Laser diode photoacoustic and FTIR laser spectroscopy of formaldehyde in the 2.3 μm and 3.5 μm spectral range

The room temperature operating GaInAsSb/AlGaAsSb based diode laser and 66 K InAsSb/InAsSbP laser diode both operating in spectral range of formaldehyde absorption 4350-4361 cm⁻¹ and 2821-2823 cm⁻¹ have been characterized and compared. Very precise arrangement of laser absorption together with high resolution Fourier transform technique was tested. The photoacoustic technique was employed to determine the detection limit of formaldehyde (less than 1 ppmV) diluted by nitrogen for the strongest absorption line of the ν₃ + ν₅ band in the emission region of the GaInAsSb/AlGaAsSb diode laser. The detection limit (less than 10 ppbV) of formaldehyde was achieved in the 2820 cm⁻¹ spectral range in case of InAsSb/InAsSbP laser (fundamental bands of ν₁, ν₅)_.     

Infrared diode laser spectroscopy

Three types of lasers (double-heterostructure 66 K InAsSb/InAsSbP laser diode, room temperature, multi quantum wells with distributed feedback (MQW with DFB) (GaInAsSb/AlGaAsSb based) diode laser and vertical cavity surface emitting lasers (VCSELs) (GaSb based) have been characterized using Fourier transform emission spectroscopy and compared. The photoacoustic technique was employed to determine the detection limit of formaldehyde (less than 1 ppmV) for the strongest absorption line of the v₃ + v₅ band in the emission region of the GaInAsSb/AlGaAsSb diode laser. The detection limit (less than 10 ppbV) of formaldehyde was achieved in the 2820 cm⁻¹ spectral range in case of InAsSb/InAsSbP laser (fundamental bands of v₁, v₅). Laser sensitive detection (laser absorption together with high resolution Fourier transform infrared technique including direct laser linewidth measurement, infrared photoacoustic detection of neutral molecules (methane, form-aldehyde) is discussed.     

Continuous wave optical parametric oscillator for quartz-enhanced photoacoustic trace gas sensing

A continuous wave optical parametric oscillator, generating up to 300 mW idler output in the 3–4 μm wavelength region, and pumped by a fiber-amplified DBR diode laser is used for trace gas detection by means of quartz-enhanced photoacoustic spectroscopy (QEPAS). Mode-hop-free tuning of the OPO output over 5.2 cm^-1 and continuous spectral coverage exceeding 16.5 cm^-1 were achieved via electronic pump source tuning alone. Online monitoring of the idler wavelength, with feedback to the DBR diode laser, provided an automated closed-loop control allowing arbitrary idler wavelength selection within the pump tuning range and locking of the idler wavelength with a stability of 1.7×10^-3 cm^-1 over at least 30 min. Using this approach, we locked the idler wavelength at an ethane absorption peak and obtained QEPAS data to verify the linear response of the QEPAS signal at different ethane concentrations (100 ppbv-20 ppmv) and different power levels. The detection limit for ethane was determined to be 13 ppbv (20 s averaging), corresponding to a normalized noise equivalent absorption coefficient of 4.4×10^-7 cm^-1  W/Hz^1/2. PACS 42.55.Wd; 42.65.Yj; 42.62.Fi     

Carbon dioxide and ammonia detection using 2 μm diode laser based quartz-enhanced photoacoustic spectroscopy

Quartz-enhanced photoacoustic spectroscopy was employed for trace gas concentration measurements of CO₂ and NH₃ using a continuous wave thermoelectrically cooled, distributed feedback diode laser operating at 2 μm. A normalized noise equivalent absorption coefficient, NNEA(1σ)=1.4×10^-8 cm^-1W/ was obtained for CO₂ using the R18 line of the 2ν₁+ν₃ band at 4991.26 cm^-1. This corresponds to minimum detection limit (1σ) of 18 parts per million (ppm) for a 1 s lock-in time constant. The influence of the H₂O presence in the sample gas mixture on the CO₂ sensor performance was investigated. Ammonia detection was performed using the ^P P ₆(6)_S line of the ν₃+ν₄ band at 4986.99 cm^-1. A detection limit (1σ) of 3 ppm for NH₃ concentration with a 1 s lock-in time constant was achieved. This results in a normalized noise equivalent absorption of NNEA(1σ)=8.9×10^-9 cm^-1W/. PACS 82.80.Kq; 46.62.Fi; 42.55.Px     

Ultra-sensitive carbon monoxide detection by using EC-QCL based quartz-enhanced photoacoustic spectroscopy

A quartz-enhanced photoacoustic spectroscopy (QEPAS) based sensor for carbon monoxide detection at ppbv levels was developed with a 4.65???m external-cavity quantum cascade laser operating both in continuous wave (cw) and pulsed modes. A?23-fold enhancement of the measured CO signal amplitude was obtained when water vapor, acting as a catalyst for vibrational energy transfer, was added to the targeted analyte mixture. In the cw mode, a noise-equivalent sensitivity (NES, 1??) of 2 ppbv was achieved at a gas pressure of 100?Torr, for 1-s lock-in amplifier (LIA) time constant (TC), which corresponds to a normalized noise equivalent absorption coefficient (NNEA) of $1.48\times 10^{-8}~\mathrm{cm}^{-1}\,\mathrm{W}/\sqrt{\mathrm{Hz}}$ . In the pulsed mode, the determined NES and NNEA were 46?ppbv and $1.07\times 10^{-8}~\mathrm{cm}^{-1}\,\mathrm{W}/\sqrt{\mathrm{Hz}}$ , respectively, for a 3-ms LIA TC at atmospheric pressure with a laser scan rate of 18?cm^-1/s and a 50?% duty cycle. An intercomparison between cw and pulsed QEPAS-based CO detection is also reported.     

Application of a continuous-wave tunable erbium-doped fiber laser to molecular spectroscopy in the near infrared

Development of a continuous-wave tunable fiber laser-based spectrometer for applied spectroscopy is reported. Wide wavelength tunability of an erbium-doped fiber laser (EDFL) was investigated in the near-infrared region of 1543–1601 nm. Continuous mode-hop free fine frequency tuning has been accomplished by temperature tuning in conjunction with mechanical tuning. The overall spectroscopic performance of the EDFL was evaluated in terms of frequency tunability along with its suitability for molecular spectroscopy. High-resolution absorption spectra of acetylene (C₂H₂) were recorded near 1544 nm with a minimum measurable absorption coefficient of about 3.5×10^-7 cm^-1/Hz^1/2 for direct absorption spectroscopy associated with a 100-m long multipass cell. Detections of C₂H₂ at different concentration levels were performed as well with high dynamic detection range varying from 100% purity to sub ppmv using cavity ring down spectroscopy. A 3σ-detection-limited minimum detectable concentration (MDC) of 400 ppbv has been obtained by using the transition line P_e(22) of the ν₁+ν₃+ν₅ ¹(Π_g)-ν₅ ¹(Π_u) hot band near 1543.92 nm with a detection bandwidth of 2.3 Hz. This corresponds to a minimum detectable absorption coefficient of 6.6×10^-11 cm^-1/Hz^1/2. The sensitivity limit could be further improved by almost one order of magnitude (down to ∼60 ppbv) by use of the P_e(27) line of the ν₁+ν₃(Σ_u ⁺)-0(Σ_g ⁺)combination band near 1543.68 nm. PACS 42.55.Wd; 42.62.Fi; 07.57.Ty; 07.88.+y     

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.     

The rotationally-resolved absorption spectrum of formaldehyde from 6547 to 6804 cm

The room temperature absorption spectrum of formaldehyde, H₂CO, from 6547 to 6804 cm⁻¹ (1527-1470 nm) is reported with a spectral resolution of 0.001 cm⁻¹. The spectrum was measured using cavity-enhanced absorption spectroscopy (CEAS) and absorption cross-sections were calculated after calibrating the system using known absorption lines of H₂O and CO₂. Several vibrational combination bands occur in this region and give rise to a congested spectrum with over 8000 lines observed. Pressure broadening coefficients in N₂, O₂, and H₂CO are reported for an absorption line at 6780.871 cm⁻¹, and in N₂ for an absorption line at 6684.053 cm⁻¹.     

Formaldehyde sensor using interband cascade laser based quartz-enhanced photoacoustic spectroscopy

A novel continuous-wave mid-infrared distributed feedback interband cascade laser was utilized to detect and quantify formaldehyde (H₂CO) using quartz-enhanced photoacoustic spectroscopy. The laser was operated at liquid-nitrogen temperatures and provided single-mode output powers of up to 12 mW at 3.53 m (2832.5 cm^-1). The noise equivalent (1) detection sensitivity of the sensor was measured to be 2.2×10^-8 cm^-1W(Hz)^-1/2 for H₂CO in ambient air, which corresponds to a detection limit of 0.6 parts in 10⁶ by volume (ppmv) for a 10 s sensor time constant and 3.4 mW laser power delivered to the sensor module. PACS 42.62.Fi; 72.50.+b     

Relaxation effects and high sensitivity photoacoustic detection of NO<Subscript>2</Subscript> with a blue laser diode

A detection limit of 200 ppt of NO₂ in N₂ at atmospheric pressure was obtained with a photoacoustic detector and a high power blue laser diode. This corresponds to a normalized noise (1σ) equivalent absorption coefficient of 2×10^-9 cm^-1W/Hz^0.5. Measurements at different laser modulation frequencies showed no frequency dependence of the photoacoustic signal, indicating a relaxation time τ < 4 μs. Mixing O₂ into the NO₂ containing gas results in a decrease of the photoacoustic signal. A simple model shows that this effect can be attributed to an increased vibrational-vibrational relaxation of NO₂ to O₂. PACS 31.70.Hq; 34.50.Ez; 42.55.Px     

Photoacoustic measurement of N2O concentrations in ambient air with a pulsed optical parametric oscillator

Photoacoustic spectroscopy, in combination with a pulsed grazing-incidence optical parametric oscillator (GIOPO), was used for sensitive detection of nitrous oxide (N₂O) in ambient air. The ν₁+ν₃ combination band of N₂O was excited with the idler beam of the GIOPO in the 2.76 μm–2.91 μm spectral region, where CO₂ and water-absorption lines are also present. Three chemical filters filled with KOH, CaCl₂, and P₂O₅ were used to reduce the CO₂ and water concentrations to the level of several parts per billion (10⁹) by volume (ppbv). Photoacoustic spectra containing several absorption lines were recorded and the concentration was determined by an integral evaluation method and a fast Fourier transform evaluation method. The photoacoustic signal was calibrated by a standard mixture of 50.6 parts per million by volume (ppmv) of N₂O in synthetic air. Values of 311±5 ppbv, 314±5 ppbv, and 316±5 ppbv were found for three ambient samples collected at nearby roads. PACS 42.62.Fi; 42.65.Yj; 07.07.Df; 42.68.Ca     

Measurements of carbon monoxide mixing ratios in Houston using a compact high-power CW DFB-QCL-based QEPAS sensor

Measurements of carbon monoxide (CO) mixing ratios in Houston, Texas, during the period from May 16, 2013 to May 28, 2013 were performed using a sensitive, selective, compact, and portable quartz-enhanced photoacoustic spectroscopy (QEPAS)-based CO sensor employing a high-power continuous wave (CW) distributed feedback quantum cascade laser (DFB-QCL). The minimum detectable CO concentration was 3 ppbv for the strong, interference-free R(6) absorption line at 2,169.2 cm^?1 and a 5 s data acquisition time. The average CO concentration during the measurement period was 299.1 ± 81.4 ppb with observed minimum and maximum values of 210.5 and 4,307.9 ppb, respectively. A commercially available electrochemical sensor was employed in-line for simultaneous measurements to confirm the response of the CW DFB-QCL-based QEPAS sensor to variations of the CO mixing ratios. Moderate agreement (R ² = 0.7) was found between both sets of CO measurements.     

Resonance photoacoustic spectroscopy and gas analysis of gaseous flow at reduced pressure

The results of theoretical and experimental studies of sensitivity of a resonant photoacoustic Helmholtz resonator detector for gas flowing through a photoacoustic cell under reduced pressure are presented. The measurements of the sensitivity and ultimate sensitivity of the differential photoacoustic cell were performed with a near-IR room-temperature diode laser using the well-known H₂O absorption line (12496.1056 cm^-1) as a reference. The measured value of the sensitivity (6–17 Pa W m^-1) is in satisfactory agreement with the calculated one, which equals 6–35 Pa W m^-1. The obtained value of the ultimate sensitivity ((3–5)×10^-7 W m^-1 Hz^-1/2) provides measurements of the concentration of molecules at the ppb–ppm level. Received: 19 April 2001 / Revised version: 18 September 2001 / Published online: 7 November 2001     

The photoacoustic absorption spectrum of VO2+ ions in cerium orthophoshate

The photoacoustic absorption spectrum of vanadium-doped CePO₄ samples has been observed at room temperature. Two absorption peaks are seen, one at 11200 cm^-1 and another at 14800 cm^-1. They are attributed to VO²⁺ ions in interstitial sites of distorted octahedral symmetry.     

Laser-based photoacoustic ammonia sensors for industrial applications

An industrial trace-ammonia sensor based on photoacoustic spectroscopy and CO₂ lasers has been developed for measuring ammonia with a 1σ detection limit of 220 parts-per-trillion (ppt) in an integration time of 30 s. The instrument response time for measuring ammonia was 200 s, limited by adsorption effects due to the polar nature of ammonia. The minimum detectable fractional absorbance was 2.0×10^-7, and the minimum normalized detectable absorption coefficient for this system was 2.4×10^-7 W cm^-1/z. The 9R(30) transition of the CO₂ laser at 9.22 μm with 2 W of output power was used to probe the strong sR(5,K) multiplet of ammonia at the same wavelength. This sensor was demonstrated with an optically multiplexed configuration for simultaneous measurement in four cells. Received: 3 April 2002 / Revised version: 31 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-310/458-0171, E-mail: webber@pranalytica.com     

Near infrared cw-CRDS coupled to laser photolysis: Spectroscopy and kinetics of the HO2 radical

We present in this work a new experimental set-up for sensitive detection of reactive species: continuous wave cavity ring-down spectroscopy (cw-CRDS) as a detection method in laser photolysis reactor. HO₂ radicals were generated by using a 248 nm photolysis of SOCl₂/CH₃OH/O₂ mixtures and were detected in the first vibrational overtone of the OH stretch around 6625 cm^-1, using a DFB diode laser. In order to perform the spectroscopic and kinetic measurements of the HO₂ radical, two different timing schemes have been used. The absorption line strength of the transition at 6625.784 cm^-1 has been extracted from kinetic measurement to (5.2±1.0)×10^-21 cm² molecule^-1cm^-1. The detection limit for the actual set-up is 2×10¹² molecules cm^-3. PACS 42.62.Fi; 82.33.Tb; 82.20.W     

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.     

Off-axis continuous-wave cavity-enhanced absorption spectroscopy of narrow-band and broadband absorbers using red diode lasers

We present an application of continuous-wave (cw) cavity-enhanced absorption spectroscopy (CEAS) with off-axis alignment geometry of the cavity and with time integration of the cavity output intensity for detection of narrow-band and broadband absorbers using single-mode red diode lasers at λ=687.1 nm and λ=662 nm, respectively. Off-axis cw CEAS was applied to kinetic studies of the nitrate radical using a broadband absorption line at λ=662 nm. A rate constant for the reaction between the nitrate radical and E-but-2-eneof (3.78±0.17)×10^-13 cm³ molecule^-1 s^-1 was measured using a discharge-flow system. A nitrate-radical noise-equivalent (1σ≡ root-mean-square variation of the signal) detection sensitivity of 5.5×10⁹ molecule cm^-3 was achieved in a flow tube with a diameter of 4 cm and for a mirror reflectivity of ∼99.9% and a lock-in amplifier time constant of 3 s. In this case, a noise-equivalent fractional absorption per one optical pass of 1.6×10^-6 was demonstrated at a detection bandwidth of 1 Hz. A wavelength-modulation technique (modulation frequency of 10 kHz) in conjunction with off-axis cw CEAS has also been used for recording 1f- and 2f-harmonic spectra of the ^RR(15) absorption of the b¹Σ_g ⁺-X³Σ_g ^- (1,0) band of molecular oxygen at =14553.947 cm^-1. Noise-equivalent fractional absorptions per one optical pass of 1.35×10^-5, 6.9×10^-7 and 1.9×10^-6 were obtained for direct detection of the time-integrated cavity output intensity, 1f- and 2f-harmonic detection, respectively, with a mirror reflectivity of ∼99.8%, a cavity length of 0.22 m and a detection bandwidth of 1 Hz. Received: 24 June 2002 / Revised version: 12 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: vlk@physchem.ox.ac.uk     

Measurements of long-term changes in atmospheric OCS (carbonyl sulfide) from infrared solar observations

Multi-decade atmospheric OCS (carbonyl sulfide) infrared measurements have been analyzed with the goal of quantifying long-term changes and evaluating the consistency of the infrared atmospheric OCS remote-sensing measurement record. Solar-viewing grating spectrometer measurements recorded in April 1951 at the Jungfraujoch station (46.5°N latitude, 8.0°E longitude, 3.58 km altitude) show evidence for absorption by lines of the strong ν₃ band of OCS at 2062 cm⁻¹. The observation predates the earliest previously reported OCS atmosphere remote-sensing measurement by two decades. More recent infrared ground-based measurements of OCS have been obtained primarily with high-resolution solar-viewing Fourier transform spectrometers (FTSs). Long-term trends derived from this record span more than two decades and show OCS columns that have remained constant or have decreased slightly with time since the Mt. Pinatubo eruption, though retrievals assuming different versions of public spectroscopic databases have been impacted by OCS ν₃ band line intensity differences of ∼10%. The lower stratospheric OCS trend has been inferred assuming spectroscopic parameters from the high-resolution transmission (HITRAN) 2004 database. Volume mixing ratio (VMR) profiles measured near 30°N latitude with high-resolution solar-viewing FTSs operating in the solar occultation mode over a 22 years time span were combined. Atmospheric Trace MOlecucle Spectroscopy (ATMOS) version 3 FTS measurements in 1985 and 1994 were used with Atmospheric Chemistry Experiment (ACE) measurements during 2004-2007. Trends were calculated by referencing the measured OCS VMRs to those of the long-lived constituent N₂O to account for variations in the dynamic history of the sampled airmasses. Means and 1-sigma standard deviations of VMRs (in ppbv, or 10⁻⁹ per unit air volume) averaged over 30-100 hPa from measurements at 25-35°N latitude are 0.334±0.089 ppbv from 1985 (ATMOS Spacelab 3 measurements), 0.297±0.094 ppbv from 1994 ATLAS 3 measurements, 0.326±0.074 ppbv from ACE 2004 measurements, 0.305±0.096 ppbv from ACE 2005 measurements, 0.328±0.074 from ACE 2006 measurements, and 0.305±0.090 ppbv from ACE measurements through August 2007. Assuming these parameters, we conclude that there has been no statistically significant trend in lower stratospheric OCS over the measurement time span. We discuss past measurement sets, quantify the impact of changes in infrared spectroscopic parameters on atmospheric retrievals and trend measurements, and discuss OCS spectroscopic uncertainties of the current ν₃ band parameters in public atmospheric databases.     

Determination of the low absorption coefficients of thick semi-conductor samples using rear side photoacoustic spectroscopy detection

Based on the Rosencwaig and Gersho theory, we have theoretically derived the photoacoustic signal in the gaz behind the unilluminated surface of thick samples and presented a simple analytical procedure for determining the low optical absorption spectra of these samples.The rear side photoacoustic spectroscopy (PAS) detection has been employed on thick samples of GaP (0,2-1mm) and optical absorption coefficients in the region between 15 to 200 cm^?1 were measured.Our results are discussed in comparison with those obtained by usual front side PAS detection and spectroscopic ellipsometry.