Gas Sensors Based on Coated and Doped Carbon Nanotubes

An array of carbon nanotubes (CNTs) in a substrate is connected to a variable-pulse voltage source. The CNT tips are spaced appropriately from the second electrode maintained at a constant voltage. A sequence of voltage pulses is applied and a pulse discharge breakdown threshold voltage is estimated for one or more gas components, from an analysis of the current-voltage characteristics. Each estimated pulse discharge breakdown threshold voltage is compared with known threshold voltages for candidate gas components to estimate whether at least one candidate gas component is present in the gas. The procedure can be repeated at higher pulse voltages to estimate a pulse discharge breakdown threshold voltage for a second component present in the gas. The CNTs in the gas sensor have a sharp (low radius of curvature) tip; they are preferably multiwall carbon nanotubes (MWCNTs) or carbon nanofibers (CNFs), to generate high-strength electrical fields adjacent to the current collecting plate, such as a gold plated silicon wafer or a stainless steel plate for breakdown of the gas components with lower voltage application and generation of high current. The sensor system can provide a high-sensitivity, low-power-consumption tool that is very specific for identification of one or more gas components. The sensors can be multiplexed to measure current from multiple CNT arrays for simultaneous detection of several gas components.

A resistor-type sensor was fabricated which has a network of cross-linked SWCNTs with purity over 99%. An ordinary cellulose paper used for filtration was employed as the substrate. The filter paper exhibits medium porosity with a flow rate of 60 mL/min and particle retention of 5-10m. The roughness and porosity of the papers are attractive because they increase the contact area with the ambient air and promote the adhesion to carbon nanotubes. The SWCNTs were functionalized with carboxylic acid (COOH) to render them hydrophilic, thus increasing the adhesion with the substrate. The functionalized SWCNTs were dispersed in dimethylformamide solution. The film composed of networks of cross-linked CNTs was formed using drop-cast coating followed by evaporation of the solvent. Adhesive copper foil tape was used for contact electrodes. Our sensors outperformed the oxide nanowire-based humidity sensors in terms of sensitivity and response/recovery times.

NASA Ames has developed very small-sized oxygen sensors made of a graphene and titanium dioxide (TiO2) hybrid material. With ultraviolet (UV) illumination, these sensors are capable of detecting oxygen (O2) gas at room temperature and at ambient pressure. The sensors are able to detect oxygen at concentrations ranging from about 0.2% to about 10% by volume under 365nm UV light, and at concentrations ranging from 0.4% to 20% by volume under short wave 254nm UV light. These sensors have fast response and recovery times and can also be used to detect ozone. This unique room temperature O2 sensor provides significant advantages in O2 sensing applications, especially those applications where high operating temperature requirements cannot be met, or would result in inefficient manufacturing processes. Since graphene is not intrinsically responsive to O2, and TiO2 is not responsive to oxygen at room temperature, the materials are first synthesized as a hybrid material. The synthesized graphene- TiO2 hybrid material is then ultrasonicated and then drop-casted onto a series of Interdigitated Electrodes (IDE) to form the sensors. Ultrasonication ensures effective charge transfer at the graphene- TiO2 interphase. The graphene and the titanium dioxide may be present in the composite material in different ratios to ensure optimal oxygen detection. It is the combination of graphene with TiO2 that yields a semiconducting material capable of O2 sensing at room-temperature operation.

Because chemical sensors are used in many aspects of space missions, NASA researchers are continually developing ever smaller and more robust sensors that can be manufactured inexpensively and in high quantities; e.g., in batches. Glenn has developed a way to inexpensively fabricate microsensors using a sacrificial template approach. A nanostructure, such as a carbon nanotube, serves as a template, which can then be coated with a high-temperature oxide material. The carbon nanotube can be burned off, or sacrificed, leaving only the metal oxide. The resulting structure provides the unique morphology and properties of the carbon nanotube, which are advantageous for sensing, along with the material durability and high-temperature sensing capabilities of the metal oxide. This technique increases the surface area available for sensing because both the interior and exterior of the resulting microsensor can be used for gas detection, significantly increasing performance. The fabrication of these microsensors includes three major steps: (1) synthesis of the porous metal or metal oxide nanostructures using a sacrificial template, (2) deposition of the electrodes onto alumina substrates, and (3) alignment of the nanostructures between the electrodes. The invention has been demonstrated for methane detection at room temperature (using tin oxide, with carbon nanotubes as the sacrificial template). The microsensor offers low power consumption (no heating required), compact size, extremely low cost, and simple batch-fabrication.

Current bulk or thick film solid electrolyte CO2 sensors are expensive, difficult to batch fabricate, and large in size. In contrast, this new amperometric, solid-state, oxide-based electrolyte CO2 microsensor is affordable, easy to fabricate, and is so small that it could easily be integrated onto a substrate the size of a postage stamp. The basic composition of the sensor is identical to a previously designed NASA Glenn technology in which a solid electrolyte of Na3Zr2Si2PO12 is deposited between interdigitated electrodes on an alumina substrate and is covered by Na2CO3/BaCO3. Unlike its predecessor, however, this innovation includes an additional layer of nanocrystalline SnO2 sol gel, an electron donor type (N-type) semiconductor, on top of the Na2CO3/BaCO3 . This new layer provides a greater number of electrons for reduction reaction at the working electrode to detect CO2. As a result, overall performance is enhanced, and this new state-of-the-art sensor has the ability to operate at temperatures as low as 375°C. This low temperature capability significantly decreases the amount of power required to operate the sensor, opening the door to a multitude of new applications that were previously unattainable.