A quantum cascade laser-based optical feedback cavity-enhanced absorption spectrometer for the simultaneous measurement of CH4 and N2O in air

Optical feedback cavity-enhanced absorption spectroscopy (OF CEAS) has been demonstrated with a thermoelectrically cooled continuous wave distributed feedback quantum cascade laser (QCL) operating at wavelengths around 7.84 μm. The QCL is coupled to an optical cavity which creates an absorption pathlength greater than 1000 m. The experimental design allows optical feedback of infra-red light, resonant within the cavity, to the QCL, which initiates self-locking at each TEM₀₀ cavity mode frequency excited. The QCL linewidth is narrowed to below the mode linewidth, greatly increasing the efficiency of injection of light into the cavity. At the frequency of each longitudinal cavity mode, the absorption coefficient of an intracavity sample is obtained from the transmission at the mode maximum, measured with a thermoelectrically cooled detector: spectral line profiles of CH₄ and N₂O in ambient air were recorded simultaneously and with a resolution of 0.01386 cm^?1. A minimum detectable absorption coefficient of 5.5×10^?8 cm^?1 was demonstrated after an averaging time of 1 s for this completely thermoelectrically cooled system. The bandwidth-normalised limit for a single cavity mode is 5.6×10^?9 cm^?1?Hz^?1/2 (1σ).     

Simultaneous detection of trace gases using multiplexed tunable diode lasers and a photoacoustic cell containing a cantilever microphone

We report what we believe to be a novel demonstration of simultaneous detection of multiple trace gases by near-IR tunable diode laser photoacoustic spectroscopy using a cell containing a cantilever microphone. Simultaneous detection of carbon monoxide (CO), ethyne (C₂H₂), methane (CH₄) and combined carbon monoxide/carbon dioxide (CO+CO₂) in nitrogen-based gas mixtures was achieved by modulation frequency division multiplexing the outputs of four near-IR tunable diode lasers. Normalized noise-equivalent absorption coefficients of 3.4×10^?9, 3.6×10^?9 and 1.4×10^?9 cm^?1?W?Hz^?1/2 were obtained for the simultaneous detection of CO, C₂H₂ and CH₄ at atmospheric pressure. These corresponded to noise-equivalent detection limits of 249.6 ppmv (CO), 1.5 ppmv (C₂H₂) and 293.7 ppmv (CH₄) respectively over a measurement period of 2.6 s at the relevant laser power. The performance of the system was not influenced by the number of lasers deployed, the main source of noise arising from ambient acoustic effects. The results confirm that small-volume photoacoustic cells can be used with low optical power tunable diode lasers for rapid simultaneous detection of trace gases with high sensitivity and specificity.     

CW DFB RT diode laser-based sensor for trace-gas detection of ethane using a novel compact multipass gas absorption cell

The development of a continuous wave, thermoelectrically cooled (TEC), distributed feedback diode laser-based spectroscopic trace-gas sensor for ultra-sensitive and selective ethane (C₂H₆) concentration measurements is reported. The sensor platform used tunable diode laser absorption spectroscopy (TDLAS) and wavelength modulation spectroscopy as the detection technique. TDLAS was performed using an ultra-compact 57.6 m effective optical path length innovative spherical multipass cell capable of 459 passes between two mirrors separated by 12.5 cm and optimized for the 2.5–4 μm range TEC mercury–cadmium–telluride detector. For an interference-free C₂H₆ absorption line located at 2,976.8 cm^?1, a 1σ minimum detection limit of 740 pptv with a 1 s lock-in amplifier time constant was achieved.     

Detection of C2H2 and HCl using mid-infrared degenerate four-wave mixing with stable beam alignment: towards practical in situ sensing of trace molecular species

A stable and convenient optical system to realize the forward phase-matching geometry for degenerate four-wave mixing (DFWM) is demonstrated in the mid-infrared spectral region by measuring DFWM signals generated in acetylene (C₂H₂) and hydrogen chloride (HCl) molecules by probing the fundamental ro-vibrational transitions. IR laser pulses tunable from 2900 cm^?1 to 3350 cm^?1 with a 0.025 cm^?1 linewidth were obtained using a laser system composed of an injection seeded Nd:YAG laser, a dye laser, and a frequency mixing unit. At room temperature and atmospheric pressure, a detection limit of 35 ppm (～ 9.5×10¹⁴ molecules/cm³) for C₂H₂ was achieved in a gas flow of a C₂H₂/N₂ mixture by scanning the P(11) line of the (010(11)⁰)–(0000⁰0⁰) band. The detection limit of the HCl molecule was measured to be 25 ppm (～6.8×10¹⁴ molecules/cm³) in the same environment by probing the R(4) line. The dependences of signal intensities on molecular concentrations and laser pulse energies were demonstrated using C₂H₂ as the target species. The variations of the signal line shapes with changes in the buffer gas pressures and laser intensities were recorded and analyzed. The experimental setup demonstrated in this work facilitates the practical implementation of in situ, sensitive molecular species sensing with species-specific, spatial and temporal resolution in the spectral region of 2.7–3.3 μm (3000–3700 in cm^?1), where various molecular species important in combustion have absorption bands.     

Optical-feedback cavity-enhanced absorption spectroscopy with a quantum-cascade laser yields the lowest formaldehyde detection limit

We report on the first application of Optical Feedback-Cavity Enhanced Absorption Spectroscopy to formaldehyde trace gas analysis at mid-infrared wavelengths. A continuous-wave room-temperature, distributed-feedback quantum cascade laser emitting around 1,769 cm^?1 has been successfully coupled to an optical cavity with finesse 10,000 in an OF-CEAS spectrometer operating on the ν₂ fundamental absorption band of formaldehyde. This compact setup (easily transportable) is able to monitor H₂CO at ambient concentrations within few seconds, presently limited by the sample exchange rate. The minimum detectable absorption is 1.6 × 10^?9 cm^?1 for a single laser scan (100 ms, 100 data points), with a detectable H₂CO mixing ratio of 60 pptv at 10 Hz. The corresponding detection limit at 1 Hz is 5 × 10^?10 cm^?1, with a normalized figure of merit of 5 × 10^?11cm $^{-1}/\sqrt{\rm Hz}$ (100 data points recorded in each spectrum taken at 10 Hz rate). A preliminary Allan variance analysis shows white noise averaging down to a minimum detection limit of 5 pptv at an optimal integration time of 10 s, which is significantly better than previous results based on multi-pass or cavity-enhanced tunable QCL absorption spectroscopy.     

Quartz-enhanced photoacoustic spectroscopy-based sensor system for sulfur dioxide detection using a CW DFB-QCL

Sulfur dioxide (SO₂) trace gas detection based on quartz-enhanced photoacoustic spectroscopy (QEPAS) using a continuous wave, distributed feedback quantum cascade laser operating at 7.24 μm was performed. Influence of water vapor addition on monitored QEPAS SO₂ signal was also investigated. A normalized noise equivalent absorption coefficient of NNEA (1σ) = 1.21 × 10^?8 cm^?1 W Hz^?1/2 was obtained for the ν ₃ SO₂ line centered at 1,380.93 cm^?1 when the gas sample was moisturized with 2.3 % H₂O. This corresponds to a minimum detection limit (1σ) of 63 parts per billion by volume for a 1 s lock-in time constant.     

Cavity-enhanced optical feedback-assisted photo-acoustic spectroscopy with a 10.4 μm external cavity quantum cascade laser

An ultra-sensitive photo-acoustic spectrometer using a 10.4 μm broadly tunable mid-IR external cavity quantum cascade laser (EC-QCL) coupled with optical feedback to an optical power buildup cavity with high reflectivity mirrors was developed and tested. A laser optical power buildup factor of 181 was achieved, which corresponds to an intra-cavity power of 9.6 W at a wavelength of 10.4 μm. With a photo-acoustic resonance cell placed inside the cavity this resulted in the noise-equivalent absorption coefficient of 1.9 × 10^?10 cm^?1 Hz^?1/2, and a normalized noise-equivalent absorption of 1.1 × 10^?11 cm^?1 W Hz^?1/2. A novel photo-acoustic signal normalization technique makes the photo-acoustic spectrometer’s response immune to changes and drifts in the EC-QCL excitation power, EC-QCL to cavity coupling efficiency and cavity mirrors aging and contamination. An automatic lock of the EC-QCL to the cavity and optical feedback phase optimization permitted long wavelength scans within the entire EC-QCL spectral tuning range.     

Tunable erbium-doped fiber ring laser for applications of infrared absorption spectroscopy

We fabricate a low noise erbium-doped fiber ring laser that can be continuously tuned over 102 nm by insertion of the fiber Fabry-Perot tunable filter (FFP-TF) in the ring cavity with a novel cavity structure and the optimal gain medium length. As an application of this fiber ring laser, we performed the absorption spectroscopy of acetylene (¹³C₂H₂) and hydrogen cyanide (H¹³C¹⁴N) and measure the absorption spectra of more than 50 transition lines of these gases with an excellent signal to noise ratio (SNR). The pressure broadening coefficients of four acetylene transition lines are obtained using this fiber ring laser and an external cavity laser diode.     

A compact resonant Π-shaped photoacoustic cell with low window background for gas sensing

A resonant photoacoustic cell capable of detecting the traces of gases at an amplitude-modulation regime is represented. The cell is designed so as to minimize the window background for the cell operation at a selected acoustic resonance. A compact prototype cell (the volume of acoustic cavity of ~0.2 cm³, total cell weight of 3.5 g) adapted to the narrow diffraction-limited beam of near-infrared laser is produced and examined experimentally. The noise-associated measurement error and laser-initiated signals are studied as functions of modulation frequency. The background signal and useful response to light absorption by the gas are analyzed in measurements of absorption for ammonia traces in nitrogen flow with the help of a pigtailed DFB laser diode operated near a wavelength of 1.53 µm. The performance of absorption detection and gas-leak sensing for the prototype operated at the second longitudinal acoustic resonance (the resonance frequency of ~4.38 kHz, Q-factor of ~13.9) is estimated. The noise-equivalent absorption normalized to laser-beam power, and detection bandwidth is ~1.44 × 10^?9 cm^?1 W Hz^?1/2. The amplitude of the window-background signal is equivalent to an absorption coefficient of ~2.82 × 10^?7 cm^?1.     

In situ TDLAS measurement of absolute acetylene concentration profiles in a non-premixed laminar counter-flow flame

Acetylene (C₂H₂), as an important precursor for chemiluminescence species, is a key to understand, simulate and model the chemiluminescence and the related reaction paths. Hence we developed a high resolution spectrometer based on direct Tunable Diode Laser Absorption Spectroscopy (TDLAS) allowing the first quantitative, calibration-free and spatially resolved in situ C₂H₂ measurement in an atmospheric non-premixed counter-flow flame supported on a Tsuji burner. A fiber-coupled distributed feedback diode laser near 1535 nm was used to measure several absolute C₂H₂ concentration profiles (peak concentrations up to 9700 ppm) in a laminar non-premixed CH₄/air flame (T up to 1950 K) supported on a modified Tsuji counter-flow burner with N₂ purge slots to minimize end flames. We achieve a fractional optical resolution of up to 5×10^?5 OD (1σ) in the flame, resulting in temperature-dependent acetylene detection limits for the P17e line at 6513 cm^?1 of up to 2.1 ppm?m. Absolute C₂H₂ concentration profiles were obtained by translating the burner through the laser beam using a DC motor with 100 μm step widths. Intercomparisons of the experimental C₂H₂ profiles with simulations using our new hydrocarbon oxidation mechanisms show excellent agreement in position, shape and in the absolute C₂H₂ values.     

Line strength and collisional broadening coefficients of H2O at 2.7 μm for natural gas quality assurance applications

We employed tunable diode laser absorption spectroscopy to measure the line strength, the methane (CH₄), ethane (C₂H₆) and the propane (C₃H₈) broadening coefficients for the 523–422 H₂O transition at 3619.61 cm^?1. Water amount fractions generated by a stable and accurate humidity transfer standard, traceable to the SI units via the German national humidity standard, were used to calibrate the spectroscopic line strength measurements. We focus on the traceability of the measured line data to the SI and on uncertainty assessments following the guidelines of the Guide to the Expression of Uncertainty in Measurement. We determined the line strength to be (8.42 ± 0.07)×10^?20 cm^?1/(cm^?2 molecule) corresponding to a relative uncertainty of ±0.8%. To the best of our knowledge, we report the first methane, ethane and propane broadening coefficients of (8.037 ± 0.056)×10^?5 cm^?1/hPa, (9.077 ± 0.064)×10^?5 cm^?1/hPa and (10.469 ± 0.073)×10^?5 cm^?1/hPa for the 523–422 H₂O transition at 3619.61 cm^?1, respectively. The relative combined uncertainties of the stated CH₄, C₂H₆ and C₃H₈ broadening coefficients are in the ±0.7% range.     

Sensitive amplitude-and phase-modulated absorption-spectroscopy with a continuously tunable diode laser

The output beam of a continuously tunable GaA1As-diode laser with external cavity is phase-modulated at 800 MHz in an electrooptic LiTaO₃ crystal. The amplitude of the rf voltage applied to the EOM is modulated at 80 kHz in order to allow lock-in detection. Using a multipass absorption cell the detection limit of the absorption coefficient α could be pushed down to α_min ≧2 × 10^?10 cm^2212;1. The sensitivity of the techique is demonstrated by examples of overtone transitions in C₂H₂ and H₂O vapor.     

Acetylene detection based on diode laser QEPAS: combined wavelength and residual amplitude modulation

Quartz-enhanced photoacoustic spectroscopy (QEPAS) is demonstrated for acetylene detection at atmospheric pressure and room temperature with a fiber-coupled distributed feedback (DFB) diode laser operating at ~1.53 μm. An efficient approach for gas concentration calibration is demonstrated. The effect of residual amplitude modulation on the performance of wavelength modulated QEPAS is investigated theoretically and experimentally. With optimized spectrophone parameters and modulation depth, a minimum detectable limit (1σ) of ~2 part-per-million volume (ppmv) was achieved with an 8.44-mW diode laser, which corresponds to a normalized noise equivalent coefficient (1σ) of 6.16 × 10^?8 cm^?1 W/Hz^1/2.     

High-sensitivity CRDS absorption spectroscopy of acetylene between 5851 and 6341 cm−1

The absorption spectrum of acetylene has been recorded at room temperature (297 K) using high-sensitivity cavity ring-down spectroscopy (α_min ～ 5×10^?11 cm^?1) in the 5851 and 6341 cm^?1 interval corresponding to a region of very weak absorption. A list of about 10,700 absorption features with estimated absolute line intensities was constructed. The smallest intensities are of the order of 5×10^?29 cm molecule^?1. The line list includes about 2500 absorption lines of ethylene present at the ppm level in the acetylene sample and identified on the basis of a high-resolution Fourier transform spectrum specifically recorded. A total of more than 2700 lines of ¹²C₂H₂ were rovibrationally assigned in comparison with accurate predictions provided by a global effective operator model. Overall, the present effort adds about 2260 new assignments to the set of about 500 assigned transitions available in the literature. The new assignments correspond to 45 new bands and 17 already-known bands, for which additional J lines were assigned. Spectroscopic parameters were derived for the upper vibrational levels from a band by band fit of the line positions (typical root mean square deviation values are of the order of 0.001 cm^?1). A few of the analysed bands were found to be affected by rovibrational perturbations, which are discussed. The new data will be valuable to refine the parameters of the global effective Hamiltonian and dipole moments of ¹²C₂H₂.     

Mid-infrared fiber-coupled QCL-QEPAS sensor

An innovative spectroscopic system based on an external cavity quantum cascade laser (EC-QCL) coupled with a mid-infrared (mid-IR) fiber and quartz enhanced photoacoustic spectroscopy (QEPAS) is described. SF₆ has been selected as a target gas in demonstration of the system for trace gas sensing. Single mode laser delivery through the prongs of the quartz tuning fork has been obtained employing a hollow waveguide fiber with inner silver–silver iodine (Ag–AgI) coatings and internal core diameter of 300 μm. A detailed design and realization of the QCL fiber coupling and output collimator system allowed almost practically all (99.4 %) of the laser beam to be transmitted through the spectrophone module. The achieved sensitivity of the system is 50 parts per trillion in 1 s, corresponding to a record for QEPAS normalized noise-equivalent absorption of 2.7 × 10^?10 W cm^?1 Hz^?1/2.     

Frequency-agile,rapid scanning spectroscopy: absorption sensitivity of 2 × 10−12 cm−1 Hz−1/2 with a tunable diode laser

We present ultrasensitive measurements of molecular absorption using frequency-agile rapid scanning, cavity ring-down spectroscopy with an external-cavity diode laser. A microwave source that drives an electro-optic phase modulator with a bandwidth of 20 GHz generates pairs of sidebands on the probe laser. The optical cavity provides for high sensitivity and filters the carrier and all but a single, selected sideband. Absorption spectra were acquired by stepping the tunable sideband from mode-to-mode of the ring-down cavity at a rate that was limited only by the cavity decay time. This approach allows for scanning rates of 8 kHz per cavity resonance, a minimum detectable absorption coefficient of 1.7 × 10^?11 cm^?1 after only 20 ms of averaging, and a noise-equivalent absorption coefficient of 1.7 × 10^?12 cm^?1 Hz^?1/2. By comparison with cavity-enhanced laser absorption spectrometers reported in the literature, the present system is, to the best of our knowledge, among the most sensitive and has by far the highest spectrum scanning rate.     

Single-QCL-based absorption sensor for simultaneous trace-gas detection of CH4 and N2O

A quantum cascade laser (QCL)-based absorption sensor for the simultaneous dual-species monitoring of CH₄ and N₂O was developed using a novel compact multipass gas cell (MGC). This sensor uses a thermoelectrically cooled, continuous wave, distributed feedback QCL operating at ~7.8 µm. The QCL wavelength was scanned over two neighboring CH₄ (1275.04 cm^?1) and N₂O (1274.61 cm^?1) lines at a 1 Hz repetition rate. Wavelength modulation spectroscopy (f = 10 kHz) with second harmonic (2f) detection was performed to enhance the signal-to-noise ratio. An ultra-compact MGC (16.9 cm long and a 225 ml sampling volume) was utilized to achieve an effective optical path length of 57.6 m. With such a sensor configuration, a detection limit of 5.9 ppb for CH₄ and 2.6 ppb for N₂O was achieved, respectively, at 1-s averaging time.     

Cavity-enhanced optical frequency comb spectroscopy in the mid-infrared application to trace detection of hydrogen peroxide

We demonstrate the first cavity-enhanced optical frequency comb spectroscopy in the mid-infrared wavelength region and report the sensitive real-time trace detection of hydrogen peroxide in the presence of a large amount of water. The experimental apparatus is based on a mid-infrared optical parametric oscillator synchronously pumped by a high-power Yb:fiber laser, a high-finesse broadband cavity, and a fast-scanning Fourier transform spectrometer with autobalancing detection. The comb spectrum with a bandwidth of 200 nm centered around 3.76 μm is simultaneously coupled to the cavity and both degrees of freedom of the comb, i.e. the repetition rate and carrier envelope offset frequency, are locked to the cavity to ensure stable transmission. The autobalancing detection scheme reduces the intensity noise by a factor of 300, and a sensitivity of 5.4×10^?9 cm^?1?Hz^?1/2 with a resolution of 800 MHz is achieved (corresponding to 6.9×10^?11 cm^?1?Hz^?1/2 per spectral element for 6000 resolved elements). This yields a noise equivalent detection limit for hydrogen peroxide of 8 parts-per-billion (ppb); in the presence of 2.8 % of water the detection limit is 130 ppb. Spectra of acetylene, methane, and nitrous oxide at atmospheric pressure are also presented, and a line-shape model is developed to simulate the experimental data.     

Continuous wave,distributed feedback diode laser based sensor for trace-gas detection of ethane

The development of a continuous wave (CW), thermoelectrically cooled (TEC), distributed feedback (DFB) laser diode based spectroscopic trace-gas sensor for ultra-sensitive and selective ethane (C₂H₆) concentration measurements is reported. The sensor platform used tunable diode laser absorption spectroscopy (TDLAS) based on a 2f wavelength modulation (WM) detection technique. TDLAS was performed with a 100 m optical path length astigmatic Herriott cell. For an interference free C₂H₆ absorption line located at 2976.8 cm⁻¹ a 1σ minimum detection limit of 240 pptv (part per trillion by volume) with a 1 second lock-in amplifier time constant was achieved. In addition, reliable and long-term sensor performance was obtained when operating the sensor in an absorption line locked mode.     

Near-infrared laser based cavity ringdown spectroscopy for applications in petrochemical industry

A simple, economic diode laser based cavity ringdown system for trace-gas applications in the petrochemical industry is presented. As acetylene (C₂H₂) is sometimes present as an interfering contaminant in the gas flow of ethylene (ethene, C₂H₄) in a polyethylene production process, an on-line monitoring of such traces is essential. We investigated C₂H₂–C₂H₄ mixtures in a gas-flow configuration in real time. The experimental setup consists of a near-infrared external cavity diode laser with an output power of a few mW, standard telecommunication fibers and a home-made gas cell providing a user-friendly cavity alignment. A noise-equivalent detection sensitivity of 4.5×10^-8 cm^-1 Hz^-1/2 was achieved, corresponding to a detection limit of 20 ppbV C₂H₂ in synthetic air at 100 mbar. In an actual C₂H₂–C₂H₄ gas-flow measurement the minimum detectable concentration of C₂H₂ added to the C₂H₄ gas stream (which may already contain an unknown C₂H₂ contamination) increased to 160 ppbV. Moreover, stepwise C₂H₂ concentration increments of 500 ppbV were resolved with a 1-min time resolution and an excellent linear relationship between the absorption coefficient and the concentration was found. PACS 07.07.Df; 42.62.Fi; 82.80.Gk