Gregory C. Frye-Mason

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.

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.

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.

Rapid detection of bacteria with miniaturized pyrolysis-gas chromatographic analysis

Rapid detection and identification of bacteria and other pathogens is important for many civilian and military applications. The profiles of biological markers such as fatty acids can be used to characterize biological samples or to distinguish bacteria at the gram-type, genera, and even species level. Common methods for whole cell bacterial analysis are neither portable nor rapid, requiring lengthy, labor intensive sample preparation and bench-scale instrumentation. These methods chemically derivatize fatty acids to produce more volatile fatty acid methyl esters (FAMEs) that can be separated and analyzed by a gas chromatograph (GC)/mass spectrometer. More recent publications demonstrate decreased sample preparation time with in situ derivatization of whole bacterial samples using pyrolysis/derivatization. Ongoing development of miniaturized pyrolysis/GC instrumentation by this department capitalizes on Sandia advances in the field of microfabricated chemical analysis systems ((mu) ChemLab). Microdevices include rapidly heated stages capable of pyrolysis or sample concentration, gas chromatography columns, and surface acoustic wave (SAW) sensor arrays. We will present results demonstrating the capabilities of these devices toward fulfilling the goal of portable, rapid detection and early warning of the presence of pathogens in air or water.

Microfabrication of membrane-based devices by HARSE and combined HARSE/wet etching

Deep-reactive ion etching (DRIE) of silicon, also known as high-aspect-ratio silicon etching (HARSE), is distinguished by fast etch rates (approximately 3 micrometer/min), crystal orientation independence, anisotropy, vertical sidewall profiles and CMOS compatibility. By using through-wafer HARSE and stopping on a dielectric film placed on the opposite side of the wafer, freestanding dielectric membranes were produced. Dielectric membrane-based sensors and actuators fabricated in this way include microhotplates, flow sensors, valves and magnetically-actuated flexural plate wave (FPW) devices. Unfortunately, low-stress silicon nitride, a common membrane material, has an appreciable DRI etch rate. To overcome this problem HARSE can be followed by a brief wet chemical etch. This approach has been demonstrated using KOH or HF/Nitric/Acetic etchants, both of which have significantly smaller etch rates on silicon nitride than does DRIE. Composite membranes consisting of silicon dioxide and silicon nitride layers are also under evaluation due to the higher DRIE selectivity to silicon dioxide.

Rapid identification of bacteria with miniaturized pyrolysis/GC analysis

Identification of bacteria and other biological moieties finds a broad range of applications in the environmental, biomedical, agricultural, industrial, and military arenas. Linking these applications are biological markers such as fatty acids, whose mass spectral profiles can be used to characterize biological samples and to distinguish bacteria at the gram-type, genera, and even species level. Common methods of sample analysis require sample preparation that is both lengthy and labor intensive, especially for whole cell bacteria. The background technique relied on here utilizes chemical derivatization of fatty acids to the more volatile fatty acid methyl esters (FAMEs), which can be separated on a gas chromatograph column or input directly into a mass spectrometer. More recent publications demonstrate improved sample preparation time with in situ derivatization of whole bacterial samples using pyrolysis at the inlet; although much faster than traditional techniques, these systems still rely on bench-top analytical equipment and individual sample preparation. Development of a miniaturized pyrolysis/GC instrument by this group is intended to realize the benefits of FAME identification of bacteria and other biological samples while further facilitating sample handling and instrument portability. The technologies being fabricated and tested have the potential of achieving pyrolysis and FAME separation on a very small scale, with rapid detection time (1-10 min from introduction to result), and with a modular sample inlet. Performance results and sensor characterization will be presented for the first phase of instrument development, encompassing the microfabricated pyrolysis and gas chromatograph elements.

Acoustic wave chemical microsensors in GaAs

High sensitivity acoustic wave chemical microsensors are being developed on GaAs substrates. These devices take advantage of the piezoelectric properties of GaAs as well as its mature microelectronics fabrication technology and nascent micromachining technology. The design, fabrication, and response of GaAs SAW chemical microsensors are reported. Functional integrated GaAs SAW oscillators, suitable for chemical sensing, have been produced. The integrated oscillator requires 20 mA at 3 VDC, operates at frequencies up to 500 MHz, and occupies approximately 2 mm2. Discrete GaAs sensor components, including IC amplifiers, SAW delay lines, and IC phase comparators have been fabricated and tested. A temperature compensation scheme has been developed that overcomes the large temperature dependence of GaAs acoustic wave devices. Packaging issues related to bonding miniature flow channels directly to the GaAs substrates have been resolved. Micromachining techniques for fabricating FPW and TSM microsensors on thin GaAs membranes are presented and GaAs FPW delay line performance is described. These devices have potentially higher sensitivity than existing GaAs and quartz SAW sensors.

Monolithic GaAs surface acoustic wave chemical microsensor array

A four-channel surface acoustic wave (SAW) chemical sensor array with associated RF electronics is monolithically integrated onto one GaAs IC. The sensor operates at 690 MHz from an on-chip SAW based oscillator and provides simple DC voltage outputs by using integrated phase detectors. This sensor array represents a significant advance in microsensor technology offering miniaturization, increased chemical selectivity, simplified system assembly, improved sensitivity, and inherent temperature compensation.

Miniature Sensors for Biological Warfare Agents using Fatty Acid Profiles: LDRD 10775 Final Report

Rapid detection and identification of bacteria and other pathogens is important for many civilian and military applications. The taxonomic significance, or the ability to differentiate one microorganism from another, using fatty acid content and distribution is well known. For analysis fatty acids are usually converted to fatty acid methyl esters (FAMEs). Bench-top methods are commercially available and recent publications have demonstrated that FAMEs can be obtained from whole bacterial cells in an in situ single-step pyrolysis/methylation analysis. This report documents the progress made during a three year Laboratory Directed Research and Development (LDRD) program funded to investigate the use of microfabricated components (developed for other sensing applications) for the rapid identification of bioorganisms based upon pyrolysis and FAME analysis. Components investigated include a micropyrolyzer, a microGC, and a surface acoustic wave (SAW) array detector. Results demonstrate that the micropyrolyzer can pyrolyze whole cell bacteria samples using only milliwatts of power to produce FAMEs from bacterial samples. The microGC is shown to separate FAMEs of biological interest, and the SAW array is shown to detect volatile FAMEs. Results for each component and their capabilities and limitations are presented and discussed. This project has produced the first published work showing successful pyrolysis/methylation of fatty acids and related analytes using a microfabricated pyrolysis device.

Sampling and Sensing Systems for High Priority Analytes

This reports summarizes the results from a Laboratory Directed Research and Development effort to develop selective coastings for detecting high priority analytes (HPAs), such as chemical warfare (CW) agents and their precursors, in the presence of common interferents. Accomplishments during this project included synthesis and testing of new derivatized sol-gel coatings for surface acoustic wave sensors (SAWs). Surfactant modified and fluoroalcohol derivatized sol-gel oxides were coated onto SAW devices and tested with volatile organic compounds (VOCs). Theses modified sol-gel coatings improved SAW sensitivity to DMMP by over three orders of magnitude when compared to standard polymeric oatings such as polyisobutylene and by over two orders of magnitude compared with polymers tailor made for enhanced sensitivity to phosphonates. SAW sensors coated with these materials exhibit highly sensitive reversible behavior at elevated temperatures (>90 degree C), possibly leading to low detection levels for semivolatile analytes while remaining insensitive to volatile organic interferants. Additionally, we have investigated the use of reactive polymers for detection of volatile and reactive CW agent precursors (Chemical Weapons Convention Schedule 3 Agents) such as phosphouous oxychloride (POCl(3)). The results obtained in this study find that sensitive and selective responses can be obtained for Schedule 3 agents using commercially available polymers and chemical guidelines from solution phase chemistry.