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.

Die vorliegende Arbeit beschäftigt sich mit der Modellerstellung und Technologie eines gravimetrischen Gassensors für organische Gase. Die Besonderheit liegt in dem verwendeten Resonatortyp. Es handelt sich um einen lateral elektrostatisch angeregten quadratischen Plattenresonator, der mit einer Rezeptorschicht versehen wird. Mit Hilfe von FEM-Berechnungen werden die Eigenfrequenzen und Eigenformen berechnet. Für die untersuchte Lamé- und Square-Mode wird die Sensorgüte unter Berücksichtigung des "Squeeze-Film-Damping" sowie der viskoelastischen Rezeptorschichteigenschaften bestimmt. Die Sensormoden werden durch ein Feder-Masse-Modell mit einem Freiheitsgrad modelliert und durch ein elektrisches Ersatzschaltbild repräsentiert. Die berechneten Nachweisgrenzen für Oktan und Toluol bei 6-facher Rauschgrenze liegen im zweistelligen ppb-Bereich. Für die technologische Umsetzung werden SOI-Wafer verwendet. Die ≤ 100 nm betragenden Spaltbreiten zwischen Elektroden und Resonator werden durch das RIE-Ätzen von Siliziumgräben mit senkrechten Seitenwänden, der Abscheidung von SiO2 als Opferschicht und dem Füllen der Gräben mit hochdotiertem Polysilizium hergestellt. Die Kontaktierung der Resonatoren erfolgt über einen leitenden Stamm, der aufgrund von selbstjustierenden Prozessen die Resonatorplatte zentriert einspannt. / The following work is concerned with the modelling and fabrication technology of a gravimetric sensor for volatile organic compounds (VOC). Novelty is the combination of a lateral electrostatic driven square plate resonator with a gas sensitive detection layer. The eigenfrequencies and -modes are calculated with FEM simulations. Especially suited for gas sensors are the Lamé- and Square eigenmodes which are studied more closely. The quality factor is determined considering "squeeze film damping" and the viscoelastic properties of the gas sensitive detection layer. To present the sensor oscillation modes a spring mass model with one degree of freedom is determined and extended by an equivalent circuit diagram. The calculated limits of detections for octane and toluene are in the binary ppb-range, working with six times the limit of frequency noise. SOI-wafers are the base material for the sensor process flow. Electrode gaps ≤100 nm, essential for the electrostatic drive, are fabricated by RIE-etching vertical trenches into the device layer down to the buried oxide and by depositing a silicon dioxide as sacrifical layer and by refilling the trenches with highly doped polysilicon. The electrical contact of the resonator plate is ensured through an electrical conducting polysilicon stem. The developed process flow enables a self alignment ot the stem, clamping the plate centered.

Die vorliegende Arbeit beschäftigt sich mit der Modellerstellung und Technologie eines gravimetrischen Gassensors für organische Gase. Die Besonderheit liegt in dem verwendeten Resonatortyp. Es handelt sich um einen lateral elektrostatisch angeregten quadratischen Plattenresonator, der mit einer Rezeptorschicht versehen wird. Mit Hilfe von FEM-Berechnungen werden die Eigenfrequenzen und Eigenformen berechnet. Für die untersuchte Lamé- und Square-Mode wird die Sensorgüte unter Berücksichtigung des "Squeeze-Film-Damping" sowie der viskoelastischen Rezeptorschichteigenschaften bestimmt. Die Sensormoden werden durch ein Feder-Masse-Modell mit einem Freiheitsgrad modelliert und durch ein elektrisches Ersatzschaltbild repräsentiert. Die berechneten Nachweisgrenzen für Oktan und Toluol bei 6-facher Rauschgrenze liegen im zweistelligen ppb-Bereich. Für die technologische Umsetzung werden SOI-Wafer verwendet. Die ≤ 100 nm betragenden Spaltbreiten zwischen Elektroden und Resonator werden durch das RIE-Ätzen von Siliziumgräben mit senkrechten Seitenwänden, der Abscheidung von SiO2 als Opferschicht und dem Füllen der Gräben mit hochdotiertem Polysilizium hergestellt. Die Kontaktierung der Resonatoren erfolgt über einen leitenden Stamm, der aufgrund von selbstjustierenden Prozessen die Resonatorplatte zentriert einspannt. / The following work is concerned with the modelling and fabrication technology of a gravimetric sensor for volatile organic compounds (VOC). Novelty is the combination of a lateral electrostatic driven square plate resonator with a gas sensitive detection layer. The eigenfrequencies and -modes are calculated with FEM simulations. Especially suited for gas sensors are the Lamé- and Square eigenmodes which are studied more closely. The quality factor is determined considering "squeeze film damping" and the viscoelastic properties of the gas sensitive detection layer. To present the sensor oscillation modes a spring mass model with one degree of freedom is determined and extended by an equivalent circuit diagram. The calculated limits of detections for octane and toluene are in the binary ppb-range, working with six times the limit of frequency noise. SOI-wafers are the base material for the sensor process flow. Electrode gaps ≤100 nm, essential for the electrostatic drive, are fabricated by RIE-etching vertical trenches into the device layer down to the buried oxide and by depositing a silicon dioxide as sacrifical layer and by refilling the trenches with highly doped polysilicon. The electrical contact of the resonator plate is ensured through an electrical conducting polysilicon stem. The developed process flow enables a self alignment ot the stem, clamping the plate centered.