High-resolution photoacoustic and direct absorption spectroscopy of main greenhouse gases by use of a pulsed entangled cavity doubly resonant OPO

An entangled cavity doubly resonant optical parametric oscillator (ECOPO) has been developed to provide tunable narrow line width (<100 MHz) pulsed (8 ns) radiation over the 3.8–4.3 μm spectral range at a multi-kilohertz repetition rate with up to 100-W peak power. We demonstrate that coarse single mode tuning is obtained over the full spectral range of oscillation (300 cm⁻¹), while automated mode-hop-free fine tuning is carried out over more than 100 GHz. High-resolution spectra of main greenhouse gases (CO₂, N₂O, SO₂ and CH₄) have been obtained in good agreement with calculated spectra from the HITRAN database. These experiments outline the unique capabilities of the ECOPO for multi-gas sensing based on direct absorption as well as photoacoustic spectroscopy.     

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     

Fiber-optic ring-down spectroscopy using a tunable picosecond gain-switched diode laser

Visible and near-infrared laser light pulses were coupled into two different types of optical fiber cavities. One cavity consisted of a short strand of fiber waveguide that contained two identical fiber Bragg gratings. Another cavity was made using a loop of optical fiber. In either cavity ∼40 ps laser pulses, which were generated using a custom-built gain-switched diode laser, circulated for a large number of round trips. The optical loss of either cavity was determined from the ring-down times. Cavity ring-down spectroscopy was performed on 200 pL volumes of liquid samples that were injected into the cavities using a 100 μm gap in the fiber loop. A detection limit of 20 ppm of methylene blue dye in aqueous solution, corresponding to a minimum absorptivity of εC<6 cm^-1, was realized. PACS 42.62.Fi; 42.81.-i     

Off-axis re-entrant cavity ring-down spectroscopy with a mid-infrared continuous-wave optical parametric oscillator

We demonstrate an off-axis cavity ring-down spectroscopy system, which uses a mid-infrared continuous-wave optical parametric oscillator as a light source. Off-axis injection with re-entrant configuration of the ring-down cavity is used to achieve high spectral resolution while maintaining high measurement speed. This makes the setup suitable for sensitive molecular spectroscopy in the mid-infrared region, particularly for studies that require high temporal resolution. Formaldehyde (H₂CO) absorption spectrum at 3.4 µm is measured using the off-axis re-entrant cavity ring-down spectrometer.     

Detection of N2O by photoacoustic spectroscopy with a compact, pulsed optical parametric oscillator

A pulsed optical parametric oscillator (OPO) operated in an optical cavity with a grazing-incidence grating configuration (GIOPO) was used for sensitive photoacoustic detection of trace quantities of dinitrogen oxide (N₂O). The (ν₁+ν₃) combination vibration band of N₂O was excited with the idler beam of the GIOPO at 2.86 μm using an optical cavity optimized for the idler beam. The linewidth of the GIOPO could be reduced to 0.4 cm^-1, allowing the rotational structure of the absorption spectrum to be resolved. A concentration sensitivity (signal-to-noise ratio=3) of 60 parts in 10⁹ by volume (60 ppb V) N₂O in synthetic air was obtained. This may be sufficient for continuous monitoring of N₂O in the atmosphere. Received: 29 April 2002 / Revised version: 4 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-6221/54-4255, E-mail: peter.hess@urz.uni-heidelberg.de     

Frequency-stabilized cavity ring-down spectrometer for high-sensitivity measurements of water vapor concentration

We present a portable spectrometer that uses the frequency-stabilized cavity ring-down spectroscopy technique capable of high-precision measurements of trace water vapor concentration. Measuring one of the strongest rovibrational transitions in the ν₁+ν₃ water vapor combination band near ˜ν=7181.156 cm^-1, we compare spectroscopic and thermodynamic determinations of trace water vapor in N₂, and find systematic differences attributable to water vapor background effects and/or uncertainties in line intensities. We also compare the frequency-stabilized ring-down method with other cavity ring-down approaches that are based on unstabilized probe lasers and unstabilized ring-down cavities. We show that for the determination of water vapor concentration, the frequency-stabilized cavity ring-down method has the minimum measurement uncertainty of these techniques. The minimum noise-equivalent absorption coefficient of the spectrometer was 1.2×10^-10 cm^-1 Hz^-1/2, which further corresponds to a minimum detectable water vapor mole fraction equal to 0.7×10^-9 for an absorption spectrum of 10 minutes duration. PACS 33.20.-t; 33.70.Jg; 33.70.Fd; 42.62.Fi     

A pump-resonant signal-resonant optical parametric oscillator for spectroscopic breath analysis

We report on a widely tunable continuous-wave single-frequency pump-resonant signal-resonant optical parametric oscillator (PRSRO) delivering 20 mW to 50 mW of idler power spanning an octave bandwidth in the mid-infrared (1.7 μm and 3.5 μm). The PRSRO is pumped by a Ti:Al₂O₃ ring laser delivering 760 mW around λ _p =795 nm, and thanks to the pump enhancement a threshold as low as 110 mW is achieved with a multi-grating temperature-tuned MgO-doped periodically-poled LiNbO₃. This PRSRO will be used for multi-species trace gas sensing based on cavity ring-down spectroscopy.     

Photoacoustic trace-gas detection using a cw single-frequency parametric oscillator

2 H₆) at 3.34 μm using a widely tunable cw single-frequency optical parametric oscillator. The high frequency and power stability and the continuous tunability of the parametric oscillator make it ideally suited for this application. Detection sensitivities of 0.5 ppb for ethane are obtained, which is comparable to the best results previously obtained with intracavity detection using line-tunable CO overtone lasers. The flexibility and compact size of cw single-frequency parametric oscillators can lead to portable photoacoustic trace-gas detection systems for environmental monitoring and process control. Received: 28 January 1998/Revised version: 9 April 1998     

Ultra-sensitive mid-infrared cavity leak-out spectroscopy using a cw optical parametric oscillator

We report a portable, all-solid-state, mid-infrared spectrometer for trace-gas analysis. The light source is a continuous-wave optical parametric oscillator based on PPLN and pumped by a Nd:YAG laser at 1064 nm. The generated single-frequency idler output covers the wavelength region between 2.35 and 3.75 μm. With its narrow line width, this light source is suitable for precise trace-gas analysis with very high sensitivity. Using cavity leak-out spectroscopy we achieved a minimum detectable absorption coefficient of 1.2×10^-9 /cm (integration time: 16 s), corresponding, for example, to a detection limit of 300 parts per trillion ethane. This sensitivity and the compact design make this trace-gas analyzer a promising tool for various in situ environmental and medical applications. Received: 19 September 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +49-228/733-474, E-mail: frank.kuehnemann@iap.uni-bonn.de     

Quasi-simultaneous detection of CH2O and CH by cavity ring-down absorption and laser-induced fluorescence in a methane/air low-pressure flame

The combination of two-dimensional, planar laser-induced fluorescence (PLIF) and cavity ring-down (CRD) absorption spectroscopy is applied to map quantitatively the spatial distributions of CH₂O and CH in a methane/air flame at 25 Torr. Both species are detected in the same spectral region using the overlapping CH₂O A ¹ A ₂ -X ¹ A ₁ 4₁ ⁰ and CH B-X(1,0 )bands. The combination of diagnostic techniques exploits the spatial resolution of LIF and the quantitative CRD absorption measure of column density. The spatially resolved PLIF provides the distribution of absorbers and line-of-sight CRD absorption the absolute number density needed for quantitative concentration images. The peak CH₂O concentration is (3.5±1.4 )×10¹⁴ cm^-3, or 1450±550 ppm at 1000 K. The lack of precise absorption cross-section data produces these large error limits. Although a flame model predicts lower amounts, these large uncertainties limit this measurement’susefulness as a test of the flame chemistry. Received: 24 April 2001 / Revised version: 10 July 2001 / Published online: 10 October 2001     

Photoacoustic spectroscopy of formaldehyde with tunable laser radiation at the parts per billion level

Selective and sensitive detection of formaldehyde (CH₂O) was achieved using a grazing-incidence optical parametric oscillator (GIOPO), pumped at high repetition rate, as a light source for photoacoustic spectroscopy. The photoacoustic spectrum of formaldehyde was measured in the range from 2785 to 2840 cm^-1 and an absorption line at 2805.0 cm^-1 was selected for detection. Concentrations down to 20 ppbv (parts per billion by volume) formaldehyde in nitrogen were recorded. The detection limit determined by background fluctuations was 3 ppbv (S/N=1) for 3 s lock-in time constant and 3 min acquisition time. The 2805.0 cm^-1 absorption line of the ν₁ vibrational mode was chosen because of the absence of interference with water and carbon-dioxide bands. This allowed the direct detection of formaldehyde in laboratory air without filtering. PACS 42.62.Fi; 42.68.Ca; 42.65.Yj; 07.07.Df     

Influence of ethylene spectral lines on methane concentration measurements with a diode laser methane sensor in the 1.65 μm region

Spectra measurements around 1.65 μm have revealed that spectral lines of ethylene are present in this range along with methane spectral lines. Furthermore, the HITRAN database has no parameters of these ethylene lines. In particular, it was found that several ethylene absorption lines are located near the methane feature often used for quantitative spectroscopy (R3 triplet of the 2ν₃ band). Ethylene can be present together with methane in the samples under study, perturbing the recorded spectrum of CH₄. This perturbation by an interfering species can produce systematic errors in the derived CH₄ concentration. We have found in this work by numerical modelling that when measuring the methane concentration by a diode laser methane sensor operating in the 6046–6048 cm^-1 range, the systematic error on the retrieved CH₄ concentration decreases, as a rule, when decreasing the width of the fitted spectral window. At equal concentrations of ethylene and methane in the sample under study, the error on the concentration of CH₄ determined by the correlation technique can reach 15%. When using the technique based on the 2nd or 3rd derivative of the spectrum, interfering or impurity lines induce a systematic error on the derived CH₄ concentration, which is less than 2%. PACS 07.07.Df; 07.88.+y; 42.62.-b     

12 W mid-infrared output,singly resonant,continuous-wave optical parametric oscillator pumped by a Yb<Superscript>3+</Superscript>-doped fiber amplifier

We report a continuous-wave singly resonant optical parametric oscillator (SRO) with more than 12 W of idler power at 3414 nm when it was operated at 30°C. The SRO was directly pumped by a single-frequency, ytterbium-doped fiber laser with 49 W linear polarization pump powers, and based on 50 mm long periodically poled MgO:LiNbO₃ crystal (PPMgLN) in two-mirror linear cavity with 30.5 μm grating period. It’s pump power at threshold was 5.4 W. The slope-efficiency and quantum-limited performance reached 26 and 79.2%, respectively. The beam polarization matched the e → e + e interaction in crystal. The idler waves were temperature tuned in the range of 3654 to 3811 nm and 3248 to 3414 nm based on two 50 mm long PPMgLN with 29.5 and 30.5 μm grating period. To the best of our knowledge, this is the highest continuouswave mid-IR output obtained for a fiber laser pumped optical parametric oscillator (OPO).     

Wavelength modulated off-axis integrated cavity output spectroscopy in the near infrared

A novel instrument based on an improved off-axis alignment of integrated cavity output spectroscopy (OA-ICOS) in conjunction with a wavelength modulation (WM) technique, was developed using a DFB diode laser operating in the near infrared at 1.573 μm (6357.3 cm^-1). The laser-based sensor employed a 44 cm optical cavity that provided an effective absorption path length of ∼68 m. A minimum detectable absorption of approximately 3.6 ppmv Hz^-1/2 or 2.3×10^-7 Hz^-1/2 per optical pass was obtained using second harmonic detection. We demonstrated that by implementation of the WM technique to OA-ICOS in the near infrared, the detection sensitivity was improved by a factor of 14 compared to that obtained with OA-ICOS. Measurements of CO₂ mixing ratios in ambient air have been performed by using both OA-ICOS and WM-OA-ICOS techniques for performance comparison. PACS 42.62.Fi; 07.07.Df; 33.20.Ea     

Frequency-stabilized cavity ring-down spectroscopy measurements of carbon dioxide isotopic ratios

Carbon dioxide (CO₂) isotopic ratios on samples of pure CO₂ were measured in the 1.6 μm wavelength region using the frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) technique. We present CO₂ absorption spectra with peak signal-to-noise ratios as high as 28,000:1. Measured single-spectrum signal-to-noise ratios were as high as 8900:1, 10,000:1, and 1700:1 for ¹³C/¹²C, ¹⁸O/¹⁶O, and ¹⁷O/¹⁶O, respectively. In addition, we demonstrate the importance of utilizing the Galatry line profile in the spectrum analysis. The use of the Voigt line profile, which neglects the observed collisional narrowing, leads to large systematic errors which are transition-dependent and vary with temperature and pressure. While the relatively low intensities of CO₂ transitions near λ=1.6 μm make this spectral region non-optimal, the sensitivity and stability of FS-CRDS enabled measurement precision of pure CO₂ samples which are comparable to those of other optical techniques which operate at far more propitious wavelengths. These results indicate that a FS-CRDS spectrometer designed to probe CO₂ bands near wavelengths of 2.0 μm or 4.3 μm could achieve significantly improved precision over the present instrument and likely be competitive with mass spectrometric methods.     

Optical parametric oscillator-based photoacoustic detection of CO2 at 4.23 μm allows real-time monitoring of the respiration of small insects

A continuous wave, single frequency and continuously tunable optical parametric oscillator is used in combination with photoacoustic spectroscopy to detect trace emissions of CO₂ from insects under atmospheric conditions. The optical parametric oscillator (OPO) contains a periodically poled lithium niobate crystal and is tunable over the 3.9 to 4.8 μm infrared wavelength region. With the strong rotational-vibrational absorption band of CO₂ at 4.23 μm, it is possible to detect CO₂ down to 7 parts per billion volume using 20 mW of the OPO beam. This detection sensitivity was achieved by adding 4% of SF₆ gas to the atmospheric gas mixture to overcome the slow vibrational relaxation of the excited CO₂ levels. The usefulness of this system is demonstrated by real-time measuring of the fluctuations of the CO₂ concentration in the breath of a single ant (Lasius niger) and individual fruit flies (Drosophila melanogaster). PACS 42.65.Yj; 82.80.Kq; 42.62.Fi     

Rapid and sensitive trace gas detection with continuous wave Optical Parametric Oscillator-based Wavelength Modulation Spectroscopy

A fiber-amplified Distributed Bragg Reflector diode laser is used to pump a continuous wave, singly resonant Optical Parametric Oscillator (OPO). The output radiation covers the 3–4 μm with ability of rapid (100 THz/s) and broad mode-hop-free tuning (5 cm⁻¹). Wavelength Modulation Spectroscopy is combined with the OPO to take optimal advantage of the spectral scan speed. The sensitivity of the system was determined as 0.8 ppbv (parts-per-billion by volume) for ethane (C₂H₆) for the absorption peak at 2996.9 cm⁻¹ recorded in 1.3 seconds, corresponding to a noise equivalent absorption sensitivity (NEAS) of 1.2×10⁻⁹ cm⁻¹/Hz^1/2. A comparison between results using the 1^st, 2^nd and 4^th harmonic derivative signal from wavelength modulation was performed. The broad continuous tunability was demonstrated by covering 35 cm⁻¹ while recording absorption features of ethane, methane and water.     

Isotopic ratio measurement of methane in ambient air using mid-infrared cavity leak-out spectroscopy

We report on infrared laser spectroscopic measurements of the isotopic composition of methane (¹²CH₄, ¹³CH₄) in natural air samples with a cavity ring-down technique. A CO overtone sideband laser is utilized to excite a high-finesse cavity which provides an effective optical absorption path length of 3.6 km. We achieved a detection limit of 105 ppt methane in ambient air using an integration time of 20 s. This corresponds to a minimum detectable absorption of 1.9×10^-9 /cm. Rapid determination of the ¹³C/¹²Cisotopic ratio of methane in ambient air without sample preconcentration or gas processing is realized. The present system requires only few minutes for an isotopic ratio measurement with a precision of 11%o . Received: 14 July 2000 / Revised version: 25 October 2000 / Published online: 6 December 2000     

Spectroscopic characteristics of erbiumand ytterbium-activated laser media

Judd–Ofelt parameters (Ω₂ = 5.09∙10^–20, Ω₄ = 0.92∙10^–20, and Ω₆ = 0.63∙10^–20 cm²) and oscillator strengths of fundamental optical transitions involved in lasing at wavelength 1.54 μm have been calculated for borosilicophosphate glass co-activated with Er³⁺ and Tb³⁺ ions based on experimental luminescence and absorption spectra and refractive indices. The results were used to determine the emission (6∙10^–23 cm²) and absorption (5∙10^–21 cm²) cross sections for λ = 1.54 μm and the gain cross section as a function of inverse population levels.     

Femtosecond fiber laser based methane optical clock

An optical clock based on an Er³⁺ fiber femtosecond laser and a two-mode He–Ne/CH₄ optical frequency standard (λ=3.39 μm) is realized. Difference-frequency generation is used to down convert the 1.5-μm frequency comb of the Er³⁺ femtosecond laser to the 3.4-μm range. The generated infrared comb overlaps with the He–Ne/CH₄ laser wavelength and does not depend on the carrier–envelope offset frequency of the 1.5-μm comb. In this way a direct phase-coherent connection between the optical frequency of the He–Ne/CH₄ standard and the radio frequency pulse repetition rate of the fiber laser is established. The stability of the optical clock is measured against a commercial hydrogen maser. The measured relative instability is 1×10⁻¹² at 1 s and for averaging times less than 50 s it is determined by the microwave standard, while for longer times a drift of the He–Ne/CH₄ optical standard is dominant.