Mid-infrared Dual-comb Spectrometer Research Articles

Compact mid-infrared dual-comb spectrometer over 3–4 μm via intra-pulse difference frequency generation in LiNbO3 waveguides

Abstract The mid-infrared optical frequency comb is a powerful tool for gas sensing. In this study, we demonstrate a simple mid-infrared dual-comb spectrometer covering 3–4 μm in LiNbO3 waveguides. Based on a low-power fiber laser system, the mid-infrared comb is achieved via intra-pulse difference frequency generation in the LiNbO3 waveguide. We construct pre-chirp management before supercontinuum generation to control spatiotemporal alignment for pump and signal pulses. The supercontinuum is directly coupled into a chirped periodically poled LiNbO3 waveguide for the 3–4 μm idler generation. A mid-infrared dual-comb spectrometer based on this approach provides a 100 MHz resolution over 25 THz coverage. To evaluate the applicability for spectroscopy, we measure the methane spectrum using the dual-comb spectrometer. The measured results are consistent with the HITRAN database, in which the root mean square of the residual is 3.2%. This proposed method is expected to develop integrated and robust mid-infrared dual-comb spectrometers on chip for sensing.

Improving the performance of artificial neural networks trained on synthetic data in gas spectroscopy – a study on two sensing approaches

Abstract Artificial neural networks (ANNs) are used in quantitative infrared gas spectroscopy to predict concentrations on multi-component absorption spectra. Training of ANNs requires vast amounts of labelled training data which may be elaborate and time consuming to obtain. Additional data can be gained by the utilization of synthetically generated spectra, but at the cost of systematic deviations to measured data. Here, we present two approaches to train ANNs with a combination of comparatively small, measured data sets and synthetically generated data. For the first approach a neural network is trained hybridly with synthetically generated infrared absorption spectra of mixtures of N2O and CO and measured zero-gas spectra, taken with a mid-infrared dual comb spectrometer. This improves the mean absolute error (MAE) of the network predictions from 0.46 to 0.01 ppmV and 0.24 to 0.01 ppmV for the concentration predictions of N2O and CO respectively for zero-gas measurements which was previously observed for training with purely synthetic data. At the same time a similar performance on spectra from gas mixtures of 0–100 ppmV N2O and 0 to 60 ppmV CO was achieved. For the second approach an ANN pre-trained on synthetic infrared spectra of mixtures of acetone and ethanol is retrained on a small dataset consisting of 26 spectra taken with a mid-infrared photoacoustic spectrometer. In this case the MAE for the concentration predictions of ethanol and acetone are improved by 45 % and 20 % in comparison to purely synthetic training. This shows the capability of using synthetically generated data to train ANNs in combination with small amounts of measured data to further improve neural networks for gas sensing and the transferability between different sensing approaches.

Open-path dual-comb spectroscopy of methane and VOC emissions from an unconventional oil well development in Northern Colorado.

We present results from a field study monitoring methane and volatile organic compound emissions near an unconventional oil well development in Northern Colorado from September 2019 to May 2020 using a mid-infrared dual-comb spectrometer. This instrument allowed quantification of methane, ethane, and propane in a single measurement with high time resolution and integrated path sampling. Using ethane and propane as tracer gases for methane from oil and gas activity, we observed emissions during the drilling, hydraulic fracturing, millout, and flowback phases of well development. Large emissions were seen in drilling and millout phases and emissions decreased to background levels during the flowback phase. Ethane/methane and propane/methane ratios varied widely throughout the observations.

Rapid Quantitative Analysis of IR Absorption Spectra for Trace Gas Detection by Artificial Neural Networks Trained with Synthetic Data.

Infrared absorption spectroscopy is a widely used tool to quantify and monitor compositions of gases. The concentration information is often retrieved by fitting absorption profiles to the acquired spectra, utilizing spectroscopic databases. In complex gas matrices an expanded parameter space leads to long computation times of the fitting routines due to the increased number of spectral features that need to be computed for each iteration during the fit. This hinders the capability of real-time analysis of the gas matrix. Here, an artificial neural network (ANN) is employed for rapid prediction of gas concentrations in complex infrared absorption spectra composed of mixtures of CO and N2O. Experimental data is acquired with a mid-infrared dual frequency comb spectrometer. To circumvent the experimental collection of huge amounts of training data, the network is trained on synthetically generated spectra. The spectra are based on simulated absorption profiles making use of the HITRAN database. In addition, the spectrometer’s influence on the measured spectra is characterized and included in the synthetic training data generation. The ANN was tested on measured spectra and compared to a non-linear least squares fitting algorithm. An average evaluation time of 303 µs for a single measured spectrum was achieved. Coefficients of determination were 0.99997 for the predictions of N2O concentrations and 0.99987 for the predictions of CO concentrations, with uncertainties on the predicted concentrations between 0.04 and 0.18 ppm for 0 to 100 ppm N2O and between 0.05 and 0.18 ppm for 0 to 60 ppm CO.

Broadband Time-Resolved Absorption and Dispersion Spectroscopy of Methane and Ethane in a Plasma Using a Mid-Infrared Dual-Comb Spectrometer.

Conventional mechanical Fourier Transform Spectrometers (FTS) can simultaneously measure absorption and dispersion spectra of gas-phase samples. However, they usually need very long measurement times to achieve time-resolved spectra with a good spectral and temporal resolution. Here, we present a mid-infrared dual-comb-based FTS in an asymmetric configuration, providing broadband absorption and dispersion spectra with a spectral resolution of 5 GHz (0.18 nm at a wavelength of 3333 nm), a temporal resolution of 20 μs, a total wavelength coverage over 300 cm−1 and a total measurement time of ~70 s. We used the dual-comb spectrometer to monitor the reaction dynamics of methane and ethane in an electrical plasma discharge. We observed ethane/methane formation as a recombination reaction of hydrocarbon radicals in the discharge in various static and dynamic conditions. The results demonstrate a new analytical approach for measuring fast molecular absorption and dispersion changes and monitoring the fast dynamics of chemical reactions over a broad wavelength range, which can be interesting for chemical kinetic research, particularly for the combustion and plasma analysis community.

Compact mid-infrared dual-comb spectrometer for outdoor spectroscopy.

This manuscript describes the design of a robust, mid-infrared dual-comb spectrometer operating in the 3.1-µm to 4-µm spectral window for future field applications. The design represents an improvement in system size, power consumption, and robustness relative to previous work while also providing a high spectral signal-to-noise ratio. We demonstrate a system quality factor of 2×106 and 30 hours of continuous operation over a 120-meter outdoor air path.

Mid-infrared dual-comb spectroscopy with absolute frequency calibration using a passive optical reference.

We demonstrate an absolute-frequency-calibrated mid-infrared dual-comb spectrometer by using a reference absorption cell. The source is based on a singly-resonant OPO containing two MgO:PPLN crystals in a common ring cavity, synchronously pumped by two mode-locked Yb-fiber lasers. The repetition-rate of the two pumps are stabilized while their offset frequencies and the OPO cavity length are not actively controlled. The reference spectrum is used to correct the frequency fluctuations in the sample spectrum providing a high-quality averaged spectrum with spectral resolution of 6 GHz and calibration precision of 120 MHz, without adding any complexity to the experimental setup or signal processing.

Real-time liquid-phase organic reaction monitoring with mid-infrared attenuated total reflectance dual frequency comb spectroscopy

We combine mid-infrared dual-comb spectroscopy with attenuated total reflectance measurements to provide in-situ monitoring of a chemical reaction. The mid-infrared dual-comb spectrometer measures quantitative absorption cross-sections of mesityl oxide and diacetone alcohol in the region of 3300–2700 cm−1 (3.0–3.7 μm). Based on these spectra, the system is then used to monitor the hydration of mesityl oxide to diacetone alcohol from which we extract reaction kinetics values. This work shows the potential of dual comb systems to measure and monitor reactions in the condensed phase.

High-coherence mid-infrared dual-comb spectroscopy spanning 2.6 to 5.2 μm

Mid-infrared dual-comb spectroscopy has the potential to supplant conventional high-resolution Fourier transform spectroscopy in applications that require high resolution, accuracy, signal-to-noise ratio, and speed. Until now, dual-comb spectroscopy in the mid-infrared has been limited to narrow optical bandwidths or to low signal-to-noise ratios. Using a combination of digital signal processing and broadband frequency conversion in waveguides, we demonstrate a mid-infrared dual-comb spectrometer that can measure comb-tooth resolved spectra across an octave of bandwidth in the mid-infrared from 2.6-5.2 $\mu$m with sub-MHz frequency precision and accuracy and with a spectral signal-to-noise ratio as high as 6500. As a demonstration, we measure the highly structured, broadband cross-section of propane (C3H8) in the 2860-3020 cm-1 region, the complex phase/amplitude spectrum of carbonyl sulfide (COS) in the 2000 to 2100 cm-1 region, and the complex spectra of methane, acetylene, and ethane in the 2860-3400 cm-1 region.