The detection and measurement of gas concentrations using the characteristic optical absorption of the gas species is important for both understanding and monitoring a variety of phenomena from industrial processes to environmental change. This study reviews the field, covering several individual gas detection techniques including non-dispersive infrared, spectrophotometry, tunable diode laser spectroscopy and photoacoustic spectroscopy. We present the basis for each technique, recent developments in methods and performance limitations. The technology available to support this field, in terms of key components such as light sources and gas cells, has advanced rapidly in recent years and we discuss these new developments. Finally, we present a performance comparison of different techniques, taking data reported over the preceding decade, and draw conclusions from this benchmarking.

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Optical gas sensing: a review

This Review discusses the emerging field of mid-infrared frequency comb generation, including technologies based on novel laser gain media, nonlinear frequency conversion and microresonators, as well as the applications of these combs in precision spectroscopy and direct frequency comb spectroscopy. Laser frequency combs are coherent light sources that emit a broad spectrum of discrete, evenly spaced narrow lines whose absolute frequency can be measured to within the accuracy of an atomic clock. Their development in the near-infrared and visible domains has revolutionized frequency metrology while also providing numerous unexpected opportunities in other fields such as astronomy and attosecond science. Researchers are now exploring how to extend frequency comb techniques to the mid-infrared spectral region. Versatile mid-infrared frequency comb generators based on novel laser gain media, nonlinear frequency conversion or microresonators promise to significantly expand the applications of frequency combs. In particular, novel approaches to molecular spectroscopy in the 'fingerprint region', with dramatically improved precision, sensitivity, recording time and/or spectral bandwidth may lead to new discoveries in the various fields relevant to molecular science.

Mid-infrared frequency combs

Dual-comb spectroscopy is an emerging new spectroscopic tool that exploits the frequency resolution, frequency accuracy, broad bandwidth, and brightness of frequency combs for ultrahigh-resolution, high-sensitivity broadband spectroscopy. By using two coherent frequency combs, dual-comb spectroscopy allows a sample’s spectral response to be measured on a comb tooth-by-tooth basis rapidly and without the size constraints or instrument response limitations of conventional spectrometers. This review describes dual-comb spectroscopy and summarizes the current state of the art. As frequency comb technology progresses, dual-comb spectroscopy will continue to mature and could surpass conventional broadband spectroscopy for a wide range of laboratory and field applications.

Dual-comb spectroscopy

A laser frequency comb is a broad spectrum composed of equidistant narrow lines. Initially invented for frequency metrology, such combs enable new approaches to spectroscopy over broad spectral bandwidths, of particular relevance to molecules. The performance of existing spectrometers — such as crossed dispersers employing, for example, virtual imaging phase array etalons, or Michelson-based Fourier transform interferometers — can be dramatically enhanced with optical frequency combs. A new class of instruments, such as dual-comb spectrometers without moving parts, enables fast and accurate measurements over broad spectral ranges. The direct self-calibration of the frequency scale of the spectra within the accuracy of an atomic clock and the negligible contribution of the instrumental line-shape will enable determinations of all spectral parameters with high accuracy for stringent comparisons with theories in atomic and molecular physics. Chip-scale frequency comb spectrometers promise integrated devices for real-time sensing in analytical chemistry and biomedicine. This Review gives a summary of the developments in the emerging and rapidly advancing field of atomic and molecular broadband spectroscopy with frequency combs. Frequency comb spectroscopy is a recent field of research that has blossomed in the past five years. This Review discusses developments in the emerging and rapidly advancing field of atomic and molecular broadband spectroscopy with frequency combs.

Frequency comb spectroscopy

The sensitivity of molecular fingerprinting is dramatically improved when the absorbing sample is placed in a high-finesse optical cavity, because the effective path length is increased. When the equidistant lines from a laser frequency comb are simultaneously injected into the cavity over a large spectral range, multiple trace gases may be identified1 within a few milliseconds. However, efficient analysis of the light transmitted through the cavity remains challenging. Here, a novel approach—cavity-enhanced, frequency-comb, Fourier-transform spectroscopy—fully overcomes this difficulty and enables measurement of ultrasensitive, broad-bandwidth, high-resolution spectra within a few tens of microseconds without any need for detector arrays, potentially from the terahertz to ultraviolet regions. Within a period of just 18 µs, we recorded the spectra of the ammonia 1.0 µm overtone bands comprising 1,500 spectral elements and spanning 20 nm, with a resolution of 4.5 GHz and a noise equivalent absorption at 1 s averaging of 1 × 10−10 cm−1 Hz−1/2, thus opening a route to time-resolved spectroscopy of rapidly evolving single events. By combining Fourier transform spectroscopy with two frequency-shifted combs and cavity ring-down spectroscopy, scientists demonstrate a powerful new tool for ultrahigh sensitivity spectroscopy. The scheme can measure broadband, high-resolution spectra in tens of microseconds, does not require detector arrays and may allow tuning from terahertz to ultraviolet frequencies.

https://hal.archives-ouvertes.fr/hal-00409826/document

Cavity-enhanced dual-comb spectroscopy

Molecular fingerprinting using absorption spectroscopy is a powerful analytical method, particularly in the infrared, the region of intense spectral signatures Fourier transform spectroscopy—the widely used and essential tool for broadband spectroscopy—enables the recording of multi-octave-spanning spectra, exhibiting 100 MHz resolution with an accuracy of 1 × 10−9 and 1 × 10−2 in wavenumber and intensity determination, respectively Typically, 1 × 106 independent spectral elements may be measured simultaneously within a few hours, with only average sensitivity Here, we show that by using laser frequency combs as the light source of Fourier transform spectroscopy it is possible to record well-resolved broadband absorption and dispersion spectra in a single experiment, from the beating signatures of neighbouring comb lines in the interferogram The sensitivity is thus expected to increase by several orders of magnitude Experimental proof of principle is here carried out on the 15-µm overtone bands of acetylene, spanning 80 nm with a resolution of 15 GHz Consequently, without any optical modification, the performance of Fourier spectrometers may be drastically boosted By using an optical frequency comb as the light source for Fourier transform spectroscopy, scientists show that well-resolved broadband absorption and dispersion spectra can be recorded in a single experiment, providing sensitive detection of multiple molecular species over a broad spectral window

Fourier transform spectroscopy with a laser frequency comb

An ultrashort-pulse Cr2+:ZnSe laser is a novel broadband source for sensitive high resolution molecular spectroscopy. A 130-fs pulse allows covering of up to 380 cm-1 spectral domain around 2.4 µm which is analyzed simultaneously with a 0.12 cm-1 (3.6 GHz) resolution by a Fourier-transform spectrometer. Recorded in 13 s, from 70-cm length absorption around 4150 cm-1, acetylene and ammonia spectra exhibit a 3800 signal-to-noise ratio and a 2.4·10-7 cm-1·Hz-1/2 noise equivalent absorption coefficient at one second averaging per spectral element, suggesting a 0.2 ppbv detection level for HF molecule. With the widely practiced classical tungsten lamp source instead of the laser, identical spectra would have taken more than one hour.

https://hal.archives-ouvertes.fr/hal-00179536/document

Sensitive multiplex spectroscopy in the molecular fingerprint 2.4 µm region with a Cr 2+ :ZnSe femtosecond laser

Michelson-less Fourier spectra, comprising 500,000,000 spectral elements spanning 1 nm with 2.3 kHz (7.7 10^-8 cm^-1) resolution, are recorded within 6s. Moving mirror of equivalent interferometers should cover 130 km at 78,000 km/hour velocity.

Frequency Comb Fourier Transform Spectroscopy with kHz Optical Resolution

We demonstrate chirped-pulse operation of a Cr:YAG passively mode-locked laser. Different operation regimes of the laser are extensively investigated in the vicinity of zero dispersion both experimentally and numerically. It is shown that for a given laser configuration, transition to the positive dispersion regime allows a 5-fold increase in the output pulse energy, which is otherwise limited by the onset of the multipulsing or 'chaotic' mode- locking. The output pulses have 1.4ps duration and are compressible down to 120fs in a 3m piece of silica fiber, enabling supercontinuum generation in a nonlinear fiber. The spectrum shape and operation stability of the chirped-pulse regime depend strongly on the amount and shape of the intracavity dispersion. The numerical model predicts the existence of the minimum amount of the positive dispersion, above which the chirped-pulse regime can be realized. Once located, the chirped-pulse regime can be reliably reproduced and is sufficiently stable for applications.

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Cr 4+ :YAG chirped-pulse oscillator

A new method, FM-FTS, combining Frequency Modulation heterodyne laser spectroscopy and Fourier Transform Spectroscopy is presented. It provides simultaneous sensitive measurement of absorption and dispersion profiles with broadband spectral coverage capabilities. Experimental demonstration is made on the overtone spectrum of C2H2 in the 1.5 µm region.

/pdf/frequency-modulation-fourier-transform-spectroscopy-a-3dhcb6g3nm.pdf

Julien Mandon

Papers

Fourier transform spectroscopy with a laser frequency comb

Sensitive multiplex spectroscopy in the molecular fingerprint 2.4 µm region with a Cr 2+ :ZnSe femtosecond laser

Frequency Comb Fourier Transform Spectroscopy with kHz Optical Resolution

Cr 4+ :YAG chirped-pulse oscillator

Frequency-modulation Fourier transform spectroscopy: a broadband method for measuring weak absorptions and dispersions