Tunable Quantum Cascade Laser Research Articles

Infrared Photodissociation Spectroscopy of Water-Tagged Ions with a Widely Tunable Quantum Cascade Laser for Planetary Science Applications.

This work presents a benchtop method for collecting the room temperature gas phase infrared (IR) action spectra of protonated amino acids and their isomers. The adopted setup uses a minimally modified commercial electrospray ionization linear ion trap mass spectrometer (ESI-LIT-MS) coupled to a broadband continuous wave (cw) quantum cascade laser (QCL) source. This approach leverages messenger assisted action spectroscopic techniques using water-tagged molecular ions with complex formation, irradiation, and subsequent analysis, all taking place within a single linear ion trap stage. This configuration thus circumvents the use of multiple mass selection and analysis stages, cryogenic buffer cells, and complex high-power laser systems typically called upon to execute these techniques. The benchtop action spectrometer is used to collect the 935-1600 cm-1 (6.2-10.7 μm) IR action spectrum of a collection of amino acids and a dipeptide with results cross referenced against literature examples obtained with a free electron laser source. Recorded IR spectra are used for the analysis of binary mixture samples composed of constitutional isomers α-alanine and β-alanine with ratios determined to ∼4% measurement uncertainty without the aid of a front-end separation stage. This turn-key QCL-based approach is a major step in showing the viability of tag-based action spectroscopic techniques for use in future in situ planetary science sensors and general analytical applications.

Performance of a High-Speed Pyroelectric Receiver as Cryogen-Free Detector for Terahertz Absorption Spectroscopy Measurements

The application of terahertz (THz) radiation in scientific research as well as in applied and commercial technology has expanded rapidly in recent years. One example is the progress in high-resolution THz spectroscopy based on quantum cascade lasers, which has enabled new observations in astronomy, atmospheric research, and plasma diagnostics. However, the lack of easy-to-use and miniaturised detectors has hampered the development of compact THz spectroscopy systems out of the laboratory environment. In this paper, we introduce a new high-speed pyroelectric receiver as a cryogen-free detector for THz absorption spectroscopy. Its performance is characterised by absorption spectroscopy measurements on a reference gas cell (RGC) with ammonia using a tunable THz quantum cascade laser at approximately 4.75 THz as the light source. It is shown that the receiver can record spectra up to 281 Hz without any artefacts to the observed spectral absorption profile, and the results reproduce the known pressure of ammonia in the RGC. This demonstrates that the pyroelectric receiver can be reliably used as an alternative to helium-cooled bolometers for absorption spectroscopy measurements in the THz range, with its main advantages being the high bandwidth, compactness, relatively low cost, and room-temperature operation. Its simplicity and high sensitivity make this receiver a key component for compact THz spectroscopy systems.

Mid-Infrared Photothermal Spectroscopy for the Detection of Caffeine in Beverages.

Caffeine is the most widely consumed stimulant and is the subject of significant ongoing research and discussions due to its impact on human health. The industry's need to comply with country-specific food and beverage regulations underscores the importance of monitoring caffeine levels in commercial products. In this study, we propose an alternative technique for caffeine analysis that relies on mid-infrared laser-based photothermal spectroscopy (PTS). PTS exploits the high-power output of the quantum cascade laser (QCL) sources to enhance the sensitivity of the mid-IR measurement. The laser-induced thermal gradient in the sample scales with the analytes' absorption coefficient and concentration, thus allowing for both qualitative and quantitative assessment. We evaluated the performance of our experimental PTS spectrometer, incorporating a tunable QCL and a Mach-Zehnder interferometer, for detecting caffeine in coffee, black tea, and an energy drink. We calibrated the setup with caffeine standards (0.1-2.5 mg mL-1) and we benchmarked the setup's capabilities against gas chromatography (GC) and Fourier-transform infrared (FTIR) spectroscopy. Quantitative results aligned with GC analysis, and limits of detection matched the research-grade FTIR spectrometer, indicating an excellent performance of our custom-made instrument. This method offers an alternative to established techniques, providing a platform for fast, sensitive, and non-destructive analysis without consumables as well as with high potential for miniaturization.

An Experimental and Detailed Kinetics Modeling Study of Norbornadiene in Hydrogen and Methane Mixtures: Ignition Delay Time and Spectroscopic CO Measurements

High-energy-density compounds such as norbornadiene (NBD) are being considered as potential cost-effective fuel additives, or partial replacements, for high-speed propulsion applications. To assess the ability of NBD to influence basic fuel reactivity enhancement and to build a database for developing future NBD kinetics models, ignition delay times were measured in two shock-tube facilities at Texas A&M University for H2/O2, CH4/O2, H2/NBD/O2, and CH4/NBD/O2 mixtures (ϕ = 1) that were highly diluted in argon. The reflected-shock temperatures ranged from 1014 to 2227 K, and the reflected-shock pressures remained near 1 atm for all of the experiments, apart from the hydrogen mixtures, which were also tested near 7 atm, targeting the second-explosion limit. The molar concentrations of NBD were supplemented to the baseline mixtures representing 1–2% of the fuel by volume. A chemiluminescence diagnostic was used to track the time history of excited hydroxyl radical (OH*) emission, which was used to define the ignition delay time at the sidewall location. Spectroscopic CO data were also obtained using a tunable quantum cascade laser to complement both the ignition and the chemiluminescence data. The CH4/O2 mixtures containing NBD demonstrated reduced ignition delay times, with a pronounced effect at lower temperatures. Conversely, this additive increased the ignition delay time dramatically in the H2/O2 mixture, which was attributed to changes in the fundamental chemistry with the introduction of molecules containing carbon bonds, which require stronger activation energies for ignition. Correlations were developed to predict the ignition delay time, which depends on species concentration, temperature, and pressure. Additionally, one tentative mechanism was tested, combining base chemistry from NUIGMech 1.1 with pyrolysis and oxidation reactions for NBD using the recent efforts from experimental and theoretical literature studies. The numerical predictions show that the rapid decomposition of NBD provides a pool of active H-radicals, significantly increasing the reactivity of methane. This study represents the first set of gas-phase ignition and CO time-history data measured in a shock tube for hydrogen and methane mixtures containing the additive NBD.

Long wavelength mid-infrared multi-gases spectroscopy using tunable single-mode slot waveguide quantum cascade laser.

Single-mode tunable quantum cascade lasers (QCLs) are promising for high-resolution and highly sensitive trace gases sensing across the mid-infrared (MIR) region. We report on the development of a tunable single-mode slot waveguide QCL array in the long wavelength part of the MIR regime (>12 µm). This laser array exhibits a tuning range of around 12 cm-1, from 735.3 to 747.3 cm-1. Using this developed single-mode tunable QCL, we demonstrate individual gas sensing, yielding the detection limit of 940 ppb and 470 ppb for acetylene and o-xylene, respectively. To verify the potential of the developed QCL array in multi-species gas detection, laser absorption measurements of two mixed gases of acetylene and o-xylene were conducted, showing the absorption features of the corresponding gases agree well with the theoretical predictions.

A mid-infrared laser microscope for the time-resolved study of light-induced protein conformational changes.

We have developed a confocal laser microscope operating in the mid-infrared range for the study of light-sensitive proteins, such as rhodopsins. The microscope features a co-aligned infrared and visible illumination path for the selective excitation and probing of proteins located in the IR focus only. An external-cavity tunable quantum cascade laser provides a wavelength tuning range (5.80-6.35 µm or 1570-1724cm-1) suitable for studying protein conformational changes as a function of time delay after visible light excitation with a pulsed LED. Using cryogen-free detectors, the relative changes in the infrared absorption of rhodopsin thin films around 10-4 have been observed with a time resolution down to 30ms. The measured full-width at half maximum of the Airy disk at λ = 6.08 µm in transmission mode with a confocal arrangement of apertures is 6.6 µm or 1.1λ. Dark-adapted sample replacement at the beginning of each photocycle is then enabled by exchanging the illuminated thin-film location with the microscope mapping stage synchronized to data acquisition and LED excitation and by averaging hundreds of time traces acquired in different nearby locations within a homogeneous film area. We demonstrate that this instrument provides crucial advantages for time-resolved IR studies of rhodopsin thin films with a slow photocycle. Time-resolved studies of inhomogeneous samples may also be possible with the presented instrument.

Rovibrational Spectroscopy of Trans and Cis Conformers of 2-Furfural from High-Resolution Fourier Transform and QCL Infrared Measurements.

The ortho-isomer 2-furfural (2-FF), which is a primary atmospheric pollutant produced from biomass combustion, is also involved in oxidation processes leading to the formation of secondary organic aerosols. Its contribution to radiative forcing remains poorly understood. Thus, monitoring 2-FF directly in the atmosphere or in atmospheric simulation chambers to characterize its reactivity is merited. The present study reports an extensive jet-cooled rovibrational study of trans and cis conformers of 2-FF in the mid-IR region using two complementary setups: a continuous supersonic jet coupled to a high-resolution Fourier transform spectrometer on the IR beamline of the SOLEIL synchrotron (JET-AILES), and a pulsed jet coupled to a mid-IR tunable quantum cascade laser spectrometer (SPIRALES). Firstly, jet-cooled spectra recorded at rotational temperatures ranging between 20 and 50 K were exploited to derive reliable excited-state molecular parameters of trans- and cis-2-FF vibrational bands in the fingerprint region. The parameters were obtained from global fits of 11,376 and 3355 lines distributed over eight and three vibrational states (including the ground state), respectively, with a root mean square of 12 MHz. In a second step, the middle resolution spectrum of 2-FF recorded at 298.15 K and available in the HITRAN database was reconstructed by extrapolating the data derived from our low-temperature high-resolution analyses to determine the cross sections of each vibrational band of both 2-FF conformers in the 700-1800 cm-1 region. Finally, we clearly demonstrated that the contribution of hot bands observed in the room temperature 2-FF spectrum, estimated between 40 and 63% of the fundamental band, must be imperatively introduced in our simulation to correctly reproduce the HITRAN vibrational cross sections of 2-FF with a deviation smaller than 10%.

Improving transmittance of long-wave infrared guided-mode resonant filters

The long-wave infrared (LWIR) spectral region spanning from 8 to 12 μm is useful for many scientific and industrial applications. Many of these applications require use of either a bandpass or a bandstop filter that can be realized by the guided-mode resonance (GMR) effect with subwavelength periodic features in layered dielectric materials transparent in the LWIR. The GMR filters operating in the LWIR region are fabricated by depositing an amorphous germanium (Ge) film to form a zero-contrast (ZC) waveguide-grating (WGG) on a polished zinc selenide (ZnSe) substrate. In general, the backside of a ZnSe substrate with refractive index 2.41 is uncoated causing a 17% Fresnel-reflection loss in the light transmitted through the filter due to a large impedance mismatch at the ZnSe/air interface. Because we use such filters in the LWIR laser experiments for notch filtering, to improve the filter transmittance we used ZnSe substrates coated on one-side with broadband antireflection coating (ARC) covering the 7 to 12 μm spectral range to fabricate GMRFs with one-dimensional (1D) Ge ZC WGG. We employed high-spatial resolution e-beam lithography and reactive-ion etching nanofabrication techniques to achieve high-performance large-area (12 × 12 mm2) 1D notch filters with subwavelength periods. We characterized polarization dependent spectral performance of the prototype filters with both coherent and incoherent incident light using a tunable quantum cascade laser system that spans the 7 to 12 μm region, and a Fourier transform infrared spectrometer with collimated incident beam to achieve close to 15% improvement in the peak transmittance as well as significant reduction in coherent noise compared to our earlier results with GMRFs without ARC. Here, we present the filter design simulation and measurement results.

Polarization independent electron-beam written 2-D longwave infrared guided-mode resonant filters

We fabricated guided mode resonance filters (GMRFs) with two-dimensional (2-D) gratings operating in the 8 to 12 µm long-wave infrared (LWIR) region by depositing amorphous germanium (Ge) film to form a zero-contrast (ZC) waveguide-grating (WGG) on polished zinc selenide (ZnSe) substrates with and without antireflection coating (ARC). We employed high-spatial resolution e-beam lithography and reactive-ion etching (RIE) nanofabrication techniques. We characterized the fabricated filters for their polarization independent spectral performance using a tunable quantum cascade laser (QCL) system and a modified Fourier transform infrared (FTIR) spectrometer. Here, we will present both theoretical and experimental results and their comparison.

Применение машинного обучения для диагностики некоторых социально значимых заболеваний по выдыхаемому человеком воздуху методом инфракрасной лазерной спектроскопии

The infrared spectra of the air exhaled by several groups of volunteers were studied: those suffering from type 1 diabetes, bronchial asthma, and pneumonia. To record infrared spectra, a tunable quantum-cascade laser (QCL) was used. QCL emits in the wavelength range from 5.3 to 12.8 μm in a pulsed mode with a pulse width of 50 ns, a power of up to 150 mW, and a tuning step of 1 cm-1. The laser is optically coupled to an astigmatic gas cell of the Herriot type with an optical path length of 76 m. A difference was found in the intensity of selective lines of biomarker molecules in the spectra of exhaled air of healthy volunteers compared to similar indicators of volunteers suffering from a certain disease. For an example of methods such as the support vector machine (SVM), the k-nearest neighbors (k-NN) and the random forest algorithm (RandomForest), the possibility of classifying volunteers by the infrared spectra of their exhaled air is shown. The use of dimensionality reduction methods (PCA and t-SNE) made it possible to increase the accuracy of disease classification up to 98% in terms of the accuracy metric.

Dual-Beam Photothermal Spectroscopy Employing a Mach-Zehnder Interferometer and an External Cavity Quantum Cascade Laser for Detection of Water Traces in Organic Solvents.

We report on a mid-infrared (mid-IR) photothermal spectrometer for liquid-phase samples for the detection of water in organic solvents, such as ethanol or chloroform, and in complex mixtures, such as jet fuel. The spectrometer is based on a Mach-Zehnder interferometer (MZI) employing a He-Ne laser, a mini-flow cell with two embedded channels placed in the interferometer's arms, and a tunable external cavity quantum cascade laser (EC-QCL) for selective analyte excitation in a collinear arrangement. In this study, the bending vibration of water in the spectral range 1565-1725 cm-1 is targeted. The interferometer is locked to its quadrature point (QP) for most stable and automated operation. It provides a linear response with respect to the water content in the studied solvents and photothermal analyte spectra, which are in good agreement with FTIR absorbance spectra. The method is calibrated and validated against coulometric Karl Fischer (KF) titration, showing comparable performance and sensitivity. Limits of detection (LODs) for water detection in the single-digit ppm range were obtained for chloroform and jet fuel due to their low background absorption, whereas lower sensitivity has been observed for water detection in ethanol due to pronounced background absorption from the solvent. In contrast to KF titration, which requires toxic reagents and produces waste, the developed method works reagent-free. It can be applied in an online format in the chemical industry as well as for fuel quality control, being industrial applications where traces of water need to be accurately determined, preferably in real-time. It thus holds great promise as a green alternative to the offline KF titration method, which is the current standard method for this application.

Synchronous upconversion of quantum cascade lasers in AgGaS2.

We investigate synchronous upconversion of a pulsed, tunable quantum cascade laser (QCL) in the important 5.4-10.2 µm range, with a 30 kHz, Q-switched, 1064 nm laser. The possibility to accurately control the repetition rate and pulse duration of the QCL results in a good temporal overlap with the Q-switched laser, leading to an upconversion quantum efficiency of 16% in a 10 mm-long AgGaS2 crystal. We investigate the noise properties of the upconversion process in terms of pulse-to-pulse energy stability and timing jitter. For QCL pulses in the 30-70 ns range the upconverted pulse-to-pulse stability is approximately 1.75%. The demonstrated combination of broad tunability and high signal to noise in the system is well-suited for mid-IR spectral analysis of highly absorbing samples.

Multi-Modal Stand-Off Detection of Plastics for Sorting Application

Plastics are extremely valuable to our society and are widely used in many industries such as food, beverage, textile, healthcare, automotive, aerospace, construction, agriculture, oil, etc. Since plastics do not degrade easily with time, the discarded plastics pose a grave environmental problem. Only less than 10% of plastics is recycled in the US. Therefore, there is an urgent need to increase the recycling of plastic products. At present, sorting of plastic waste is carried out manually which is time consuming, costly and manual labor intensive. To address this problem, a novel multi-modal sensor platform capable of improving the accuracy of automated sorting of various plastics by using molecular identification has been developed. This multimodal technique of standoff photothermal-photoacoustic detection is a combination of mid-infrared (MIR) photo-thermal spectroscopy and photoacoustic spectroscopy for characterizing surfaces. Since MIR is free of overtones, this region is known as the molecular fingerprint region. In this technique, the plastic surface is illuminated with a pulsed laser beam from a tunable quantum cascade laser (QCL). The photothermal detection is accomplished by collecting the scattered light from the plastic surface which contains the molecular vibration spectrum of the sample. A silicon bi-material microcantilever, fabricated by depositing a thin metal film on one of its sides is used as a sensitive uncooled infrared detector. Monitoring the bi-material cantilever bending as a function of illumination wavelength provides the IR absorption spectrum of the plastic material. Simultaneously, the photoacoustic signal generated by the absorption of light is monitored by a sensitive microphone. A highly sensitive microfabricated acoustic resonator is used for collecting the photoacoustic signal. Monitoring the microphone response as a function of wavelength produces photoacoustic spectrum (PAS) of the sample. This non-destructive characterization technique will help in enhancing the quality of plastic sorting process at materials recovery facilities and other industries by making the process inexpensive and time efficient.

Beam combining of a broadly and continuously tunable quantum cascade laser.

We report a cost-efficient method to demonstrate the beam combining of five laser elements in an array of tunable slot waveguide quantum cascade lasers in the mid-infrared region at around 10 µm. An aspherical lens with five fine-tuned mini mirrors was employed to collimate the individual beams from the laser array. To verify the feasibility of this beam combining approach, the combined beams were coupled into a hollow-core fiber gas cell with a low numerical aperture (N.A.) of 0.03 and a coupling efficiency >= 0.82, for gas sensing of binary compound gases of ammonia and ethylene simultaneously.

Time-resolved CO2, CO, and N2 vibrational population measurements in Ns pulse discharge plasmas

Time-resolved CO2 and N2 vibrational populations and translational-rotational temperature are measured in a CO2–N2 plasma sustained by a ns pulse discharge burst in plane-to-plane geometry. Time-resolved, absolute number density of CO generated in the plasma is also inferred from the experimental data. CO2 and CO vibrational populations are measured by mid-IR, tunable quantum cascade laser absorption spectroscopy, and N2 vibrational populations are measured by the ns broadband vibrational CARS. Transient excitation of N2 and CO2 asymmetric stretch vibrational energy modes is detected during the discharge burst. The time-resolved rate of CO generation does not correlate with N2 or CO2(ν 3) vibrational temperatures, indicating that CO2 dissociation via the vibrational excitation is insignificant at the present conditions. The rate of CO generation decreases gradually during the discharge burst. The estimated specific energy cost of the CO product is close to that of N atoms in pure nitrogen, measured previously at similar operating conditions. Comparison of the experimental data with the kinetic modeling analysis indicates that CO2 dissociation in collisions with electronically excited N2 molecules is the dominant channel of CO generation at the present conditions, although the inferred CO yield in these processes is significantly lower than 1. The effect of vibrational energy transfer between N2 and CO2 on the plasma chemical processes is insignificant. The kinetic model underpredicts a rapid reduction of the N2 and CO2(ν 3) vibrational temperatures during the later half of the discharge burst and in the afterglow. V–T relaxation of N2 by N and O atoms generated in the ns pulse discharge plasma does not affect the vibrational relaxation rate in a significant way. However, rapid V–T relaxation of CO2 by O atoms has a significant effect on the relaxation rate. The difference between the experimental data and the modeling predictions may be due to the unknown scaling of the CO2–O V–T rates with the vibrational quantum number.

Accurately Measuring Molecular Rotational Spectra in Excited Vibrational Modes.

Although gas phase rotational spectroscopy is a mature field for which millions of rotational spectral lines have been measured in hundreds of molecules with sub-MHz accuracy, it remains a challenge to measure these rotational spectra in excited vibrational modes with the same accuracy. Recently, it was demonstrated that virtually any rotational transition in excited vibrational modes of most molecules may be made to lase when pumped by a continuously tunable quantum cascade laser (QCL). Here, we demonstrate how an infrared QCL may be used to enhance absorption strength or induce lasing of terahertz rotational transitions in highly excited vibrational modes in order to measure their frequencies more accurately. To illustrate the concepts, we used a tunable QCL to excite v3 R-branch transitions in N2O and either enhanced absorption or induced lasing on 20 v3 rotational transitions, whose frequencies between 299 and 772 GHz were then measured using either heterodyne or modulation spectroscopy. The spectra were fitted to obtain the rotational constants B3 and D3, which reproduce the measured spectra to within the experimental uncertainty of ± 5 kHz. We then show how this technique may be generalized by estimating the threshold power to make any rotational transition lase in any N2O vibrational mode.

Simultaneous detection of CF4 and SIF4 using external cavity quantum cascade laser absorption spectroscopy

Direct and quantitative access to plasma etch processes (like the concentration of precursors or of molecular etch products) plays a key role for the industrial production of semiconductor devices. In this paper, a laser absorption spectroscopy sensor based on a pulsed, broadband tunable external cavity quantum cascade laser (ECQCL) was developed for potential plasma diagnostic analysis. To demonstrate this detection technique, the typical precursor molecule CF4 and the etch product SiF4 were selected as analytic targets. Composition attribution and concentration analysis for different CF4 and SIF4 mixture samples were experimentally investigated by selecting proper spectral window and self-established signal processing algorithm. By using a direct absorption spectroscopy detection scheme with a short path absorption cell of 29.6 cm, Allan deviation analysis indicates that detection limits of 9.39 ppm for CF4 and 46.66 ppm for SiF4 were obtained with a 1 s integration time, which can be further improved to ~ 1.63 ppm and ~ 7.28 ppm by averaging up to 120 s, respectively.

Protein conformational changes and protonation dynamics probed by a single shot using quantum-cascade-laser-based IR spectroscopy.

Mid-IR spectroscopy is a powerful and label-free technique to investigate protein reactions. In this study, we use quantum-cascade-laser-based dual-comb spectroscopy to probe protein conformational changes and protonation events by a single-shot experiment. By using a well-characterized membrane protein, bacteriorhodopsin, we provide a comparison between dual-comb spectroscopy and our homebuilt tunable quantum cascade laser (QCL)-based scanning spectrometer as tools to monitor irreversible reactions with high time resolution. In conclusion, QCL-based infrared spectroscopy is demonstrated to be feasible for tracing functionally relevant protein structural changes and proton translocations by single-shot experiments. Thus, we envisage a bright future for applications of this technology for monitoring the kinetics of irreversible reactions as in (bio-)chemical transformations.

A reliable method for the isolation and characterization of microplastics in fish gastrointestinal tracts using an infrared tunable quantum cascade laser system

Societal and environmental concern due to frequent reports of microplastics in fish stomachs raised as they may accumulate along the trophic chain. The request for analysing microplastics in fish stresses two major analytical issues: sample treatment and final characterization. The, so far, workhorse for chemical characterization is infrared spectroscopy which is time-consuming. Here, a quantum cascade laser-based device is used to accelerate the characterization stage. Its novelty poses new challenges for sample processing and particle handling because the unknown particles must be transferred to a reflective slide. In this study, three sample digestion protocols (alkaline-oxidative with H2O2, and alkaline-oxidative with NaClO and enzymatic-oxidative) and three different procedures to transfer the filter cake to reflective slides are compared. A simplified enzymatic-oxidative digestion (validated through an interlaboratory exercise) combined with a Syncore® automatic evaporation system and a Laser Direct Infrared Imaging (LDIR) device is proposed first time as a reliable and relatively fast method to treat gastrointestinal tracts of fish. Analytical recoveries were studied using samples of Scomber scombrus and they were ca. 100% for big –i.e., >500 μm- and ca. 90% for medium –i.e., 200–300 μm- particles and ca. 75% for 10 μm thick fibres.

Longwave infrared polarization independent monolithic guided-mode resonance filters with double-sided orthogonal linear gratings

We present novel polarization independent, high-quality monolithic spectral filters based on the guided-mode resonance (GMR) effect with orthogonal linear gratings on either side of the substrate operating in the longwave infrared (LWIR) spectral region. We employ high-spatial resolution e-beam lithography and reactive-ion etching (RIE) nanofabrication techniques to achieve large-area (10×10 mm2) notch filters with subwavelength features. We fabricated prototype filters and characterized their polarization independent spectral performance with both coherent and incoherent incident light using a tunable quantum cascade laser (QCL) system that spans the ∼8–12 µm spectral band as well as a Fourier transform infrared (FTIR) spectrometer with collimated incident beam.