Distributed Feedback Interband Cascade Laser Research Articles

Highly sensitive and selective laser-based BTEX sensor for occupational and environmental monitoring

A mid-infrared laser-based sensor is designed and demonstrated for trace detection of benzene, toluene, ethylbenzene, and xylene isomers at ambient conditions. The sensor is based on a distributed feedback inter-band cascade laser emitting near 3.29 µm and an off-axis cavity-enhanced absorption spectroscopy configuration with an optical gain of 2800. Wavelength tuning and a deep neural network (DNN) model were employed to enable simultaneous and selective BTEX measurements. The sensor performance was demonstrated by measuring BTEX mole fractions in various mixtures. At an integration time of 10 s, minimum detection limits of 11.4, 9.7, 9.1, 10, 15.6, and 12.9 ppb were achieved for benzene, toluene, ethylbenzene, m-xylene, o-xylene, and p-xylene, respectively. The sensor can be used to detect tiny BTEX leaks in petrochemical facilities and to monitor air quality in residential and industrial areas for workplace pollution.

Atmospheric HDO Abundance Measurements in the Tibetan Plateau Based on Laser Heterodyne Radiometer

The Tibet Plateau is known as the “third pole” of the world, and its environmental change profoundly impacts East Asia and even the global climate. HDO is the stable isotope of water vapor, which acts as an ideal tracer for studying the water cycle, and which is commonly used for atmospheric circulation and climatic studies. To monitor the water vapor isotopic abundance in the Tibetan Plateau, a portable laser heterodyne radiometer was operated in Golmud in August 2019. The radiometer utilizes a narrow-linewidth 3.66 μm distributed feedback interband cascade laser as the local oscillator, the heterodyne module is been optimized and the radiometer performs with high resolution and stability in obtaining spectral data. Furthermore, the absorption spectra of atmospheric HDO and H2O are obtained, and the retrieval method for water vapor isotopic abundance is discussed. The optimal estimation method is adopted to retrieve the density of HDO and H2O. The average column density of H2O was 1.22 g/cm2, and the HDO/H2O ratio in Golmud was 178 ± 15 × 10−6 during the observation. For a better understanding of the retrieval, the retrieval errors are analyzed and compared. The results indicate that the smoothing error is significantly higher than the measurement error in this work. The backward trajectory analysis of atmospheric transport is used to investigate the relationship between water vapor density and atmospheric motion. The results indicate that the variation of H2O column density and HDO/H2O ratio have a relationship with atmospheric movements.

A neural network filter based high-sensitive MIR CO2 sensor

A low-power consumption, small-size and high measurement sensitivity mid-infrared (MIR) carbon dioxide (CO2) sensor was developed based on wavelength modulation spectroscopy (WMS) technology, utilizing a mid-infrared distributed feedback interband cascade laser (DFB-ICL) operating around 2682 nm. The sensor incorporated two key components, a home-made multi-pass gas cell with base length of 10 cm achieving 1.5 m optical path and a highly integrated FPGA board, which were used to reduce the size of the sensor. A novel second harmonic-neural network filter (SH-NNF) was also proposed and implemented in this sensor. The sensor’s performance was evaluated through a 20 mins continuous experiment using calibrated gas with 500 ppm concentration. The results, before and after SH-NNF, demonstrated an improvement in sensitivity and detection precision from 1.68 ppm (1 σ) to 1.17 ppm and from 2.14 ppm to 1.45 ppm, respectively. The optimum limit of detection of 0.392 ppm with integration time of 218 s was obtained. The ppm detection and compact characteristics of the developed MIR sensor show its potential for detecting CO2 in the ambient air.

Transient analysis of solar pyrolysis and hydrogen yield via interband cascade laser absorption spectroscopy of methane, acetylene, ethylene, and ethane

A mid-infrared laser absorption sensing method has been developed to measure species concentrations of four hydrocarbons and gas temperature over a range of temperatures in mixture compositions relevant to the pyrolytic decomposition of natural gas. The four measured species (methane, acetylene, ethylene, and ethane) are the most abundant hydrocarbons during the pyrolysis of natural gas, and provide a means to monitor decomposition progress and hydrogen yield through molar balance. In this work, time-division multiplexed signals of three distributed-feedback interband cascade lasers are used to make simultaneous measurements of select C-H stretch rovibrational transitions of the target hydrocarbons in the 3.00–3.34 μm range. The sensor was validated over a range of temperatures and pressures (300–1000 K, 0.03–1 atm) at relevant mixture compositions, with correction methods developed to mitigate cross-species interference. The sensor was demonstrated on a solar-thermal pyrolysis reactor, where time-resolved measurements of species mole fractions were performed across a range of insolation conditions to capture the transient response of the reactor.

High-temperature absorption cross-sections and interference-immune sensing method for formaldehyde near 3.6-µm

Absorption cross-sections of formaldehyde (CH2O) were measured at elevated temperatures near 3.6 µm, a region of strong intensity due to the overlapping QQ5 branch of the v1 band and the PQ7 branch of the v2+v4 combination band. 1,3,5-trioxane was shock-heated in an argon bath gas to produce controlled mixtures of formaldehyde over a range of temperatures (900–1500 K) and pressures (0.4–4.8 atm). Spectrally-resolved absorption measurements of formaldehyde were obtained using a rapidly-tunable distributed-feedback interband cascade laser scanned at 40 kHz over 2778.1–2778.9 cm−1 behind reflected shock waves. The resulting absorption cross-sections were fit with functions reflecting the temperature and pressure dependence of the targeted features, enabling spectral reconstruction at any temperature and pressure within the range of the study. By exploiting the strong temperature and pressure sensitivity of the cross-sections, it is demonstrated that CH2O concentration, temperature, and pressure can be inferred from a measured absorbance spectrum. Cross-sections of common combustion species were also measured over the selected wavelength range to validate that the region is largely free of narrow-band interference. Further, the multi-parameter spectral fitting method is shown to correct for baseline interference and demonstrated in experiments involving transient gas properties.

A selective laser-based sensor for fugitive methane emissions

A mid-infrared laser-based sensor is reported for the quantification of fugitive methane emissions. The sensor is based on a distributed feedback inter-band cascade laser operating near 3.3 μm. Wavelength tuning with cepstral analysis is employed to isolate methane absorbance from (1) fluctuations in the baseline laser intensity, and (2) interfering species. Cepstral analysis creates a modified form of the time-domain molecular free-induction-decay (m-FID) signal to temporally separate optical and molecular responses. The developed sensor is insensitive to baseline laser intensity imperfections and spectral interference from other species. Accurate measurements of methane in the presence of a representative interfering species, benzene, are performed by careful selection of the scan index (ratio of laser tuning range to spectral linewidth) and initial and final time of m-FID signal fitting. The minimum detection limit of the sensor is ~ 110 ppm which can be enhanced with an optical cavity. The proposed sensing strategy can be utilized to measure methane leaks in harsh environments and in the presence of interfering species in environment-monitoring applications.

Highly sensitive methane detection using a mid-infrared interband cascade laser and an anti-resonant hollow-core fiber.

For over a decade hollow-core fibers have been used in optical gas sensors in the role of gas cells. However, very few examples of actual real-life applications of those sensors have been demonstrated so far. In this paper, we present a highly-sensitive hollow-core fiber based methane sensor. Mid-infrared distributed feedback interband cascade laser operating near 3.27 µm is used to detect gas inside anti-resonant hollow-core fiber. R(3) line near 3057.71 cm-1 located in ν3 band of methane is targeted. Compact, lens-free optical setup with an all-silica negative curvature hollow-core fiber as the gas cell is demonstrated. Using wavelength modulation spectroscopy and 7.5-m-long fiber the detection limit as low as 1.54 ppbv (at 20 s) is obtained. The demonstrated system is applied for a week-long continuous monitoring of ambient methane and water vapor in atmospheric air at ground level. Diurnal cycles in methane concentrations are observed, what proves the sensor's usability in environmental monitoring.

GaSb surface grating distributed feedback interband cascade laser emitting at 3.25 µm.

A second-order distributed feedback interband cascade laser emitting at 3.25 µm was designed, grown, and fabricated. By coherent epitaxy of a GaSb cap layer instead of the conventional thin InAs cap on top of the laser structure, a high-quality surface grating was made of GaSb and gold. Enough coupling strength and a significant inter-modal loss difference were predicted according to the simulation within the framework of couple-wave theory. Lasers having 2-mm-long cavities and 4.5-µm-wide ridges with high-/anti-reflection coatings were fabricated. The continuous-wave threshold current and maximum single-mode output power were 60 mA and 24 mW at 20°C, respectively. The output power of 5 mW was still kept at 55°C. Continuous tuning free from mode hopping and high single-mode suppression ratios (>20 dB) were realized at all injection currents and heat-sink temperatures, covering a spectral range of over 20 cm-1.

Laser-based selective BTEX sensing using deep neural networks.

A mid-infrared absorption-based laser sensor is developed for selective and simultaneous benzene, toluene, ethylbenzene, and xylenes (BTEX) measurements under ambient conditions. The sensor is based on a distributed feedback inter-band cascade laser emitting near 3.3 µm. Wavelength tuning and deep neural networks were employed to differentiate the broadband absorbance of BTEX species. The sensor was validated with gas mixtures and real-time measurements were demonstrated at a temporal resolution of 1 s. Minimum detection limits for BTEX in air are 8, 20, 5, and 46 ppm, respectively. This sensor can be utilized to monitor BTEX emissions in the petrochemical, rubber, and paint industries to avoid hazardous health effects.

Distributed Feedback Interband Cascade Laser Based Laser Heterodyne Radiometer for Column Density of HDO and CH4 Measurements at Dunhuang, Northwest of China

Remote sensing of HDO and CH4 could provide valuable information on environmental and climatological studies. In a recent contribution, we reported a 3.53 μm distributed feedback (DFB) inter-band cascade laser (ICL)-based heterodyne radiometer. In the present work, we present the details of measurements and inversions of HDO and CH4 at Dunhuang, Northwest of China. The instrument line shape (ILS) of laser heterodyne radiometer (LHR) is discussed firstly, and the spectral resolution is about 0.004 cm−1 theoretically according to the ILS. Furthermore, the retrieval algorithm, optimal estimation method (OEM), combined with LBLRTM (Line-by-line Radiative Transfer Model) for retrieving the densities of atmospheric HDO and CH4 are investigated. The HDO densities were retrieved to be less than 1.0 ppmv, while the CH4 densities were around 1.79 ppmv from 20 to 24 July 2018. The correlation coefficient of water vapor densities retrieved by LHR and EM27/SUN is around 0.6, the potential reasons for the differences were discussed. Finally, in order to better understand the retrieval procedure, the Jacobian value and the Averaging Kernels are also discussed.

Interband Cascade Laser Arrays for Simultaneous and Selective Analysis of C1-C5 Hydrocarbons in Petrochemical Industry.

The detection and measurement of hydrocarbons are of high interest for a variety of applications, for example within the oil and gas industry from extraction throughout the complete refining process, as well as for environmental monitoring and for portable safety devices. This paper presents a highly sensitive, selective, and robust tunable laser analyzer that has the capability to analyze several components in a gas sample stream. More specifically, a multi-gas system for simultaneous detection of C1 to iC5 hydrocarbons, using a room temperature distributed feedback interband cascade laser array, emitting in the 3.3 µm band has been realized. It combines all the advantages of the tunable laser spectroscopy method for a fast, sensitive, and selective in-line multicomponent tunable laser analyzer. Capable of continuous and milliseconds fast monitoring of C1-iC5 hydrocarbon compositions in a process stream, the analyzer requires no consumables (e.g., purging, carrier gas) and no in-field calibration, enabling a low cost of ownership for the analyzer. The system was built based on an industrial GasEye series platform and deployed for the first time in field at Preem refinery in Lysekil, Sweden, in autumn 2018. Results of the measurement campaign and comparison with gas chromatography instrumentation are presented.

Cavity-Enhanced Measurements of Benzene for Environmental Monitoring

A mid-infrared laser-based sensor is designed and demonstrated for trace detection of benzene at ambient conditions. The sensor is based on a distributed feedback inter-band cascade laser operating near $3.3~\mu \text{m}$ and off-axis cavity-enhanced absorption spectroscopy. A multidimensional linear regression algorithm was applied to enable benzene measurements in the presence of interfering species, such as ethylene, methane and water vapor. A minimum detection limit of 2 ppb was achieved for benzene at an integration time of 6 seconds; the detection limit reduces to 200 ppt in dry conditions. A cross-sensitivity analysis was performed to study the effect of interfering species on benzene measurements. The sensor can be used to detect tiny leaks of benzene in petrochemical facilities and to monitor air quality in residential and industrial areas. The sensor performance was demonstrated by measuring air samples collected from various locations such as a petrol station, parking garage and ambient air.

High-resolution and -precision spectra of acetonitrile at the ν5-band for laser remote sensing

Ultrahigh-resolution and -precision air-broadened acetonitrile (CH3CN) spectra of the v5-band in the region of 3039.0–3041.5 cm−1 were recorded and analyzed using tunable laser absorption spectroscopy (TLAS) technology with a distributed feedback interband cascade laser. The spectral line profile of methane (CH4) was used as the standard to correct the nonlinearity and baseline drift in the CH3CN spectra. The recorded spectra are very close to that in the Pacific Northwest National Laboratory (PNNL) database, however it has a much lower absorbance uncertainty of 1.02%. The air-broadened CH3CN absorption at the v5-band with a spectral resolution of 2.15 × 10−5 cm−1 (~23 fm/637 kHz) and an estimated uncertainty of 1.1% was derived at a temperature of 296.75 K and a pressure of 1 atm. The ultrahigh-resolution and -precision spectra of CH3CN provide reference data for absolute spectral measurements, laser remote sensing, and atmospheric inversion.

Multivariate Analysis of Photoacoustic Spectra for the Detection of Short-Chained Hydrocarbon Isotopologues.

We report, to our knowledge, the first optical detection scheme for short-chained hydrocarbon isotopologues. The sensor system is based on photoacoustic spectroscopy (PAS). Two continuous wave, thermoelectrically cooled, distributed feedback interband cascade lasers (DFB-ICLs) with emission wavelengths around 3.33 and 3.38 μm, respectively, served as light sources. The investigations comprised the main stable carbon isotopologues of methane (12CH4, 13CH4), ethane (12CH3-12CH3, 13CH3-12CH3, 13CH3-13CH3), and propane (12CH3-12CH2-12CH3, 13CH3-12CH2-12CH3). They were selected because of their importance for numerous applications from climate and planetary research to natural gas exploration. Multiple measurements of single components in nitrogen and synthetic mixtures were conducted at room temperature and atmospheric pressure. Depending on the investigated hydrocarbon isotopologue, detection limits ranging from 0.043 ppmv to 3.4 ppmv were achieved. For a selective concentration determination, multivariate analysis (MVA) was applied. Partial least-squares regression (PLSR) was used to calculate concentrations from the PA spectra. The implementation of MVA has shown that the PA setup in principle works reliably and that the selective concentration determination of short-chained hydrocarbon isotopologues is possible.

Ultrahigh resolution spectroscopy for dimethyl sulfide at the ν1- and ν8-bands by a distributed feedback interband cascade laser

The ultrahigh-resolution, air-broadened mid-infrared absorption spectrum of dimethyl sulfide (DMS) was recorded in the spectral region of 2994.17–2999.03 cm−1, where the strong ν1-/ν8-bands are located. Benefitting from the tunable laser absorption spectrometry with a distributed feedback interband cascade laser, the spectral resolution achieved 5.69 × 10−6 cm−1. The recorded spectra of DMS are very close to that in the Pacific Northwest National Laboratory (PNNL) database, however it has a much lower absorbance uncertainty of 0.38%. And the maximum relative difference of the full width at half maximum and the integrated area of spectral peaks between the recorded spectra and the PNNL data are as large as 16.7% and 27.9%, respectively, which could mainly come from the difference of the spectral resolution. The more accurate reference spectrum is hopeful to be applied to absolute measurement and remote sensing for gaseous DMS.

Interband cascade laser absorption of hydrogen chloride for high-temperature thermochemical analysis of fire-resistant polymer reactivity.

A mid-infrared absorption spectroscopy technique has been developed to quantitatively and spatially resolve gas temperature and molecular abundance of $ ^1{{\rm H}^{35}}{\rm Cl} $1H35Cl in the high-temperature pyrolysis and oxidation layers of chlorinated polymers. Two transitions in the R-branch of the fundamental vibrational band of HCl near 3.34 µm are selected due to their relative strength and spectral isolation from other combustion products at elevated temperatures, and they are probed using a distributed feedback interband cascade laser. A scanned-wavelength direct absorption method is employed with a Voigt line-fitting routine to recover projected absorbance areas across the exit plane of a cylindrical polymeric slab, wherein the gaseous core comprises the axisymmetric reaction layer. Tikhonov-regularized Abel inversion of the projected absorbance areas yields line-integrated radial absorption coefficients, from which a two-line ratio is used to infer a radially resolved temperature between the gas core and solid polymer surface. The method is demonstrated to provide insights into the gas-phase combustion physics that lead to the formation of toxicants when a fire-resistant polymer, polyvinyl chloride (PVC), is burned in the presence of oxygen. Two-dimensional images were generated by assembling multiple tomographic reconstructions for several cylinder lengths. The quantitative images highlight the technique's ability to characterize the thermochemical evolution and toxicant formation during the burning of a halogenated polymer fuel.

Ppb-level formaldehyde detection system based on a 3.6 µm interband cascade laser and mode-locked cavity enhanced absorption spectroscopy with self-calibration of the locking frequency

A mid-infrared formaldehyde (H2CO) detection system was demonstrated using a continuous-wave distributed-feedback interband cascade laser (DFB-ICL) emitting at 3.6 μm as light source and an assembly F-P cavity with 20 m effective optical path length as gas chamber. The laser and the cavity were locked to the H2CO absorption peak simultaneously by an electro-optic modulation based automatic Pound-Drever-Hall (PDH) scheme which consist of two steps: dynamic PDH locking and continuous PDH locking. Before continuous PDH locking, the dynamic PDH locking was conducted to acquire the H2CO absorption spectrum and calibration the locking frequency. Then, the cavity transmitted intensity was detected continuously to characterize the gas concentration. H2CO measurements were conducted to evaluate the performance of the sensor system. A linear relationship was observed between the voltage of the absorption signal and the H2CO concentration within the range of 0–6 ppm. Based on Allan deviation analysis, a minimum detection limit of 5.8 ppb was achieved with an averaging time of 30 s.

Silica Hollow-Core Negative Curvature Fibers Enable Ultrasensitive Mid-Infrared Absorption Spectroscopy

Ultrasensitive mid-infrared absorption spectroscopy is demonstrated by the use of a novel silica-based hollow-core negative curvature fiber (HC-NCF). The HC-NCF used in this article consists of a single ring of six nontouching cladding capillaries around the hollow core, thus forming a unique core boundary with a negative curvature. Such a silica HC-NCF enables the broadband single-mode transmission in the mid-infrared. By using the HC-NCF as a compact gas cell, a proof-of-principle experiment is conducted to detect the N2O line at 2778.37 cm−1 with a distributed-feedback interband cascade laser emitting at 3.6 μm. A minimum detectable absorbance of 3 × 10−5 is achieved for a fiber length of 120 cm, corresponding to a noise equivalent absorption (NEA) coefficient of 2.5 × 10−7 cm−1. Silica HC-NCFs offer a new opportunity of developing sensitive and compact gas sensors using mid-infrared absorption spectroscopy.

Atmospheric CH4 measurement near a landfill using an ICL-based QEPAS sensor with V-T relaxation self-calibration

A quartz-enhanced photoacoustic spectroscopy methane (CH4) sensor with vibrational to translational (V-T) relaxation self-calibration was realized and tested for atmospheric CH4 detection near a landfill. To normalize the influence of H2O vapor on the CH4 energy relaxation rate, CH4 and H2O concentrations were detected simultaneously by means of a frequency division multiplexing technique, in which a custom quartz tuning fork was operated in the fundamental and first overtone combined vibration mode. A continuous wave, thermoelectrically cooled distributed feedback interband cascade laser emitting at 3.3 μm and a near-infrared DFB laser emitting at 1.37 μm were used as the excitation source for CH4 and H2O detection, respectively. A theoretical model of V-T relaxation and self-calibration method were developed to allow this CH4 sensor to have a simple setup and a small sensor size. Continuous field measurements were carried out near the largest sanitary landfill in Shanxi province, China, to demonstrate the stability and ruggedness of the realized CH4 sensor.

Sensitive acetone detection with a mid-IR interband cascade laser and wavelength modulation spectroscopy

An efficient method for the detection of acetone, an important biomarker in exhaled breath, by utilizing wavelength modulation spectroscopy (WMS) with a mid-infrared distributed feedback interband cascade laser (DFB-ICL) is presented. The performance of the DFB-ICL laser is characterized, and its linewidth is measured to be $\mbox{(3}.\mbox{39} \pm 0.\mbox{15)}$(3.39±0.15) MHz by beating the output with an auxiliary mid-IR frequency comb over 50 ms. The measured asymmetric acetone absorption profile with the center wavelength around 3367 nm is fitted by the pseudo-Voigt function. The phase shift between the intensity and frequency modulations is determined and used for processing the results. The sensor is tested by performing measurements with calibration mixtures of acetone in nitrogen, and the detection limits of 0.58 ppm and 0.12 ppm were determined with 1 s and 60 s signal averaging times, respectively. Our work shows that wavelength modulation spectroscopy with a DFB-ICL laser complimented by a multipass cell for higher sensitivity can be efficiently used for acetone detection and is promising for sensitive breath analysis.