Ronald P. Manginell

Microfabricated silicon gas chromatographic micro-channels: fabrication and performance

Using both wet and plasma etching, we have fabricated micro- channels in silicon substrates suitable for use as gas chromatography (GC) columns. Micro-channel dimensions range from 10 to 80 micrometer wide, 200 to 400 micrometer deep, and 10 cm to 100 cm long. Micro-channels 100 cm long take up as little as 1 cm2 on the substrate when fabricated with a high aspect ratio silicon etch (HARSE) process. Channels are sealed by anodically bonding Pyrex lids to the Si substrates. We have studied micro-channel flow characteristics to establish model parameters for system optimization. We have also coated these micro-channels with stationary phases and demonstrated GC separations. We believe separation performance can be improved by increasing stationary phase coating uniformity through micro-channel surface treatment prior to stationary phase deposition. To this end, we have developed microfabrication techniques to etch through silicon wafers using the HARSE process. Etching completely through the Si substrate facilitates the treatment and characterization of the micro-channel sidewalls, which dominate the GC physico- chemical interaction. With this approach, we separately treat the Pyrex lid surfaces that form the top and bottom surfaces of the GC flow channel.

A monolithically-integrated μGC chemical sensor system.

Gas chromatography (GC) is used for organic and inorganic gas detection with a range of applications including screening for chemical warfare agents (CWA), breath analysis for diagnostics or law enforcement purposes, and air pollutants/indoor air quality monitoring of homes and commercial buildings. A field-portable, light weight, low power, rapid response, micro-gas chromatography (μGC) system is essential for such applications. We describe the design, fabrication and packaging of μGC on monolithically-integrated Si dies, comprised of a preconcentrator (PC), μGC column, detector and coatings for each of these components. An important feature of our system is that the same mechanical micro resonator design is used for the PC and detector. We demonstrate system performance by detecting four different CWA simulants within 2 min. We present theoretical analyses for cost/power comparisons of monolithic versus hybrid μGC systems. We discuss thermal isolation in monolithic systems to improve overall performance. Our monolithically-integrated μGC, relative to its hybrid cousin, will afford equal or slightly lower cost, a footprint that is 1/2 to 1/3 the size and an improved resolution of 4 to 25%.

Mass-Sensitive Microfabricated Chemical Preconcentrator

This paper describes a mass-sensitive microfabricated preconcentrator for use in chemical detection microsystems. The device combines mass sensing and preconcentration to create a smart preconcentrator (SPC) that determines when it has collected sufficient analyte for analysis by a downstream chemical microsystem. The SPC is constructed from a Lorentz-force-actuated pivot-plate resonator with an integrated heater. Subsequent to microfabrication, the SPC is coated with an adsorbent for collection of chemical analytes. The frequency of operation varies inversely with the mass of collected analyte. Such shifts can be measured by a back-EMF in the SPCs drive/transducer line. By using a calibrated vapor system, the limit of detection of the SPC was determined to be less than 50 ppb for dimethyl-methyl-phosphonate (DMMP) (actual limits of detection are omitted due to export control limitations). At 1 ppm of DMMP, 1-s collection was sufficient to trigger analysis in a downstream microsystem; other micropreconcentrators would require an arbitrary collection time, normally set at 1 min or longer. This paper describes the theory of operation, design, fabrication, coating, vapor system testing, and integration of the SPC into microanalytical systems. The theory of operation, which is applicable to other torsional oscillators, is used to predict a shear modulus of silicon (100) of G = 57.0 GPa plusmn2.2 GPa.

Characterization of the embedded micromechanical device approach to the monolithic integration of MEMS with CMOS

Recently, a great deal of interest has developed in manufacturing processes that allow the monolithic integration of microelectromechanical systems (MEMS) with driving, controlling, and signal processing electronics. This integration promises to improve the performance of micromechanical devices as well as lower the cost of manufacturing, packaging, and instrumenting these devices by combining the micromechanical devices with a electronic devices in the same manufacturing and packaging process. In order to maintain modularity and overcome some of the manufacturing challenges of the CMOS-first approach to integration, we have developed a MEMS-first process. This process places the micromechanical devices in a shallow trench, planarizes the wafer, and seals the micromechanical devices in the trench. Then, a high-temperature anneal is performed after the devices are embedded in the trench prior to microelectronics processing. This anneal stress-relieves the micromechanical polysilicon and ensures that the subsequent thermal processing associated with fabrication of the microelectronic processing does not aversely affect the mechanical properties of the polysilicon structures. These wafers with the completed, planarized micromechanical devices are then used as starting material for conventional CMOS processes. The circuit yield for the process has exceeded 98 percent. A description of the integration technology, the refinements to the technology, and wafer- scale parametric measurements of device characteristics is presented. Additionally, the performance of integrated sensing devices built using this technology is presented.

High-speed two-dimensional gas chromatography using microfabricated GC columns combined with nanoelectromechanical mass sensors

We report here for the first time the combination of microfabricated gas chromatography (GC) columns with pneumatic modulation to achieve high-speed comprehensive two-dimensional gas chromatography (GCxGC) using microfabricated components. The GCxGC system is in turn combined with nanoelectromechanical (NEMS) resonator mass sensors that have been coated with a chemically-selective polymer to enhance detection of phosphonate compounds that are useful surrogates for chemical warfare agents (CWA). GC elution peak widths on the order of 20 msec have been achieved. Retention times on the order of 2–4 seconds have been demonstrated for polar compounds, indicating that this microfabricated GCxGC system can be applied for rapid analyses.

Integrated Chemical Analysis Systems for Gas Phase CW Agent Detection

A miniature, integrated chemical laboratory (μChemLab) is being developed that utilizes microfabrication to provide faster response, smaller size, and an ability to utilize multiple analysis channels for enhanced versatility and chemical discrimination. Improved sensitivity and selectivity are achieved by using a cascaded approach where each channel includes a sample collector/concentrator, a gas chromatographic (GC) separator, and a chemically selective surface acoustic wave (SAW) array detector. Prototypes of all three components have been developed and demonstrated individually and current work is focused on integrating these into a complete analysis system.

An overview of micromachined platforms for thermal sensing and gas detection

Micromachined hotplates, membranes, filaments, and cantilevers have all been used as platforms for thermal sensing and gas detection. Compared with conventional devices, micromachined sensors are characterized by low power consumption, high sensitivity, and fast response time. Much of these gains can be attributed to the size reductions achieved by micromachining. In addition, micromachining permits easy, yet precise tailoring of the heat transfer characteristics of these devices. By simple alterations in device geometry and materials used, the relative magnitudes of radiation, convection and conduction losses and Joule heat gains can be adjusted, and in this way device response can be optimized for specific applications. The free- standing design of micromachined platforms, for example, reduces heat conduction losses to the substrate, thereby making them attractive as low-power, fast-response heaters suitable for a number of applications. However, while micromachining solves some of the heat transfer problems typical of conventionally produced devices, it introduces some of its own. These trade-offs will be discussed in the context of several micromachined thermal and gas sensors described in the literature. These include micromachined flow sensors, gas thermal conductivity sensors, pressure sensors, uncooled IR sensors, metal-oxide and catalytic/calorimetric gas sensors. Recent results obtained for a microbridge-based catalytic/calorimetric gas sensor will also be presented as a means of further illustrating the concepts of thermal design in micromachined sensors.

Microcombustor array and micro-flame ionization detector for hydrocarbon detection

This paper describes results from using a microcombustor to create two hydrocarbon gas sensors: one utilizing calorimetry and the other a flame ionization detector (FID) mechanism. The microcombustor consists of a catalytic film deposited on the surface of a microhotplate. This micromachined design has low heat capacity and thermal conductivity, making it ideal for heating catalysts placed on its surface. The catalytic materials provide a natural surface-based method for flame ignition and stabilization and are deposited using a micropen system, which allows precise and repeatable placement of the materials. The catalytic nature of the microcombustor design expands the limits of flammability (LoF) as compared with conventional diffusion flames; an unoptimized LoF of 1-32% for natural gas in air was demonstrated with the microcombustor, whereas conventionally 4-16% is observed. The LoF for hydrogen, methane, propane and ethane are likewise expanded. Expanded LoF permit the use of this technology in applications needing reduced temperatures, lean fuel/air mixes, or low gas flows. By coupling electrodes and an electrometer circuit with the microcombustor, the first ever demonstration of a microFID utilizing premixed fuel and a catalytically-stabilized flame has been performed; the detection of 1.2-2.9 % of ethane in a hydrogen/air mix is shown.

Microfabricated gas phase chemical analysis systems

A portable, autonomous, hand-held chemical laboratory (/spl mu/ChemLab/sup TM/) is being developed for trace detection (ppb) of chemical warfare (CW) agents and explosives in real-world environments containing high concentrations of interfering compounds. Microfabrication is utilized to provide miniature, low-power components that are characterized by rapid, sensitive and selective response. Sensitivity and selectivity are enhanced using two parallel analysis channels, each containing the sequential connection of a front-end sample collector/concentrator, a gas chromatographic (GC) separator, and a surface acoustic wave (SAW) detector. Component design and fabrication and system performance are described.

Two-Dimensional Modeling and Simulation of Mass Transport in Microfabricated Preconcentrators

The adsorption and desorption behavior of a planar microfabricated preconcentrator (PC) has been modeled and simulated using the computational fluid dynamics (CFD) package CFDRC-ACE+trade. By comparison with the results of a designed experiment, model parameters were determined. Assuming a first-order reaction for the adsorption of a light hydrocarbon chemical analyte onto the PC adsorbent and a unity-value sticking coefficient, a rate constant of 36 500 s-1 was obtained. This compares favorably with the value of 25 300 s-1 obtained by application of the Modified-Wheeler equation. The modeled rate constant depends on the concentration of adsorbent sites, estimated to be 6.94 ldr 10-8 kmol/m2 for the Carboxen 1000 adsorbent used. Using the integral method, desorption was found to be first order with an Arrhenius temperature dependence and an activation energy of 30.1 kj/mol. Validation of this model is reported herein, including the use of Aris-Taylor dispersion to predict the influence of fluidics surrounding the PC. A maximum in desorption peak area with flow rate, predicted from a quadratic fit to the results of the designed experiment, was not observed in the 2-D simulation. Either approximations in the simulated model or the nonphysical nature of the quadratic fit are responsible. Despite the apparent simplicity of the model, the simulation is internally self consistent and capable of predicting performance of new device designs. To apply the method to other analytes and other adsorbent materials, only a limited number of comparisons to experiment are required to obtain the necessary rate constants.