élaborés par la technique de sérigraphie qui permet la production en masse de capteurs robustes sur substrat alumine. En vue de l’application automobile visée, les capteurs ont été optimisés par l’ajout d’une couche protectrice poreuse déposée sur l’élément sensible de SnO2. Le comportement de ces capteurs a été étudié en fonction de différents paramètres, comme la température et la vitesse des gaz, représentatifs de conditions d’échappement automobile. De plus, une modélisation « simple » de la réponse électrique des capteurs en fonction de la concentration d’un ou plusieurs gaz polluants cibles a été proposée. / This study is dedicated to the optimization of chemical gas sensors based on resistive type tin dioxide (SnO2) for automotive exhaust application. The sensors were produced by screen-printing technique which allows mass production of robust sensors on alumina substrate. In regards of the automotive application, the sensors were optimized by adding a porous protective layer deposited on the sensing element SnO2. The behaviour of this type of gas sensors was studied depending on gas parameters such as gas temperature and velocity, representative of real operation conditions. In addition, a “simple” modelisation of the electrical response of sensors depending on the concentration of one or more gaseous targets is proposed.

<p>Chemical gas sensors can be used in a variety of applications such as process control, security systems and medical diagnosis. In the research for new functions and new sensing materials a “breadboard” would be useful. A technique that has been investigated for such a purpose is the grid-gate device which is a metal-oxide-semiconductor (MOS) based gas sensor. It is a MOS capacitor consisting of a passive grid-gate with depositions of sensing materials overlapping the grid. The measuring is carried out with a light addressable method called scanning light pulse technique (SLPT) which enables the detection of spatially distributed gas response.</p><p>A development of the grid-gate sensor would be to separate the sensing materials from the chip. In this thesis the aim was to see if this was possible by depositing the sensing material on a slide of micro pillars which was put on top of a biased grid-gate chip.</p><p>The test was made with palladium depositions in an ambient of synthetic air and 2500 ppm hydrogen, and the measuring technique was SLPT as for the preceding device.</p><p>The result of the test was that the new device showed a combined gas response of both charge content shift at flat-band voltage and at inversion voltages. The conclusion is therefore that the sensing material can be separated from the grid-gate chip and that the response will be caused by several mechanisms. The two-dimensional image response utilized for the preceding grid-gate device will instead be a multi-dimensional response consisting of the curve for the charge content shift at every measuring position.</p>

A sensor is a device that transforms a physical, chemical, or biological stimulus into a readable signal. The integral part that sensors make in modern technology is considerable and many are those trying to take the development of sensor technology further. Sensor systems are becoming more and more complex and may contain a wide range of different sensors, where each may deliver a multitude of signals.Although the data generated by modern sensor systems contain lots of information, the information may not be clearly visible. Appropriate handling of data becomes crucial to reveal what is sought, but unfortunately, that process is not always straightforward and there are many aspects to consider. Therefore, analysis of multidimensional sensor data has become a science.The topic of this thesis is signal processing of multidimensional sensordata. Surveys are given on methods to explore data and to use the data to quantify or classify samples. It is also discussed how to avoid the rise of artifacts and how to compensate for sensor deficiencies. Special interest is put on methods being practically applicable to chemical gas sensors. The merits and limitations of chemical sensors are discussed and it is argued that multivariate data analysis plays an important role using such sensors. The contribution made to the public by this thesis is primarily on techniques dealing with difficulties related to the operation of sensors in applications. In the second paper, a method is suggested that aims at suppressing the negative effects caused by unwanted sensor-to-sensor differences. If such differences are not suppressed sufficiently, systems where sensors occasionally must be replaced may degrade and lose performance. The strong-point of the suggested method is its relative ease of use considering large-scale production of sensor components and when integrating sensors into mass-market products. The third paper presents a method that facilitates and speeds up the process of assembling an array of sensors that is optimal for a particular application. The method combines multivariate data analysis with the `Scanning Light Pulse Technique'. In the first and fourth papers, the problem of source separation is studied. In two separate applications, one using gas sensors for combustion control and one using acoustic sensors for ground surveillance, it has been identified that the current sensors outputs mixtures of both interesting- and interfering signals. By different means, the two papers applies and evaluates methods to extract the relevant information under such circumstances. / En sensor är en komponent som överför en fysikalisk, kemisk, eller biologisk storhet eller kvalitet till en utläsbar signal. Sensorer utgör idag en viktig del i flertalet högteknologiska produkter och sensorforskning är ett aktivt område. Komplexiteten på sensorbaserade system ökar och det blir möjligt att registrera allt er olika typer av mätsignaler. Mätsignalerna är inte alltid direkt tydbara, varvid signalbehandling blir ett väsentligt verktyg för att vaska fram den viktiga information som sökes. Signalbehandling av sensorsignaler är dessvärre inte en okomplicerad procedur och det finns många aspekter att beakta. Av denna anledning har signalbehandling och analys av sensorsignaler utvecklats till ett eget forskningsområde. Denna avhandling avhandlar metoder för att analysera komplexa multidimensionella sensorsignaler. En introduktion ges till metoder för att, utifrån mätningar, klassificera och kvantifiera egenskaper hos mätobjekt. En överblick ges av de effekter som kan uppstå på grund av imperfektioner hos sensorerna och en diskussion föres kring metoder för att undvika eller lindra de problem som dessa imperfektioner kan ge uppkomst till. Speciell vikt lägges vid sådana metoder som medför en direkt applicerbarhet och nytta för system av kemiska sensorer. I avhandlingen ingår fyra artiklar, som vart och en belyser hur de metoder som beskrivits kan användas i praktiska situationer. / Sensor,

Chemical gas sensors can be used in a variety of applications such as process control, security systems and medical diagnosis. In the research for new functions and new sensing materials a “breadboard” would be useful. A technique that has been investigated for such a purpose is the grid-gate device which is a metal-oxide-semiconductor (MOS) based gas sensor. It is a MOS capacitor consisting of a passive grid-gate with depositions of sensing materials overlapping the grid. The measuring is carried out with a light addressable method called scanning light pulse technique (SLPT) which enables the detection of spatially distributed gas response. A development of the grid-gate sensor would be to separate the sensing materials from the chip. In this thesis the aim was to see if this was possible by depositing the sensing material on a slide of micro pillars which was put on top of a biased grid-gate chip. The test was made with palladium depositions in an ambient of synthetic air and 2500 ppm hydrogen, and the measuring technique was SLPT as for the preceding device. The result of the test was that the new device showed a combined gas response of both charge content shift at flat-band voltage and at inversion voltages. The conclusion is therefore that the sensing material can be separated from the grid-gate chip and that the response will be caused by several mechanisms. The two-dimensional image response utilized for the preceding grid-gate device will instead be a multi-dimensional response consisting of the curve for the charge content shift at every measuring position.

The work presented in this dissertation suggests novel design of chemical plasmonic sensors which have been developed based on Localized Surface Plasmon Resonance (LSPR), and Surface-enhanced Raman scattering (SERS) phenomena. The goal of the study is to understand the SERS phenomena for 3D hybrid (organic/inorganic) templates and to design of the templates for trace-level detection of selected chemical analytes relevant to liquid explosives and hazardous chemicals. The key design criteria for the development of the SERS templates are utilizing selective polymeric nanocoatings within cylindrical nanopores for promoting selective adsorption of chemical analyte molecules, maximizing specific surface area, and optimizing concentration of hot spots with efficient light interaction inside nanochannels. The organic/inorganic hybrid templates are optimized through a comprehensive understanding of the LSPR properties of the gold nanoparticles, gold nanorods, interaction of light with highly porous alumina template, and the choice of physical and chemical attributes of the selective coating. Furthermore, novel method to assemble silver nanoparticles in 3D as the active SERS-active substrate has been demonstrated by uniform, in situ growth of silver nanoparticles from electroless deposited silver seeds excluding any adhesive polymer layer on template. This approach can be the optimal for SERS sensing applications because it is not necessary to separate the Raman bands of the polyelectrolyte binding layer from those of the desired analyte. The fabrication method is an efficient, simple and fast way to assemble nanoparticles into 3D nanostructures. Addressable Raman markers from silver nanowire crossbars with silver nanoparticles are also introduced and studied. Assembly of silver nanowire crossbar structure is achieved by simple, double-step capillary transfer lithography. The on/off SERS properties can be observed on silver nanowire crossbars with silver nanoparticles depending on the exact location and orientation of decorated silver nanoparticles nearby silver nanowire crossbars. As an alternative approach for the template-assisted nanostructure design, porous alumina membrane (PAM) can be utilized as a sacrificial template for the fabrication of the nanotube structure. The study seeks to investigate the design aspects of polymeric/inorganic hybrid nanotube structures with plasmonic properties, which can be dynamically tuned by external stimuli such as pH. This research suggests several different organic/inorganic nanostructure assemblies by various template-assisted techniques. The polymeric/inorganic hybrid nanostructures including SERS property, pH responsive characteristics, and large surface area will enable us to understand and design the novel chemical plasmonic sensors.

This thesis explores the application of coiled sapphire multimode optical fibers for evanescent wave chemical sensing in both the visible spectrum and the near infrared. As has been suggested in the literature pertaining to silica fibers, bending converts low-order modes to high order ones, which leads to more evanescent absorption and thus a more sensitive chemical detector. By coiling the fiber many times, it was expected that even greater sensitivity would be attained. Experiments were performed to investigate the sensor response to different solutions and to characterize this response. In the first of three experiments, the large absorption peak of water at 3μm was examined in order to compare the sensitivity of a straight fiber versus a coiled one. In the second experiment, the effect of increasing the number of coils was investigated, as was the response of the sensor to varying concentrations of water in heavy water. In the third experiment, methylene blue dye was used to investigate the extent of adsorption of dye molecules on the sapphire fiber and its persistence

In order to address the challenges of capacitive sensing in harsh environment, self resonant passive wireless sensors are studied. The capacitive sensing elements based on interdigitated capacitor (IDC) sensor are used. A semi-empirical model providing accurate capacitance calculation for IDCs over a wide range of dimensions and dielectric constants is developed. An equivalent circuit model based on electric field distribution is proposed, leading to a closed form approximation for IDC capacitance calculation. The conductivity of the material under test is also considered and a model is proposed to calculate effective capacitance as a function of conductivity and measurement frequency. The model is used to study the design optimization of IDC sensor and suggested design procedure is proposed. To wirelessly interrogate the capacitive sensor, it is connected to an inductive element to form a resonant circuit, while the measurement is made at remote reader coil. Advantages and disadvantages of different type of resonant structure design are analyzed. In order to assist the design process, a SPICE circuit model is developed to estimate the resonant frequency of the self resonant sensor. Miniaturized sensors with different dimensions are designed, fabricated and tested. The sensor is integrated with silicon nanowire fabric coated with polymer. Measurements are made to illustrate the enhancement in sensing capability by integrating chemical selective material. / text

Este trabalho descreve o desenvolvimento de um biossensor contendo transdução condutométrica sem contato (C4D, capacitively coupled contactless conductivity detection) e ácido fólico (FA) como biorreceptor em microchip, uma nova alternativa que poderá ser utilizada na determinação do biomarcador tumoral FR-&alpha;. Essa espécie exibe interações com FA altamente específicas, com constantes de formação da ordem de 109-1010. Os dispositivos microfluídicos, os quais consistiram de uma lâmina de vidro (integrando os eletrodos), dielétrico (contendo a fase biossensora) e substrato de poli(dimetilsiloxano) (PDMS, incorporando os microcanais), foram fabricados utilizando-se processos de fotolitografia e deposição de filmes finos em fase vapor. Objetivando melhorias nos níveis de detecção da C4D, estudos de sensibilidade com base em parâmetros da curva analítica foram conduzidos alterando-se a natureza do dielétrico e a configuração dos eletrodos. Posteriormente, estudos de caracterização foram realizados para as superfícies modificadas com os intermediários de imobilização; condições reacionais distintas (reagente, concentração, solvente e tempo) foram consideradas. As técnicas de microscopia eletrônica de varredura e espectroscopia de fotoelétrons excitados por raios-X foram usadas, respectivamente, a fim de se verificar a possível formação de aglomerados e permitir determinações qualitativas e quantitativas sobre as composições químicas das superfícies. Como resultado dos experimentos de sensibilidade e caracterização de superfície, adotamos os parâmetros seguintes para os ensaios de interações biomoleculares posteriores: filme de SiO2 como dielétrico, eletrodos seletivos à C4D com formato retangular e orientação antiparalela e monocamadas automontadas do reagente 3-aminopropil(trietoxisilano) como intermediário de imobilização de FA. As duas etapas finais do trabalho foram: otimização do tempo de funcionalização com FA (3, 5 e 7 h) e caracterização da fase biossensora, realizada a partir de medidas de C4D e microscopia de força atômica (AFM). Para o primeiro caso, os microchips foram aplicados a um padrão de anticorpo monoclonal específico a FA (&alpha;-FA). Os ensaios biomoleculares indicaram uma adsorção efetiva de FA junto à superfície de SiO2 silanizada, sem a ocorrência (ao menos em níveis significativos) de impedimentos estéricos de sua espécie bioativa. Dentre os tempos de funcionalização investigados, 3 h foi aquele que resultou em uma maior sensibilidade do método. Em termos da etapa de caracterização eletroquímica da fase biossensora, seus resultados mostraram haver correlação entre a resposta analítica e as interações FA/&alpha;-FA. Em adição, conforme indicaram as medidas de AFM, não houve alterações drásticas na morfologia do substrato (SiO2) em função dos processos de modificação química de superfície. Por fim, o uso da C4D como uma técnica de transdução em biossensores mostrou-se uma alternativa promissora para a análise do biomarcador tumoral FR-&alpha;. Dentre outros aspectos, essa plataforma analítica requer uma instrumentação simples, barata e portátil, não apresenta inconvenientes relacionados ao contato eletrodo/solução, dispensa o uso de mediadores redox e permite a determinação simultânea de multianalitos. Neste ínterim, alterações no transdutor devem ser implementadas visando um aumento na sensibilidade do método, o qual representa seu fator limitante principal. / This work describes the development of a biosensor containing capacitively coupled contactless conductivity transduction (C4D) and folic acid (FA) as bioreceptor in microchip, a new alternative that can be used in FR-&alpha; tumor biomarker analysis. FR-&alpha; exhibits highly specific interactions with FA, showing formation constants of the order of 109-1010. The microfluidic devices consisted of a glass layer (integrating the electrodes), dielectric (containing the biosensor phase), and poly(dimetilsiloxane) substrate (PDMS, incorporating microchannel). The microfabrication stage evolved photolithography processes, metal adsorption via sputtering, and plasma-enhanced vapor film deposition. In order to improve detection levels of C4D, sensitivity studies were conducted by changing the dielectric nature and electrode configuration. Through flow analysis with given electrolyte standards, the limits of detection and quantification were calculated based on analytical curve parameters. Subsequently, researches were performed to characterize the modified surfaces with immobilization intermediate considering reaction conditions distinct (reagent, concentration, solvent, and time). The techniques of scanning electron microscopy and X-ray photoelectron spectroscopy were employed, respectively, aiming to verify the clusters formation and allow qualitative and quantitative determinations about the surfaces chemical composition. From the results of sensitivity experiments and surface characterization, we adopt the following parameters for the biomolecular interactions assays: SiO2 film as dielectric, C4D selective electrodes with rectangular shape and antiparallel orientation, and self-assembled monolayers of 3-aminopropyl(triethoxysilane) as intermediary for immobilization of FA. The two final steps of the work were: optimizing the FA functionalization time (3, 5, and 7 h) and phase biosensor characterization, made from measures of C4D and atomic force microscopy (AFM). For the first case, due to the absence of FR-&alpha; standard for purchase, the microchips were applied to FA specific monoclonal antibody (&alpha;-FA). The biomolecular assay indicated effective adsorption of FA, without occurrence (at least in significant levels) of steric hindrance of its bioactive specie. Among the investigated times of functionalization, 3 h resulted in a higher sensitivity of the method. In terms of biosensor phase electrochemical characterization stage, their results evidenced correlation between analytical response and FA/&alpha;-FA interactions. Additionally, as the AFM measurements showed, drastic changes in the morphology of the substrate (SiO2) with the surface modification processes did not occur. Finally, the use of the C4D as transduction technical in biosensors proved to be a promissory alternative for FR-&alpha; tumor biomarker analysis. Among other features, this platform has not drawbacks related to the electrode/solution contact, dispenses the use of redox mediators, allows the simultaneous determination of multianalytes, and employs an instrumentation that is simple, cheap, and portable. Nevertheless, changes in the transducer should be implemented to increase the method sensitivity, which represents its main limiting factor.

abstract: Monitoring of air pollutants is critical for many applications and studies. In order to access air pollutants with high spatial and temporal resolutions, it is necessary to develop an affordable, small size and weight, low power, high sensitivity and selectivity, and wireless enable device that can provide real time monitoring of air pollutants. Three different kind of such devices are presented, they are targeting environmental pollutants such as volatile organic components (VOCs), nitrogen dioxide (NO2) and ozone. These devices employ innovative detection methods, such as quartz crystal tuning fork coated with molecularly imprinted polymer and chemical reaction induced color change colorimetric sensing. These portable devices are validated using the gold standards in the laboratory, and their functionality and capability are proved during the field tests, make them great tools for various air quality monitoring applications. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2014

The focus of this project was to investigate the use of interdigitated electrodes (IDEs) as impedimetric ion-selective chemical sensors for the determination of several important analytes found within a freshwater aquarium. The overall aim of this research was to work towards a prototype sensing device that could eventually be developed into a commercial product for sale to aquarium owners. Polyvinyl chloride and sol-gels containing commercially-available ionophores for four aquarium-significant ions (NH4+, NO2-, NO3- and pH) were prepared and investigated for use within polymeric ion-selective membranes. Three separate IDE transducers were produced using either photolithography or screen-printing microfabrication techniques. A sinusoidal voltage was applied to the IDEs and an LCR meter was used to measure changes in the conductance and capacitance of the ion-selective membrane layer deposited over the electrode digits. Each ionophore, when tested within potentiometric ion-selective electrodes (ISEs), was found to be suitable for further investigation within IDE devices. Sol-gels were investigated as a potential membrane material for a coated wire electrode; however, poor response characteristics were observed. An IDE sensor fabricated in-house using lift-off photolithography and spin-coated with a polymeric membrane was found to produce non-selective responses caused by changes in the conductivity of the test solution. IDE devices with reduced geometric parameters were purchased and coated with a selective polymeric membrane. When the membrane was spin-coated, non-selective responses were observed; therefore, drop-coating of the membrane material was investigated. This initially resulted in an unacceptably long response time; however, this effect was reduced by decreasing the membrane solution viscosity prior to drop-coating. A fully-screen printed carbon IDE device was fabricated by incorporating the ionophore into a support matrix based on a commercial dielectric paste. Matrix interferences to the sensor response were reduced by printing ‘build-up’ layers over the sensing area prior to the ion-selective membrane. Two novel routes for monitoring the water quality of an aquarium, using IDE sensors fabricated by either photolithography or screen-printing, have been demonstrated. Due to the commercial aspect of this project, it is important to consider the final cost of producing these sensors. Both of the techniques used to produce ion-selective sensors require further experimentation to optimise the sensor response, prior to integration within a multi-analyte sensing prototype.