Gas Chromatography (GC) is routinely used in the laboratory to temporally separate chemical mixtures into their constituent components for improved chemical identification. This paper will provide a overview of more than twenty years of development of one-dimensional field-portable micro GC systems, highlighting key experimental results that illustrate how a reduction in false alarm rate (FAR) is achieved in real-world environments. Significantly, we will also present recent results on a micro two-dimensional GC (micro GCxGC) technology. This ultra-small system consists of microfabricated columns, NanoElectroMechanical System (NEMS) cantilever resonators for detection, and a valve-based stop-flow modulator. The separation of a 29-component polar mixture in less than 7 seconds is demonstrated along with peak widths in the second dimension ranging from 10-60 ms. For this system, a peak capacity of just over 300 was calculated for separation in about 6 s. This work has important implications for field detection, to drastically reduce FAR and significantly improve chemical selectivity and identification. This separation performance was demonstrated with the NEMS resonator and bench scale FID. But other detectors, suitably fast and sensitive can work as well. Recent research has shown that the identification power of GCxGC-FID can match that of GC-MS. This result indicates a path to improved size, weight, power, and performance in micro GCxGC systems outfitted with relatively non-specific, lightweight detectors. We will briefly discuss the performance of possible options, such as the pulsed discharge helium ionization detector (PDHID) and miniature correlation ion mobility spectrometer (mini-CIMS).
We are developing a highly miniaturized trapped ion clock to probe the 12.6 GHz hyperfine transition in the
171Yb+ ion. The clock development is being funded by the Integrated Micro Primary Atomic Clock
Technology (IMPACT) program from DARPA where the stated goals are to develop a clock that consumes
50 mW of power, has a size of 5 cm3, and has a long-term frequency stability of 10-14 at one month. One of
the significant challenges will be to develop miniature single-frequency lasers at 369 nm and 935 nm and the
optical systems to deliver light to the ions and to collect ion fluorescence on a detector.
Sandia National Laboratories has a long tradition of technology development for national security applications. In
recent years, significant effort has been focused on micro-analytical systems - handheld, miniature, or portable
instruments built around microfabricated components. Many of these systems include microsensor concepts and target
detection and analysis of chemical and biological agents. The ultimate development goal for these instruments is to
produce fully integrated sensored microsystems. Described here are a few new components and systems being explored:
(1) A new microcalibrator chip, consisting of a thermally labile solid matrix on an array of suspended-membrane
microhotplates, that when actuated delivers controlled quantities of chemical vapors. (2) New chemical vapor detectors,
based on a suspended-membrane micro-hotplate design, which are amenable to array configurations. (3) Micron-scale
cylindrical ion traps, fabricated using a molded tungsten process, which form the critical elements for a micro-mass
analyzer. (4) Monolithically integrated micro-chemical analysis systems fabricated in silicon that incorporate chemical
preconcentrators, gas chromatography columns, detector arrays, and MEMS valves.
Sandia's hand-held MicroChemLabTM system uses a micromachined preconcentrator (PC), a gas chromatography channel (GC) and a quartz surface acoustic wave array (SAW) detector for sensitive/selective detection of gas-phase chemical analytes. Requisite system size, performance, power budget and time response mandate microfabrication of the key analytical system components. In the fielded system hybrid integration has been employed, permitting optimization of the individual components. Recent improvements in the hybrid-integrated system, using plastic, metal or silicon/glass manifolds, is described, as is system performance against semivolatile compounds and toxic industrial chemicals. The design and performance of a new three-dimensional micropreconcentrator is also introduced. To further reduce system dead volume, eliminate unheated transfer lines and simplify assembly, there is an effort to monolithically integrate the silicon PC and GC with a suitable silicon-based detector, such as a magnetically-actuated flexural plate wave sensor (magFPW) or a magnetically-actuated pivot plate resonator (PPR).
Sandia is exploring two classes of integrated systems involving bioactive materials: 1) microfluidic systems that can be used to manipulate biomolecules for applications ranging from counter-terrorism to drug delivery systems, and 2) fluidic systems in which active biomolecules such as motor proteins provide specific functions
such as active transport. An example of the first class involves the development of a reversible protein trap based on the integration of the thermally-switchable polymer poly(N-isopropylacrylamide)(PNIPAM) into a micro-hotplate device. To exemplify the second class, we describe the technical challenges associated with integrating microtubules and motor proteins into microfluidic systems for: 1) the active transport of nanoparticle cargo, or 2) templated growth of high-aspect ratio nanowires. These examples illustrate the
functions of bioactive materials, synthesis and fabrication issues, mechanisms for switching surface chemistry and active transport, and new techniques such as the interfacial force microscope (IFM) that can be used to characterize bioactive surfaces.
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.
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.
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.
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.
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.
Fully CMOS-compatible, surface-micromachined polysilicon microbridges have ben designed, fabricated, and tested for use in catalytic, calorimetric gas sensing. To improve sensor behavior, extensive electro-thermal modeling efforts were undertaken using SPICE. The validity of the SPICE model was verified by comparing its simulated behavior with experimental results. The temperature distribution of an electrically-heated microbridge was measured using an IR microscope. Comparisons among the measured distribution, the SPICE simulation, and distributions obtained by analytical methods show that heating at the ends of a microbridge has important implications for device response. Additional comparisons between measured and simulated current-voltage characteristics, as well as transient response characteristics, further support the accuracy of the model. A major benefit of electro-thermal modeling with SPICE is the ability to simultaneously simulate the behavior of a device and its control/sensing electronics. Results for the combination of a unique constant-resistance control circuit and microbridge gas sensor ar given. Models of in situ techniques for monitoring catalyst deposition are shown to be in agreement with experiment. Finally, simulated chemical response of the detector is compared with the data, and methods of improving response through modifications in bridge geometry are predicted.
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.
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.
Micromirrors having diameters from a few micrometers to several millimeters have been produced on (100) silicon by wet-chemical etching in KOH:H2O. The f/#'s range from about 2.5 to at least 10. The microroughness of an etched mirror with diameter 550 μm and 9.6-μm sagitta is less than 5 nm and its surface figure is within 0.5 μm of a perfect sphere. Data over a wide range of diameters are presented and a semiempirical model is developed to explain the behavior. The concordance of the normalized etched profiles for all diameter mirrors demonstrates that the etching is dominated by surface reaction rather than diffusion limitation. Design and fabrication schemes are presented for making a wide range of mirror diameters and focal lengths, for both single micromirrors and arrays. The etched depressions can be used as templates for microlenses and as substrates for geodesic waveguide lenses and arrays. Chem-mechanical polishing on the etched structures reduces the edge curvature and produces oblate spheroidal surfaces, both of which should improve geodesic lens behavior. The etched structures can also be used as variable crystal orientation substrates for epitaxial nucleation and various surface analysis studies.