High-Sensitivity Micro-Gas Chromatograph-Photoionization Detector for Trace Vapor Detection.

Rapid in situ detection and analysis of trace vapor concentrations at a sub-parts per billion to parts per trillion level remains a challenge for many applications such as indoor air-quality analysis and detection of explosives and narcotics. Micro-gas chromatography (µGC) together with a micro-photoionization detector (µPID) is a prominent method for portable analysis of complex vapor mixtures, but current µPID technology demonstrates poor detection performance compared to benchtop flame ionization detectors (FIDs). This work demonstrates the development of a significantly improved µPID with a sub-picogram detection limit (as low as ∼0.2 pg) comparable to or exceeding that of a benchtop FID, with a large linear dynamic range (>4 orders of magnitude) and robustness (high stability over 200 h of plasma activation). Based on this µPID, a complete µGC-PID system was built and tested on standard sample chromatograms in a laboratory setting to show the system's analytical capabilities and the detection limit down to sub-parts per trillion concentrations (as low as 0.14 ppt). Practical in-field chromatograms on breath and car exhaust were also generated to demonstrate applicability for in situ experimentation. This work shows that µGC-PID systems can be competitive with traditional GC-FID methods and thus opens a door to rapid trace vapor analysis in the field.

Porous Nanophotonic Optomechanical Beams for Enhanced Mass Adsorption.

We have developed a porous silicon nanocantilever for a nano-optomechanical system (NOMS) with a universal sensing surface for enhanced sensitivity. Using electron beam lithography, we selectively applied a V2O5/HF stain etch to the mechanical elements while protecting the silicon-on-insulator photonic ring resonators. This simple, rapid, and electrodeless approach generates tunable device porosity simultaneously with the mechanical release step. By controlling the porous etchant concentration and etch time, the porous etch depth, resonant frequency, and the adsorption surface area could be precisely manipulated. Using this control, cantilever sensors ranging from nonporous to fully porous were fabricated and tested as gas-phase mass sensors of volatile organic compounds coming from a gas chromatography stream. The fully porous cantilever produced a dramatic 10-fold increase in sensing signal and a 6-fold improvement in limit of detection (LOD) compared to an otherwise identical nonporous cantilever. This signal improvement could be separated into mass responsivity increase and adsorption increase components. Allan deviation measurements indicate that a further 4-fold improvement in LOD could be expected upon speeding up characteristic peak response time from 1 s to 50 ms. These results show promise for performance enhancement in nanomechanical sensors for applications in gas sensing, gas chromatography, and mass spectrometry.

Improving mechanical sensor performance through larger damping.

Mechanical resonances are used in a wide variety of devices, from smartphone accelerometers to computer clocks and from wireless filters to atomic force microscopes. Frequency stability, a critical performance metric, is generally assumed to be tantamount to resonance quality factor (the inverse of the linewidth and of the damping). We show that the frequency stability of resonant nanomechanical sensors can be improved by lowering the quality factor. At high bandwidths, quality-factor reduction is completely mitigated by increases in signal-to-noise ratio. At low bandwidths, notably, increased damping leads to better stability and sensor resolution, with improvement proportional to damping. We confirm the findings by demonstrating temperature resolution of 60 microkelvin at 300-hertz bandwidth. These results open the door to high-performance ultrasensitive resonators in gaseous or liquid environments, single-cell nanocalorimetry, nanoscale gas chromatography, atmospheric-pressure nanoscale mass spectrometry, and new approaches in crystal oscillator stability.

Nano-Optomechanical Systems for Gas Chromatography.

Microgas chromatography (GC) is promising for portable chemical analysis. We demonstrate a nano-optomechanical system (NOMS) as an ultrasensitive mass detector in gas chromatography. Bare, native oxide, silicon surfaces are sensitive enough to monitor volatile organic compounds at ppm levels, while simultaneously demonstrating chemical selectivity. The NOMS is able to sense GC peaks from derivatized metabolites at physiological concentrations. This is an important milestone for small-molecule quantitation assays in next generation metabolite analyses for applications such as disease diagnosis and personalized medicine. The optical microring, which plays an important role in the nanomechanical signal transduction mechanism, can also be used as an analyte concentration sensor. Different adsorption kinetics regimes are realized at different temperatures allowing temporary condensation of the analyte onto the sensor surfaces. This effect amplifies the signal, resulting in a 1 ppb level limit of detection, without partition enhancement from absorbing media. This sensitivity bodes well for NOMS as universal, ultrasensitive detectors in micro-GC, breath analysis, and other chemical-sensing applications.

Direct synthesis of single-walled aminoaluminosilicate nanotubes with enhanced molecular adsorption selectivity.

Internal functionalization of single-walled nanotubes is an attractive, yet difficult challenge in nanotube materials chemistry. Here we report single-walled metal oxide nanotubes with covalently bonded primary amine moieties on their inner wall, synthesized through a one-step approach. Conclusive molecular-level structural information on the amine-functionalized nanotubes is obtained through multiple solid-state techniques. The amine-functionalized nanotubes maintain a high carbon dioxide adsorption capacity while significantly suppressing the adsorption of methane and nitrogen, thereby leading to a large enhancement in adsorption selectivity over unfunctionalized nanotubes (up to four-fold for carbon dioxide/methane and ten-fold for carbon dioxide/nitrogen). The successful synthesis of single-walled nanotubes with functional, covalently-bound organic moieties may open up possibilities for new nanotube-based applications that are currently inaccessible to carbon nanotubes and other related materials.