Andreas Muller

An optical diffraction grating spectrometer is described which achieves a spectral resolution of 1.4cm ⁻¹ over a spectral range of 3800cm ⁻¹ without moving parts. It offers high detection efficiency (>50% in the green for p-polarized light) and low noise, without requiring thermoelectric cooling. Based on a fast F0.95/50 mm camera lens that is traversed by both input light and grating-dispersed light, it occupies a volume of under 2 L. Such a device is ideally suited for high-resolution low-light spectroscopy needed in portable Raman trace-gas sensing.

A portable multipass cavity Raman gas analyzer is described, which uses the vibrational band of hydrogen as a concentration measure. Integrated into a Pelican case and combined with a desiccating gas handling system, it was tested inside a laboratory, within an atrium, and in an outdoor open space. The hydrogen concentration was measured as a function of time and distance from an electrolyzer producing up to 600 mL/min, with a total measurement duration under 5 min per sample at 0.34 MPa. The instrument was found to be capable of mapping excess hydrogen concentrations of 63 parts per billion (one standard deviation) above the ambient level from a distance of several meters away, even outdoors, enabling applications in leak detection and geological prospecting.

A simple method for reducing the linewidth of a diode laser while maintaining high output power is described. It is based on a dispersive prism and a thin etalon for retroreflective feedback. The etalon creates two weak external cavities that provide spectral selectivity that is periodic with a period equal to the etalon’s free spectral range. The method was applied to a multimode blue laser diode, which in the absence of feedback features a linewidth of several nanometers. The spectral properties of the laser were investigated for different etalon thicknesses and operating currents and tested in the presence of temperature fluctuations. With a SF11 equilateral uncoated prism near Brewster’s angle and a 0.3 mm-thick uncoated fused silica etalon, the linewidth was reduced 20-fold to 70 pm (3.6 cm−1) with an output power of 3 W at a current of 2.15 A. The largest diode current probed was 2.75 A, which resulted in a linewidth of 100 pm (5.1 cm−1) and an output power of 4 W. In contrast to the use of, for example, a volume Bragg grating, a high degree of flexibility is afforded as the same prism–etalon pair can be used across the visible and near infrared.

2,3,3,3-Tetrafluoro-2-(trifluoromethyl) propanenitrile (C4F7N) is being researched as an alternative to sulfur hexafluoride (SF6) for applications in gas-insulated switchgear. We independently assessed the effectiveness of gas chromatography-mass spectrometry (GC-MS) and a novel method of feedback-assisted multipass cavity spontaneous Raman spectroscopy (SRS) for the trace quantification of impurities in C4F7N and its related byproducts. A total of 14 gases were identified with estimated concentrations as low as 20 ppm (ppm) for C3F6 using GC-MS and 7.4 ppm for CH4 using SRS and as high as 500 ppm for CF4 using GC-MS and 1430 ppm for CO using SRS. While GC-MS is highly effective in selectively detecting and quantifying trace contaminants, it necessitates separate detectors for various gases, such as CH4 and H-2. SRS succeeded in detecting CF4 and C2F6 at concentrations of 465 and 100 ppm, respectively, and in placing an upper bound of several hundred ppm for the other analytes. Crucially, SRS holds potential for portability-and thus for field applications-in gas-insulated switchgear equipment diagnostics.

Despite its growing importance in the energy generation and storage industry, the detection of hydrogen in trace concentrations remains challenging, as established optical absorption methods are ineffective in probing homonuclear diatomics. Besides indirect detection approaches using, e.g., chemically sensitized microdevices, Raman scattering has shown promise as an alternative direct method of unambiguous hydrogen chemical fingerprinting. We investigated the suitability of feedback-assisted multipass spontaneous Raman scattering for this task and examined the precision with which hydrogen can be sensed at concentrations below 2 parts per million. A limit of detection of 60, 30, and 20 parts per billion was obtained at a pressure of 0.2 MPa in a 10-min-long, 120-min-long, and 720-min-long measurement, respectively, with the lowest concentration probed being 75 parts per billion. Various methods of signal extraction were compared, including asymmetric multi-peak fitting, which allowed the resolution of concentration steps of 50 parts per billion, determining the ambient air hydrogen concentration with an uncertainty level of 20 parts per billion.

The detection of ambient outdoor trace hydrocarbons was investigated with a multipass Raman analyzer. It relies on a multimode blue laser diode receiving optical feedback from a retroreflecting multipass optical cavity, effectively creating an external cavity diode laser within which spontaneous Raman scattering enhancement occurs. When implemented with ultra-low-loss mirrors, a more than 20-fold increase in signal-to-background ratio was obtained, enabling proximity detection of trace motor vehicle exhaust gases such as H₂, CO, NO, CH₄, C₂H₂, C₂H₄, and C₂H₆. In a 10-min-long measurement at double atmospheric pressure, the limits of detection obtained were near or below 100 ppb for most analytes.

Raman scattering with a feedback-assisted ultralow-loss multipass cavity was implemented for trace hydrogen sensing. A limit of detection (precision) of 40 (50) parts-per-billion was obtained at a pressure of 0.2 MPa in a 30-min exposure.

Feedback-assisted multipass-cavity spontaneous Raman scattering is demonstrated as an effective method of isotopologue analysis. Deuterium concentration precision near one part-per-million in water was obtained by direct vapor and indirect dihydrogen measurements.