Transport at Nanoscale Interfaces Laboratory

Rapid detection of volatile organic compounds by switch-scan tuning of Vernier quantum-cascade lasers

Brechbühler, R., Selaković, M., Scheidegger, P., Looser, H., Kupferschmid, A., Blaser, S.,  Butet J., Emmenegger L. & Tuzson, B.

Analytical Chemistry. (2023)

Volatile organic compounds (VOCs) exhibit typically broad and mutually overlapping ro-vibrational absorption fingerprints. This complexity has so far limited the applicability of laser-based spectroscopy for VOC measurements in complex gas matrices. Here, we exploit a Vernier-type quantum-cascade laser (QCL) as an electrically tunable multiwavelength source for selective and sensitive VOC analysis. This emerging class of lasers provides access to several spectral windows by discrete Vernier tuning ("switching") and continuous coverage within these windows (“scanning”). We present a versatile driving technique that efficiently combines the two tuning mechanisms. Applied to our Vernier QCL, it enables the rapid acquisition (within 360 ms) of high-resolution spectra from six individual spectral windows, distributed over a wide range from 1063 to 1102 cm-1. Gaining access to the broad absorption envelopes of VOCs at multiple frequencies, along with their superimposed fine structure, which are especially pronounced at a reduced sample pressure, offers completely new opportunities in VOC analysis. The potential of this approach is assessed in a direct-laser-absorption setup with acetaldehyde, ethanol, and methanol as benchmark compounds with significant spectral overlaps. A measurement precision of 1-10 ppb is obtained after integration for 10 s at amount fractions below 10 ppm, and excellent linearity is found over at least 3 orders of magnitude. Combined with our dedicated spectral fitting algorithm, we demonstrate highly selective multicompound analyses with less than 3.5% relative expanded uncertainty, even in the presence of a 40× excess of an interfering compound with complete spectral overlap.