Characterization and Modeling of Electrical Response of Electrode Catalyzed Reactions in AIGaN/GaN-Based Gas Sensors

AlGaN/GaN high electron mobility transistors (HEMT) and AlGaN/GaN diodes have promise for use as hydrogen and hydrocarbon sensors for a variety of industrial, military, and commercial applications. These semiconductor-based sensors have a number of advantages over other sensor technologies, such as the ability to operate at high temperatures, in corrosive environments, or under ionizing radiation. The high sensitivity of these devices to hydrogen-containing gases is associated with polarization differences within the AlGaN/GaN heterostructure that give rise to the formation of a two-dimensional electron gas (2DEG); exposure of the device to hydrogen changes the density of the 2DEG, which can be detected in a HEMT or diode structure. Although sensitivity to a range of gases has been reported, the factors that influence the behavior of the sensors are not well studied. The overarching goals of the research that follows were to determine how gas exposure conditions affect sensor behavior, to characterize and model the relationship between the electrical response of the sensors and the external gaseous environment, and to investigate the effects of using different metal catalysts on sensor behavior.;The electrical response of Pt-gated HEMT-based sensors were measured in a flowing gaseous stream consisting of hydrogen in a pure nitrogen diluent at ambient and elevated temperatures. The transistors exhibited excellent transfer characteristics for temperatures ranging from 25°C to 125°C. The absolute current change was measured as a function of hydrogen concentration and compared with simulated curves based on the Langmuir isotherm and four other modified isotherms at a sensor temperature of 125°C. The sensor response was found to monotonically increase for a wide range of hydrogen concentrations (500 ppb to 5 vol%). It was found that the Langmuir isotherm, which treats all hydrogen binding sites as equivalent, was inadequate to describe the sensor response. A simple two-state model involving two distinct hydrogen binding states that have previously been observed in surface studies was found to adequately describe the response of these sensors from 500 ppb to 5 vol% hydrogen in nitrogen. Other modified Langmuir models were also analyzed and compared with the two-state model. While the models based on modified isotherms all yielded good fits to the data, the simpler two-state model (based upon a weakly bound and strongly bound hydrogen atom) and the Sips model (with distribution of states skewed towards higher binding energies) more closely match results from surface studies of dissociative desorption of hydrogen on Pt. Either of these models should therefore serve as a reasonable foundation for understanding and modeling the response of AlGaN/GaN-based hydrogen sensors with Pt catalysts.;The electrical response of a Pt-gated HEMT-based sensor was also measured in a flowing gaseous stream consisting of hydrogen in air at elevated temperatures. The sensor response was found to monotonically increase for a narrow range of hydrogen pressures (1000 ppm to 4 vol%). Oxygen is found to decrease sensor response magnitude and increase the sensor response time. A modified Langmuir isotherm was found to adequately describe the influence of oxygen on a Pt-gated HEMT-based sensor under a narrow range of conditions. Additional sensor measurements were conducted on AlGaN/GaN diode sensors employing a variety of platinum-group catalysts. The influence of oxygen on the sensor response was found to be highly dependent upon the chemistry of hydrogen-oxygen interaction on the catalyst interface.;A sensor diode array was fabricated using a ternary Pdx CuyAu1-x-y composition spread alloy catalyst and tested in a flowing gaseous stream consisting of pure hydrogen in nitrogen at room temperature. The resulting diode sensitivity was mapped as a function of composition and revealed intriguing hot spots of hydrogen sensitivity. Numerous technological challenges prevented further exploration of the ternary alloy spread; however, the preliminary results of this structure suggest that a reduction in hydrogen binding energy on the surface can result in a substantial increase in hydrogen dipoles at the metal semiconductor interface.;The heterostructures used in this work were grown via metalorganic vapor phase epitaxy (MOVPE). Schottky diode and transistor devices employing platinum-group (Pd, Pt, Rh, Ir, Ru, and Os) catalysts were fabricated to allow electrical sensitivity in the presence of hydrogen and hydrogen containing gases. The generation of atomic hydrogen on the catalyst surface results in the rapid formation of hydrogen dipoles at the metal-semiconductor interface, which produces a measurable electronic response.;Sensitivity to methane and ethylene was demonstrated using AlGaN/GaN-based sensors. Detection of methane and ethylene require elevated temperatures to break the C-H bond and produce atomic hydrogen. The sensor response is significantly more complicated than hydrogen and not always well-behaved with respect to temperature and time. XPS measurements conducted at CMU indicate a buildup of carbon on the platinum surface upon hydrocarbon exposure, trending toward a saturated carbon content.;Lastly, operation of a diode sensor was examined in-situ under high hydrostatic pressure (2000psi) in both pure water and helium. Numerous stability issues were addressed in the course of these experiments. The steady-state influence of hydrostatic pressures on the diode sensor was found to be negligible in the absence of hydrogen. Hydrogen sensitivity was demonstrated in pure water with a hydrogen overpressure for devices employing an epoxy membrane. The same diode device failed to detect a large methane overpressure in water at room temperature and water at 80°C.