AVS2001 Session TF+MM-MoM: Thin Film Sensors

Monday, October 29, 2001 10:20 AM in Room 123

Monday Morning

Start	Invited?	Item
10:20 AM		TF+MM-MoM-3 MEMS Device Platforms as Research Tools for Developing Improved Sensing Films C.J. Taylor, S. Semancik, R.E. Cavicchi (National Institute of Standards and Technology) Gas sensing characteristics of metal oxide films are dependent on the preparation method used in their fabrication. To optimize sensing film performance, one must understand how processing parameters influence composition and microstructure, and then correlate these changes with changes in the selectivity, sensitivity and stability of a sensor. We have been using arrays of microhotplates, MEMS devices fabricated with individually addressable heaters and sensing contacts, for both combinatorial studies and gas sensing. The short thermal time constant of the microhotplates makes them excellent microsubstrates for materials research where rapid heating and cooling during deposition are desired (heating rates of 10⁵ - 10⁶ °C /s are possible). Experiments have been performed using 4- and 16-element arrays as microsubstrates for CVD processing of titanium oxide and tin oxide using the single source precursors titanium(IV) nitrate, titanium(IV) isopropoxide and tin(IV) nitrate. Sensing films have been deposited both isothermally in the temperature range 100 to 450 °C, and using variable temperature deposition. Variable temperature deposition was achieved by applying triangle or square waves of varying frequency and amplitude to the heater. Film microstructure was examined by FESEM and its composition measured by EDS. We report on correlations between processing method, film microstructure and temperature dependent sensing performance for toluene, methanol, isopropanol, carbon monoxide, acetone, and other compounds.
10:40 AM		TF+MM-MoM-4 Correlation Between Gas Response of MIS Field-Effect Sensors and the Bond Strength Between the Metal and the Insulator Layer of the Device A.E. Åbom, L. Hultman, M. Eriksson (Linköping University, Sweden) Chemical gas sensors based on the field-effect are used in so called electronic noses as a powerful tool for various applications. The response mechanism is, however, not fully understood. In this work we monitor the material properties in order to understand the sensor properties. The sensors used in this work are Metal Insulator Semiconductor field-effect capacitors. The metal, Pt in this case, is grown by dc magnetron sputtering with varying growth parameters, with the Ar pressure ranging between 3 and 60 mTorr. The response to H₂ can be described by three steps,¹ dissociation of H₂ molecules on the Pt surface, transport of H atoms through the Pt film and adsorption of H (at the metal-oxide interface) as polarized species (either as dipoles or as charged species). The polarized H affects the electric field as a shift in the applied voltage. This voltage shift increases with increasing hydrogen concentration in the ambient and reaches a saturation value depending on the amount of adsorption sites at the interface and on the magnitude of the polarization. We have found that the largest obtained voltage shift varies with the deposition process. The lower the saturation response is, the stronger the film is adhering to the substrate, as measured with e.g. scratch adhesion tests in a Hysitron TriboScope. From in-situ XPS studies it is found that no chemical reactions occur between Pt and SiO₂. We will discuss how the varying bond strength between the two materials is caused either by mechanical interlocking or electrostatic forces. We will further elaborate on whether the amount of adsorbed H at the interface changes between the different samples due to a varying electron density² at the interface, or if the separation between the charges in the dipole layer is varying. ¹ Lundström K.I., Shivaraman, M.S., Svensson, C.M., J. of Appl. Phys. 46(9) 1975 ² Norskov, J.K. Phys. Rev. B 26 (6) 1982.
11:00 AM		TF+MM-MoM-5 On the Ammonia Response Mechanism of Field-effect Gas Sensors with Thin Pt Gates M. Lofdahl, M. Eriksson, I. Lundstrom (Linköping University, Sweden) The ammonia sensitivity of Pt gate field-effect chemical sensors shows a strong dependence on the morphology of the thin metal gate. Several investigations have shown that thin Pt gates are necessary to achieve high ammonia sensitivity and that thick gates show a low or even no sensitivity to ammonia.^1,2,3 Thin thickness means in this context that the Pt gate metal has to be made so thin that the underlying oxide is partly exposed. However, there exist an optimum, and if the thickness of the metal is made too thin the sensitivity decreases again. In this contribution the morphology of the thin Pt gate has been carefully investigated and characterised by SEM and complementary TEM studies and morphological parameters have been extracted for different processing conditions of the metal film deposition. By correlating the morphological parameters to measurements of the ammonia sensitivity in inert and oxygen-containing ambient the response mechanism is attributed to the existence of Pt-SiO2 boundaries in the metal. Further experimental investigations show that the Pt-SiO2 interfaces acts as catalytic sites for the dissociation of ammonia molecules and diffusion of detectable species from these sites determine the response. The diffusion length of the detectable species from the dissociation sites is strongly dependent on the existence of oxygen in the ambient. In an inert ambient the diffusion length can be several mm, whereas in 20 % of oxygen it is only in the order of mm. The most likely candidate for the detectable species is atomic hydrogen. ¹ A. Spetz, M. Armgath, and I. Lundström, Journal of Applied Physics 63, 1274-1283 (1988). ² J. F. Ross, I. Robins, and B. C. Webb, Sensors and Actuators 11, 73 (1987). ³ M. Löfdahl, C. Utaiwasin, A. Carlsson, I. Lundström, and M. Eriksson, Submitted to Sensors and Actuators B (2001).
11:20 AM		TF+MM-MoM-6 Charge Transport Mechanisms in Epitaxial Tungsten Oxide Films Used for Chemiresistive Sensors S.C. Moulzolf, R.J. Lad (University of Maine) Chemiresistive gas sensors fabricated from ultra-thin WO₃ films containing surface catalysts can be made highly sensitive towards a variety of target gases via manipulation of oxide surface chemistry. However, other important sensor characteristics including baseline stability, response time, and reproducibility are strongly dependent on the specific film microstructure and charge transport within the film. Using in situ Hall effect measurements coupled with structural analysis and gas testing experiments, we have determined a correlation between film deposition parameters, microstructure, and electrical response. WO₃ films were grown by rf magnetron sputtering on sapphire substrates to produce either epitaxial tetragonal or epitaxial monoclinic phases as deduced by RHEED and XRD. Exact film stoichiometries were controlled via post-deposition annealing treatments in vacuum and/or synthetic air environments. Four-point van der Pauw conductivity and Hall effect measurements as a function of temperature indicate that charge mobility is very small (<2cm²V^-1s^-1) and that polaron hopping is the dominant conduction mechanism. The conductivity of the monoclinic phase is an order of magnitude larger than the tetragonal phase and exhibits temperature dependence similar to measurements from single crystal WO₃. The mobility of the tetragonal phase increases with temperature consistent with scattering from the increased number of grain boundaries and smaller grain size as observed by STM and XRD. Extended annealing in vacuum to reduce the oxide stoichiometry causes higher conductivity and temperature dependent mobility behavior that may be attributed to crystallographic shear plane defects in the WO_3-x lattice. Upon gas exposure to H₂S or methanol, the tetragonal phase shows higher sensitivity compared to the monoclinic phase but a slower response which correlates with the lower Hall mobility.