More commonly referred to as a quartz crystal microbalance (QCM), thickness-shear mode (TSM) quartz resonator devices utilize an acoustic wave to establish a bulk-detection mechanism prompting their utilization as gravimetric sensors with nanogram mass sensitivity and capability to measure various film property dynamics, due to variations in the system environment, of thin-films that are uniformly distributed across the resonator surface. The development of an absolute TSM-based nanobalance and an experimental technique using conventional TSM resonators for the real-time measurement of the change in the viscoelastic shear modulus and fractional free-hole volume of a poly(isobutylene) film due to the sorption of various organic vapors are presented in this thesis work. Development of an electrode-modified TSM quartz resonator that is responsive to nanogram mass loadings, while exhibiting a mass sensitivity profile that is independent of material placement on the sensor platform, is detailed in this thesis work. The resulting nanogram balance would greatly enhance the field of mass measurement and become useful in applications such as droplet gravimetry, the study of non-volatile residue (NVR) contamination in solvents. A ring electrode design predicted by an analytical theory for sensitivity distribution to achieve the desired uniform mass sensitivity distribution is presented in this work. Using a microvalve capable of depositing nanogram droplets of a polymer solution, and a linear stepping stage for radial positioning of these droplets across the sensor platform, measurements of the mass sensitivity distributions were conducted and are presented. The measurements agree well with theory. Further improvements are possible and are identified to achieve better uniformity and to reduce the instability in the resonant frequency of these devices. Additionally, droplet gravimetric results for NVR in methanol droplets using the modified TSM devices are presented, which compare well with determinations made by evaporation of larger volumes of the stock solutions. Storage modulus, G', loss modulus, G", and, consequently, the shear modulus, G (G=G'+jG"), of polymer and polymer/solvent systems were measured in this work using a TSM quartz resonator. The polymer poly(isobutylene) was spin-coated as a film of a few microns thickness on the surface of the TSM device and, upon inducing oscillation of the device at its resonance frequency (several mega-Hertz), the impedance characteristics were measured. In addition, the poly(isobutylene) film was exposed to known weight concentrations, up to 20%, of benzene, chloroform, n-hexane, and dichloromethane vapors diluted in nitrogen gas, and the impedance characteristics were measured. Data collected from the impedance analyzer were examined by modeling the polymer and polymer/solvent loaded TSM device with an electrical equivalent circuit and a mechanical perturbation model to reliably yield the shear modulus. Using a superposition theory and the shear modulus, the fractional free volume of the polymer/solvent systems were determined. These results correlate well with values found using the Vrentas-Duda free-volume (FV) theory. A novel experimental technique for measuring fractional free-hole volumes of polymer/solvent mixtures is established in this thesis work.

Ces travaux de thèe portent sur le développement d’un outil d’analyse numérique dédié à l’ étude de nouveaux résonateursà quartz à ondes de volume et utilisant les éléments finis. Cette méthode de caractérisation permet la détermination deséléments du schéma électrique équivalent (résistance, inductance et capacité) d’une fréquence de résonance donnée ainsique son facteur de qualité, tout en prenant en compte dans le modèle la sensibilité du cristal de quartz à la températureet aux contraintes induites par le montage. Une étape de validation est d’abord réalisée afin de vérifier nos choix, enterme de modélisation et de calcul, en confrontant les données issues de la simulation aux mesures de résonateurs déjàexistants. Les trois dispositifs analysés (40 MHz, 10 MHz et 100 MHz) montrent une bonne concordance entre théorieet expérience. Pour obtenir de tels résultats, la structure de maintien est prise en compte et modélisée sous forme dezones d’amortissement de Rayleigh lorsque le piégeage de l’énergie n’est pas optimal (présence d’un mode de plaque).Un aspect important des résonateurs est ensuite étudié : le comportement en température. En effet, les contraintes dedilatation thermique ainsi que l’évolution des coefficients élastiques en fonction de la température induisent une dérivefréquentielle. La comparaison entre théorie et expérience nous permet de vérifier l’allure des courbes et de quantifier ledegré de précision du modèle. L’effet d’une contrainte mécanique appliquée sur le pourtour de la lame de quartz est parla suite introduit dans le modèle en utilisant la méthode de perturbation de Sinha-Tiersten. Il est alors possible de définirl’impact des défauts de fabrication sur la fréquence du résonateur. Enfin, la méthode numérique est appliquée à l’étudede structures innovantes dans le cadre du projet FREQUENCE2009. Il s’agit de revisiter le concept du résonateur BVA etd’envisager des procédés de fabrication collective. L’idée consiste ainsi à remplacer le rayon de courbure d’un résonateur,dont la fréquence utile se trouve aux alentours de 9 MHz, par une série de marches, plus compatible avec les procédés dela micro électronique (DRIE : Deep Reactive Ion Etching). Bien que les résultats expérimentaux soient, dans ce cas, loin denos attentes, nous constatons que l’outil d’analyse est parfaitement capable de prédire les caractéristiques de nouvellesstructures. / This work is devoted to the development of a digital analysis tool dedicated to study new bulk acoustic waves quartz resonatorsby using finite elements. This method of characterization allows the calculation of the elements of the equivalentelectrical circuit (resistor, inductance and capacitor) of a given resonant frequency as well as the quality factor, while takinginto account its sensitivity to the temperature and to the stresses induced by the mounting support. Firstly, a validationphase is carried out in order to check our choices, in terms of modeling and computation, by comparing simulation data tothe measures of existing resonators. The three analyzed devices (40MHz, 10 MHz and 100 MHz) show good agreementbetween theory and experiment. To obtain such results, the mounting support is taken into account and modeled thanks toRayleigh damping areas when the trapping of energy is not optimal (presence of a spurious shell vibration mode). Then, animportant aspect of resonators is studied : the temperature behavior of its vibrating modes. Indeed, the thermal expansionstresses as well as the change of stiffness coefficients according to the temperature induce frequency shift. The comparisonbetween theory and experiment allows us to check the shape of curves and to quantify the accuracy of the model.Thereafter, the effect of mechanical stress applied on the edge of the blank of quartz is introduced in the model by usingthe perturbation method developed by Tiersten and Sinha. So, it is possible to define the influence of some manufacturingdefects on the resonant frequency. Finally, the digital method is applied to study innovative structures in the framework ofthe project FREQUENCE2009. The aim is to review the concept of BVA resonator and consider collective manufacturingprocesses. The idea involves replacing the radius of curvature of a resonator, for which the expected frequency is around9 MHz, by several steps, more compatible with microelectronics processes (DRIE : Deep Reactive Ion Etching). Althoughthe results are far from our expectations, we note that the analysis tool is perfectly able to anticipate the characteristics ofnew structures.