Recent Advances in Microfabricated Gas Chromatography for Process Analysis
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In this report, we evaluate a novel method for modeling the spread of COVID-19 pandemic. In this new approach we leverage methods and algorithms developed for fully-kinetic plasma physics simulations using Particle-In-Cell (PIC) Direct Simulation Monte-Carlo (DSMC) models. This approach then leverages Sandia-unique simulation capabilities, and High-Performance Computer (HPC) resources and expertise in particle-particle interactions using stochastic processes. Our hypothesis is that this approach would provide a more efficient platform with assumptions based on physical data that would then enable the user to assess the impact of mitigation strategies and forecast different phases of infection. This work addresses key scientific questions related to the assumptions this new approach must make to model the interactions of people using algorithms typically used for modeling particle interactions in physics codes (kinetic plasma, gas dynamics). The model developed uses rational/physical inputs while also providing critical insight; the results could serve as inputs to, or alternatives for, existing models. The model work presented was developed over a four-week time frame, thus far showing promising results and many ways in which this model/approach could be improved. This work is aimed at providing a proof-of-concept for this new pandemic modeling approach, which could have an immediate impact on the COVID-19 pandemic modeling, while laying a basis to model future pandemic scenarios in a manner that is timely and efficient. Additionally, this new approach provides new visualization tools to help epidemiologists comprehend and articulate the spread of this and other pandemics as well as a more general tool to determine key parameters needed in order to better predict pandemic modeling in the future. In the report we describe our model for pandemic modeling, apply this model to COVID-19 data for New York City (NYC), assess model sensitivities to different inputs and parameters and , finally, propagate the model forward under different conditions to assess the effects of mitigation and associated timing. Finally, our approach will help understand the role of asymptomatic cases, and could be extended to elucidate the role of recovered individuals in the second round of the infection, which is currently being ignored.
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Lab on a Chip
A small, consumable-free, low-power, ultra-high-speed comprehensive GC×GC system consisting of microfabricated columns, nanoelectromechanical system (NEMS) cantilever resonators for detection, and a valve-based stop-flow modulator is demonstrated. The separation of a highly polar 29-component mixture covering a boiling point range of 46 to 253 °C on a pair of microfabricated columns using a Staiger valve manifold in less than 7 seconds, and just over 4 seconds after the ensemble holdup time is demonstrated with a downstream FID. The analysis time of the second dimension was 160 ms, and peak widths in the second dimension range from 10-60 ms. A peak capacity of just over 300 was calculated for a separation of just over 6 s. Data from a continuous operation testing over 40 days and 20000 runs of the GC×GC columns with the NEMS resonators using a 4-component test set is presented. The GC×GC-NEMS resonator system generated second-dimension peak widths as narrow as 8 ms with no discernable peak distortion due to under-sampling from the detector.
Applied Physics Letters
We introduce a silicon metal-oxide-semiconductor quantum dot architecture based on a single polysilicon gate stack. The elementary structure consists of two enhancement gates separated spatially by a gap, one gate forming a reservoir and the other a quantum dot. We demonstrate that, in three devices based on two different versions of this elementary structure, a wide range of tunnel rates is attainable while maintaining single-electron occupation. A characteristic change in the slope of the charge transitions as a function of the reservoir gate voltage, attributed to screening from charges in the reservoir, is observed in all devices and is expected to play a role in the sizable tuning orthogonality of the split enhancement gate structure. The all-silicon process is expected to minimize strain gradients from electrode thermal mismatch, while the single gate layer should avoid issues related to overlayers (e.g., additional dielectric charge noise) and help improve the yield. Finally, reservoir gate control of the tunnel barrier has implications for initialization, manipulation, and readout schemes in multi-quantum dot architectures.
Applied Physics Letters
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Analytical Sciences
We describe for the first time hydrogen bonded acid (HBA) polymer, poly[methyl[3-(2-hydroxyl, 4,6-bistrifluoromethyl)- phenyl]propylsiloxane], (DKAP), as stationary phase for gas chromatography (μGC) of organophosphate (OP), chemical warfare agent (CWA) surrogates, dimethylmethylphosphonate (DMMP), diisopropylmethylphosphonate (DIMP), diethylmethylphosphonate (DEMP), and trimethylphosphate (TMP), with high selectivity. Absorption of OPs to DKAP was one-to-several orders of magnitude higher relative to commercial polar, mid-polar, and nonpolar stationary phases. We also present for the first-time thermodynamic studies on the absorption of OP vapors and quantitative binding energy data for interactions with various stationary phases. These data help to identify the best pair of hetero-polar columns for a two-dimensional GC system, employing a nonpolar stationary phase as GC1 and DKAP as the GC2 stationary phase, for selective and rapid field detection of CWAs.
Nature Communications
The silicon metal-oxide-semiconductor (MOS) material system is a technologically important implementation of spin-based quantum information processing. However, the MOS interface is imperfect leading to concerns about 1/f trap noise and variability in the electron g-factor due to spin-orbit (SO) effects. Here we advantageously use interface-SO coupling for a critical control axis in a double-quantum-dot singlet-triplet qubit. The magnetic fieldorientation dependence of the g-factors is consistent with Rashba and Dresselhaus interface-SO contributions. The resulting all-electrical, two-Axis control is also used to probe the MOS interface noise. The measured inhomogeneous dephasing time, T2m, of 1.6 ?s is consistent with 99.95% 28Si enrichment. Furthermore, when tuned to be sensitive to exchange fluctuations, a quasi-static charge noise detuning variance of 2 μeV is observed, competitive with low-noise reports in other semiconductor qubits. This work, therefore, demonstrates that the MOS interface inherently provides properties for two-Axis qubit control, while not increasing noise relative to other material choices.
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Review of Scientific Instruments
We demonstrate a capability of deterministic doping at the single atom level using a combination of direct write focused ion beam and solid-state ion detectors. The focused ion beam system can position a single ion to within 35 nm of a targeted location and the detection system is sensitive to single low energy heavy ions. This platform can be used to deterministically fabricate single atom devices in materials where the nanostructure and ion detectors can be integrated, including donor-based qubits in Si and color centers in diamond.
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Journal of Radiation Research
Neutron sensing is critical in civilian and military applications. Conventional neutron sensors are limited by size, weight, cost, portability and helium supply. Here the microfabrication of gadolinium (Gd) conversion material-based heterojunction diodes for detecting thermal neutrons using electrical signals produced by internal conversion electrons (ICEs) is described. Films with negligible stress were produced at the tensile-compressive crossover point, enabling Gd coatings of any desired thickness by controlling the radiofrequency sputtering power and using the zero-point near p(Ar) of 50 mTorr at 100 W. Post-deposition Gd oxidation-induced spallation was eliminated by growing a residual stress-free 50 nm neodymium-doped aluminum cap layer atop Gd. The resultant coatings were stable for at least 6 years, demonstrating excellent stability and product shelf-life. Depositing Gd directly on the diode surface eliminated the air gap, leading to a 200-fold increase in electron capture efficiency and facilitating monolithic microfabrication. The conversion electron spectrum was dominated by ICEs with energies of 72, 132 and 174 keV. Results are reported for neutron reflection and moderation by polyethylene for enhanced sensitivity, and γ- and X-ray elimination for improved specificity. The optimal Gd thickness was 10.4 μm for a 300 μm-thick partially depleted diode of 300 mm 2 active surface area. Fast detection (within 10 min) at a neutron source-to-diode distance of 11.7 cm was achieved with this configuration. All ICE energies along with γ-ray and K α,β X-rays were modeled to emphasize correlations between experiment and theory. Semi-conductor thermal neutron detectors offer advantages for field-sensing of radioactive neutron sources.
arXiv.org
The silicon metal-oxide-semiconductor (MOS) material system is technologically important for the implementation of electron spin-based quantum information technologies. Researchers predict the need for an integrated platform in order to implement useful computation, and decades of advancements in silicon microelectronics fabrication lends itself to this challenge. However, fundamental concerns have been raised about the MOS interface (e.g. trap noise, variations in electron g-factor and practical implementation of multi-QDs). Furthermore, two-axis control of silicon qubits has, to date, required the integration of non-ideal components (e.g. microwave strip-lines, micro-magnets, triple quantum dots, or introduction of donor atoms). In this paper, we introduce a spin-orbit (SO) driven singlet- triplet (ST) qubit in silicon, demonstrating all-electrical two-axis control that requires no additional integrated elements and exhibits charge noise properties equivalent to other more model, but less commercially mature, semiconductor systems. We demonstrate the ability to tune an intrinsic spin-orbit interface effect, which is consistent with Rashba and Dresselhaus contributions that are remarkably strong for a low spin-orbit material such as silicon. The qubit maintains the advantages of using isotopically enriched silicon for producing a quiet magnetic environment, measuring spin dephasing times of 1.6 μs using 99.95% 28Si epitaxy for the qubit, comparable to results from other isotopically enhanced silicon ST qubit systems. This work, therefore, demonstrates that the interface inherently provides properties for two-axis control, and the technologically important MOS interface does not add additional detrimental qubit noise. isotopically enhanced silicon ST qubit systems
Physical Review Applied
We introduce a silicon metal-oxide-semiconductor quantum dot structure that achieves dot-reservoir tunnel coupling control without a dedicated barrier gate. The elementary structure consists of two accumulation gates separated spatially by a gap, one gate accumulating a reservoir and the other a quantum dot. Control of the tunnel rate between the dot and the reservoir across the gap is demonstrated in the single electron regime by varying the reservoir accumulation gate voltage while compensating with the dot accumulation gate voltage. The method is then applied to a quantum dot connected in series to source and drain reservoirs, enabling transport down to the single electron regime. Finally, tuning of the valley splitting with the dot accumulation gate voltage is observed. This split accumulation gate structure creates silicon quantum dots of similar characteristics to other realizations but with less electrodes, in a single gate stack subtractive fabrication process that is fully compatible with silicon foundry manufacturing.
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Physics of Plasmas
Portable applications of microdischarges, such as the remediation of gaseous wastes or the destruction of volatile organic compounds, will mandate operation in the presence of contaminant species. This paper examines the temporal evolution of microdischarge optical and ultraviolet emissions during pulsed operation by experimental methods. By varying the pulse length of a microdischarge initiated in a 4-hole silicon microcavity array operating in a 655 Torr ambient primarily composed of Ne, we were able to measure the emission growth rates for different contaminant species native to the discharge environment as a function of pulse length. It was found that emission from hydrogen and oxygen impurities demonstrated similar rates of change, while emissions from molecular and atomic nitrogen, measured at 337.1 and 120 nm, respectively, exhibited the lowest rate of change. We conclude that it is likely that O2 undergoes the same resonant energy transfer process between rare gas excimers that has been shown for H2. Further, efficient resonant processes were found to be favored during ignition and extinction phases of the pulse, while emission at the 337.1 nm line from N2 was favored during the intermediate stage of the plasma. In addition to the experimental results, a zero-dimensional analysis is also presented to further understand the nature of the microdischarge.
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Technical Digest - International Electron Devices Meeting, IEDM
Si-MOS based QD qubits are attractive due to their similarity to the current semiconductor industry. We introduce a highly tunable MOS foundry compatible qubit design that couples an electrostatic quantum dot (QD) with an implanted donor. We show for the first time coherent two-axis control of a two-electron spin logical qubit that evolves under the QD-donor exchange interaction and the hyperfine interaction with the donor nucleus. The two interactions are tuned electrically with surface gate voltages to provide control of both qubit axes. Qubit decoherence is influenced by charge noise, which is of similar strength as epitaxial systems like GaAs and Si/SiGe.
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The temporal evolution of spectral lines from microplasma devices (MD) was studied, including impurity transitions. Long-wavelength emission diminishes more rapidly than deep UV with decreasing pulse width and RF operation. Thus, switching from DC to short pulsed or RF operation, UV emissions can be suppressed, allowing for real-time tuning of the ionization energy of a microplasma photo-ionization source, which is useful for chemical and atomic physics. Scaling allows MD to operate near atmospheric pressure where excimer states are efficiently created and emit down to 65 nm; laser emissions fall off below 200 nm, making MD light sources attractive for deep UV use. A first fully-kinetic three-dimensional model was developed that explicitly calculates electron-energy distribution function. This, and non-continuum effects, were studied with the model and how they are impacted by geometry and transient or DC operation. Finally, a global non-dimensional model was developed to help explain general trends MD physics.
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Neutron sensing is critical in civilian, military, industrial, biological, medical, basic research, and environmental applications. Conventional neutron sensors are limited by size, weight, cost, portability, and helium supply. Here the microfabrication of Gd conversion material-based heterojunction diodes is described for detecting thermal neutrons using electrical signals produced by internal conversion electrons (ICE). Films with negligible stress were produced at the tensile-compressive crossover point, enabling Gd coatings of any desired thickness by controlling the radiofrequency sputtering power and using the zero-point near p(Ar) of 50 mTorr at 100 W. Post-deposition Gd oxidation-induced spallation was eliminated by growing a residual stress-free 50 nm neodymium-doped aluminum cap layer atop Gd. Resultant coatings were stable for at least six years demonstrating excellent product shelf life. Depositing Gd on the diode surface eliminated air gap, leading to improved efficiency and facilitating monolithic microfabrication. The conversion electron spectrum was dominated by ICE with energies of 72, 132, and 174 keV. Results are reported on neutron reflection and moderation by polyethylene for enhanced sensitivity and γ- and X-ray elimination for improved specificity. Optimal Gd thickness was 10.4 μm with 300 μm thick partially depleted diode of 300 mm2 active surface area. Fast detection within 10 minutes at a neutron source-to-diode distance of 11.7 cm was achieved using this configuration. All ICE energies along with γ-ray and Kα X-ray were modeled to emphasize correlations between experiment and theory and to calculate efficiencies. Semiconductor thermal neutron detectors offer advantages for field-sensing of radioactive neutron sources.
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Review of Scientific Instruments
We report on the development of a highly miniaturized vacuum package for use in an atomic clock utilizing trapped ytterbium-171 ions. The vacuum package is approximately 1 cm3 in size and contains a linear quadrupole RF Paul ion trap, miniature neutral Yb sources, and a non-evaporable getter pump. We describe the fabrication process for making the Yb sources and assembling the vacuum package. To prepare the vacuum package for ion trapping, it was evacuated, baked at a high temperature, and then back filled with a helium buffer gas. Once appropriate vacuum conditions were achieved in the package, it was sealed with a copper pinch-off and was subsequently pumped only by the non-evaporable getter. We demonstrated ion trapping in this vacuum package and the operation of an atomic clock, stabilizing a local oscillator to the 12.6 GHz hyperfine transition of 171Y b+. The fractional frequency stability of the clock was measured to be 2 × 10-11/τ1/2.
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There is a need in many fields, such as nuclear medicine, non-proliferation, energy exploration, national security, homeland security, nuclear energy, etc, for miniature, thermal neutron detectors. Until recently, thermal neutron detection has required physically large devices to provide sufficient neutron interaction and transduction signal. Miniaturization would allow broader use in the fields just mentioned and open up other applications potentially. Recent research shows promise in creating smaller neutron detectors through the combination of high-neutron-cross-section converter materials and solid-state devices. Yet, till recently it is difficult to measure low neutron fluxes by solidstate means given the need for optimized converter materials (purity, chemical composition and thickness) and a lack of designs capable of efficient transduction of the neutron conversion products (x-rays, electrons, gamma rays). Gadolinium-based semiconductor heterojunctions have detected electrons produced by Gd-neutron reactions but only at high neutron fluxes. One of the main limitations to this type of approach is the use of thin converter layers and the inability to utilize all the conversion products. In this LDRD we have optimized the converter material thickness and chemical composition to improve capture of conversion electrons and have detected thermal neutrons with high fidelity at low flux. We are also examining different semiconductor materials and converter materials to attempt to capture a greater percentage of the conversion electrons, both low and higher energy varieties. We have studied detector size and bias scaling, and cross-sensitivity to xrays and shown that we can detect low fluxes of thermal neutrons in less than 30 minutes with high selectivity by our approach. We are currently studying improvements in performance with direct placement of the Gd converter on the detector. The advancement of sensitive, miniature neutron detectors will have benefits in energy production, nonproliferation and medicine.
Sandia journal manuscript; Not yet accepted for publication
Deterministic control over the location and number of donors is crucial to donor spin quantum bits (qubits) in semiconductor based quantum computing. A focused ion beam is used to implant close to quantum dots. Ion detectors are integrated next to the quantum dots to sense the implants. The numbers of ions implanted can be counted to a precision of a single ion. Regular coulomb blockade is observed from the quantum dots. Charge offsets indicative of donor ionization, are observed in devices with counted implants.
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This report describes initial testing of the NG Sensor GTX-1000 natural gas monitoring system. This testing showed that the retention time, peak area stability and heating value repeatability of the GTX-1000 were promising for natural gas measurements in the field or at the well head. The repeatability can be less than 0.25% for LHV and HHV for the Airgas standard tested in this report, which is very promising for a first generation prototype. Ultimately this system should be capable of 0.1% repeatability in heating value at significant size and power reductions compared with competing systems.
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Macromolecular Rapid Communications
The synthesis of two new polyphenylene vinylene (PPV) precursor polymers which can be thermally induced to eliminate pentanol is presented. Pentanol has recently been discovered to be a very useful lubricant in MicroElectroMechanical Systems. The utilization of the elimination reaction of precursor polymers to PPV as a small molecule delivery platform has, to the best of our knowledge, not been previously reported. The elimination reactions were examined using thermal gravimetric analysis, gas chromatography, and UV-Vis spectroscopy. Using PPV precursors allows for (1) a high loading of lubricant (one molecule per monomeric unit), (2) a platform that requires relatively high temperatures (>145 °C) to eliminate the lubricant, and (3) a non-volatile, mechanically and chemically stable by-product of the elimination reaction (PPV). The "on-demand" delivery of a vapor-phase lubricant to MicroElectoMechanical Systems (MEMS) will allow for scheduled or as-needed lubrication of the moving components, improving the performance, reliability, and lifespan of the devices. A delivery system utilizing a newly designed microhotplate along with two new precursor poly(p-phenylene vinylene) polymers that thermally eliminate a pentanol lubricant is described. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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This report will detail the process by which the silicon carbide (SiC) microhotplate devices, manufactured by GE, were imaged using IR microscopy equipment available at Sandia. The images taken were used as inputs to a finite element modeling (FEM) process using the ANSYS software package. The primary goal of this effort was to determine a method to measure the temperature of the microhotplate. Prior attempts to monitor the device's temperature by measuring its resistance had proven to be unreliable due to the nonlinearity of the doped SiC's resistance with temperature. As a result of this thermal modeling and IR imaging, a number of design recommendations were made to facilitate this temperature measurement. The lower heating value (LHV) of gaseous fuels can be measured with a catalyst-coated microhotplate calorimeter. GE created a silicon carbide (SiC) based microhotplate to address high-temperature survivability requirements for the application. The primary goal of this effort was to determine a method to measure the temperature of the microhotplate. Prior attempts to monitor the device's temperature by measuring its resistance had proven to be unreliable due to the non-linearity of the doped SiC's resistance with temperature. In this work, thermal modeling and IR imaging were utilized to determine the operation temperature as a function of parameters such as operation voltage and device sheet resistance. A number of design recommendations were made according to this work.
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2007 IEEE Conference on Technologies for Homeland Security: Enhancing Critical Infrastructure Dependability
Accurate, periodic calibration is required to operate IMS, GC, and portal security systems with maximum efficiency, surety, and operator confidence. To this end, we are presently developing a microfabricated device for on-demand calibration of fleldable contraband detection instruments. Using robotically-assisted picoliter dispensing methods, precise nanogram or larger amounts of calibration compound(s) are placed on micron-sized bridge structures. Resistively heating these structures delivers precisely quantified low-levels of calibration compounds to the detector systems. This provides reliable calibration for identification and quantification of explosives, narcotics, and other contraband. © 2007 IEEE.
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Sandia journal manuscript; Not yet accepted for publication
Here, self-assembled monolayers (SAMS) have been investigated for their ability to confine the absorption of the motor protein kinesin and direct the movement of microtubule shuttles (MTs) within channels of a lithographically patterned microfluidic device. Channels were made from gold films deposited on a silicon wafer to provide chemically distinct surfaces for the selective formation of a range of alkane thiol monolayers on channel walls. Devices were then exposed to solutions containing casein and kinesin to develop protein monolayers capable of propelling microtubules in the presence of adenosine triphosphate (ATP) fuel. Fluorescence microscopy images were used to observe the attachment of MTs to chemically distinct regions and to evaluate the ability of the various monolayer coatings to confine the movement of MTs within the channel system. Ellipsometry was used to characterize the protein adsorption characteristics of SAMS terminated with different functional groups to help establish confinement mechanisms. Finally, both anti-fouling and cationic monolayers were found to be effective in confining MT movement within the channels by controlling the adsorption or orientation of the casein buffer layers that mediate motor protein attachment and functionality.
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A microflame-based detector suit has been developed for sensing of a broad range of chemical analytes. This detector combines calorimetry, flame ionization detection (FID), nitrogen-phosphorous detection (NPD) and flame photometric detection (FPD) modes into one convenient platform based on a microcombustor. The microcombustor consists in a micromachined microhotplate with a catalyst or low-work function material added to its surface. For the NPD mode a low work function material selectively ionizes chemical analytes; for all other modes a supported catalyst such as platinum/alumina is used. The microcombustor design permits rapid, efficient heating of the deposited film at low power. To perform calorimetric detection of analytes, the change in power required to maintain the resistive microhotplate heater at a constant temperature is measured. For FID and NPD modes, electrodes are placed around the microcombustor flame zone and an electrometer circuit measures the production of ions. For FPD, the flame zone is optically interrogated to search for light emission indicative of deexcitation of flame-produced analyte compounds. The calorimetric and FID modes respond generally to all hydrocarbons, while sulfur compounds only alarm in the calorimetric mode, providing speciation. The NPD mode provides 10,000:1 selectivity of nitrogen and phosphorous compounds over hydrocarbons. The FPD can distinguish between sulfur and phosphorous compounds. Importantly all detection modes can be established on one convenient microcombustor platform, in fact the calorimetric, FID and FPD modes can be achieved simultaneously on only one microcombustor. Therefore, it is possible to make a very universal chemical detector array with as little as two microcombustor elements. A demonstration of the performance of the microcombustor in each of the detection modes is provided herein.
The natural gas industry seeks inexpensive sensors and instrumentation to rapidly measure gas heating value in widely distributed locations. For gas pipelines, this will improve gas quality during transfer and blending, and will expedite accurate financial accounting. Industrial endusers will benefit through continuous feedback of physical gas properties to improve combustion efficiency during use. To meet this need, Sandia has developed a natural gas heating value monitoring instrument using existing and modified microfabricated components. The instrument consists of a silicon micro-fabricated gas chromatography column in conjunction with a catalytic micro-calorimeter sensor. A reference thermal conductivity sensor provides diagnostics and surety. This combination allows for continuous calorimetric determination with a 1 minute analysis time and 1.5 minute cycle time using air as a carrier gas. This system will find application at remote natural gas mining stations, pipeline switching and metering stations, turbine generators, and other industrial user sites. Microfabrication techniques will allow the analytical components to be manufactured in production quantities at a low per-unit cost.
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Proposed for publication in Sensors and Actuators B.
This work describes the design, computational prototyping, fabrication, and characterization of a microfabricated thermal conductivity detector ({mu}TCD) to analyze the effluent from a micro-gas chromatograph column ({mu}GC) and to complement the detection efficacy of a surface acoustic wave detector in the micro-ChemLab{trademark} system. To maximize the detection sensitivity, we designed a four-filament Wheatstone bridge circuit where the resistors are suspended by a thin silicon nitride membrane in pyramidal or trapezoidal shaped flow cells. The geometry optimization was carried out by simulation of the heat transfer in the devices, utilizing a boundary element algorithm. Within microfabrication constraints, we determined and fabricated nine sensitivity-optimized geometries of the {mu}TCD. The nine optimal geometries were tested with two different flow patterns. We demonstrated that the perpendicular flow, where the gas directly impinged upon the membrane, yielded a sensitivity that is three times greater than the parallel flow, where the gas passed over the membrane. The functionality of the {mu}TCD was validated with the theoretical prediction and showed a consistent linear response to effluent concentrations, with a detection sensitivity of 1 ppm, utilizing less than 1 W of power.