Inexpensive Microsensor Fabrication Process

Conventional ambient-temperature oxygen sensors are limited in various ways: optically based sensors can be expensive and challenging to manufacture; electrochemical cells with liquid electrolytes can have limited lifetimes and become leak sources; and both types of sensors are difficult to miniaturize. These problems are addressed with Glenn's novel ambient temperature oxygen microsensor, which is based on a Nafiontm polymer electrolyte, microfabricated using thin-film technologies. In the past, one drawback of Nafiontm film has been that it can lose conductivity when the moisture content in the film is too low, potentially affecting sensor operation. Glenn researchers devised a method to use certain salts to hold water molecules in the Nafiontm film structure at room temperature. The presence of these salts provides extra sites in the film to promote proton (H+) mobility, thus improving film conductivity and overall sensor performance, particularly in arid and high-temperature environments. The innovative use of metal/metal oxide as the reference electrode enables miniaturization by eliminating the reference gas and sealing the reference electrode. The combination of interdigitized electrodes with the unique metal/metal oxide reference electrode permits sensor operation in either potentiometric or amperometric mode, as appropriate. In potentiometric mode, which measures voltage differences between working and reference electrodes in different gases, the voltage differences can be monitored with a voltmeter; however, the sensor itself does not need a power source. In room-temperature testing, the sensor achieved repeatable responses to 21 percent oxygen in nitrogen (using nitrogen as a baseline gas), and also detected oxygen from 7 to 21 percent, making Glenn's breakthrough technology usable for personal health monitoring as well as fire detection, fuel-leak detection, and environmental monitoring.

A typical sensor device includes a set of interdigitated microelectrodes fabricated by photolithography on silicon wafer or an electrically insulating substrate. In preparation for fabricating the SWCNT portion of such a sensor, a batch of treated (coated or doped) SWCNTs is dispersed in a solvent. The resulting suspension of SWCNTs is drop-deposited or injected onto the area containing the interdigitated electrodes. As the solvent evaporates, the SWCNTs form a mesh that connects the electrodes. The density of the SWCNTs in the mesh can be changed by varying the concentration of SWCNTs in the suspension and/or the amount of suspension dropped on the electrode area. To enable acquisition of measurements for comparison and to gain orthogonality in the sensor array, undoped SWCNTs can be similarly formed on another, identical set of interdigitated electrodes. Coating materials tested so far include chlorosulfonated polyethylene. Dopants that have been tested include Pd, Pt, Au, Cu and Rh nanoparticle clusters. To date, the sensor has been tested for NO2, NH3, CH4, Cl2, HCl, toluene, benzene, acetone, formaldehyde and nitrotoulene.

The nanoionic-based switches developed by NASA's Glenn Research Center exploit the properties of some amorphous materials that can incorporate relatively large amounts of metal and behave as solid electrolytes. As with liquid electrolytes found in lead-acid batteries, for example, solid electrolytes consist of mobile ions which undergo oxidation/reduction reactions at the anode and cathode of the system. The ionic conductivity of such a material can be of the same order of magnitude as the electronic conductivity of a semiconductor but without the drawbacks of an electromechanical device. In the nanoionic switch, ions are formed at an anode and migrate into the solid electrolyte, while electrons are injected from a cathode, thereby causing the growth of metal nanowires through the electrolyte from the cathode to the corresponding anode when a positive DC bias is applied. Once a nanowire has grown sufficiently to form an electrically conductive path between the electrodes, the switch is closed and no electric power is needed to maintain the connection, unlike in a MEMS or semiconductor-based switch. Moreover, the process of making the connection can easily be reversed by applying a negative bias, causing the wires to ungrow and the switch to open. Thus, NASA's state-of-the-art device is a reversible electrochemical switch that can have geometric features as small as nanometers. The process time for making or breaking the connection is very brief -- about a nanosecond. In addition, this nanoionic material can be deposited in such a way to form multilayer control circuits, which has the potential to minimize circuit footprints, reduce overall circuit losses, and provide unprecedented ease of integration.

Conventional scintillation radiation detectors make use of materials that emit light when hit by ionizing radiation. These large, bulky scintillators range anywhere from 6 inches to 6 feet in size. They are attached to glass photomultiplier tubes (PMTs), which are fragile, require high voltages, and are extremely sensitive to temperature changes. Conventional detectors also include a wave shifter (a material with a dopant to re-emit the scintillator light to match the sensitivity of the PMT or photodiode) which reduces efficiency and introduces unwanted weight and bulk. Glenn's particle counter overcomes these challenges. A prototype was constructed from off-the-shelf components, and features a small scintillator (less than six inches long) and a low-voltage, UV-sensitive, wide-bandgap photodiode as the detector. Careful matching of the properties of the light emitted from the scintillator, and tailoring the sensitivity of the photodiode eliminates the need for a PMT and a wave shifter, not only saving space, weight, and power but also eliminating potential failure modes. By using wide-bandgap detectors, it can operate in changing temperature, vibration, pressure, and gravity conditions without need for a temperature compensation system. Built from solid-state components, Glenn's device is compact and robust.

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.