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.

The technology is a solid state, Carbon Dioxide (CO2) sensor configured for sensitive detection of CO2 having a concentration within the range of about 100 Parts per Million (ppm) and 10,000 ppm in both dry conditions and high humidity conditions (e.g., > 80% relative humidity). The solid state CO2 sensor achieves detection of high concentrations of CO2 without saturation and in both dynamic flow mode and static diffusion mode conditions. The composite sensing material comprises Oxidized Multi-Walled Carbon Nanotubes (O-MWCNT) and a metal oxide, for example O-MWCNT and iron oxide (Fe2O3) nanoparticles. The composite sensing material has an inherent resistance and corresponding conductivity that is chemically modulated as the level of CO2 increases. The CO2 gas molecules absorbed into the carbon nanotube composites cause charge-transfer and changes in the conductive pathway such that the conductivity of the composite sensing material is changed. This change in conductivity provides a sensor response for the CO2 detection. The solid state CO2 sensor is well suited for automated manufacturing using robotics and software controlled operations. The solid state CO2 sensor does not utilize consumable components or materials and does not require calibration as often as conventional CO2 sensors. Since the technology can be easily integrated into existing programmable electronic systems or hardware systems, the calibration of the CO2 sensor can be automated.