Optimization of the mode matching in pulsed cavity ringdown spectroscopy by monitoring non-degenerate transverse mode beating

A simple and reliable method is presented for optimizing the mode matching of a laser beam to the high-finesse cavity used in pulsed cavity ringdown spectroscopy (CRDS). The method is based on minimizing the excitation of higher-order transverse cavity modes through monitoring the non-degenerate transverse mode beating which becomes visible with induced cavity asymmetry caused by slight misalignment. No additional instrument is required other than a pinhole aperture, thus this method can be applied for CRDS experiments in the whole wavelength range. Measurements of the CRDS absorption spectrum of acetylene (C₂H₂) near 571 nm demonstrate that the mode-matching optimization improves the sensitivity of pulsed CRDS. Received: 22 October 2001 / Revised version: 16 January 2002 / Published online: 14 March 2002     

Laser spectroscopy with a pulsed, narrowband infrared optical parametric oscillator system: a practical, modular approach

-1 in a single scan. The potential of the OPO system for linear and nonlinear-optical spectroscopy is demonstrated by recording high-resolution photoacoustic absorption and coherent anti-Stokes Raman spectra of methane, as a gas and in a pulsed supersonic free jet. This narrowband tunable infrared source is shown to scan reliably with an optical bandwidth as small as 0.007 cm^-1 (210 MHz) full width half maximum (fwhm), close to the fourier-transform limit. Received: 5 February 1998/Revised version: 6 March 1998     

Oxygen measurements at high pressures with vertical cavity surface-emitting lasers

Measurements of oxygen concentration at high pressures (to 10.9 bar) were made using diode-laser absorption of oxygen A-band transitions near 760 nm. The wide current-tuning frequency range (>30 cm^-1) of vertical cavity surface-emitting lasers (VCSELs) was exploited to enable the first scanned-wavelength demonstration of diode-laser absorption at high pressures; this strategy is more robust than fixed-wavelength strategies, particularly in hostile environments. The wide tuning range and rapid frequency response of the current tuning were further exploited to demonstrate wavelength-modulation absorption spectroscopy in a high-pressure environment. The minimum detectable absorbance demonstrated, ∼1×10^-4, corresponds to ∼800 ppm-m oxygen detectivity at room temperature and is limited by etalon noise. The rapid- and wide-frequency tunability of VCSELs should significantly expand the application domain of absorption-based sensors limited in the past by the small current-tuning frequency range (typically <2 cm^-1) of conventional edge-emitting diode lasers. Received: 26 July 2000 / Revised version: 2 January 2001 / Published online: 20 April 2001     

Flexible laser diode trace gas sensor based on cavity ringdown spectroscopy with an optical fiber-coupled high-finesse external-cavity diode laser

A flexible and portable trace nitrogen dioxide sensor based on cavity ringdown spectroscopy using an optical fiber-coupled high-finesse cavity was successfully demonstrated. Tailoring the spatial mode matching condition of the core of an optical fiber and high-finesse external cavity allows for effective optical feedback into an antireflection-coated laser diode for stable resonant enhancement of the external cavity. The external cavity, which works as a ringdown cavity, could be remotely located from the light source and receiver section by only a single mode optical fiber. The sensitivity was found to be 1.0×10⁻⁷ cm⁻¹ in a compact 1-cm³ ringdown cavity volume.     

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     

Quantification of stable minor species in confined flames by cavity ring-down spectroscopy: application to NO

Cavity ring-down spectroscopy (CRDS) is used to measure the NO mole fraction formed in the burnt gases of low-pressure premixed flames. It is shown that the line-of-sight absorption is greatly increased by the contribution of the NO molecules surrounding the burner. This contribution has been quantified by developing a mathematical procedure taking into account the spatial and spectral features of the CRDS measurement. Calculations have been undertaken in the general case of a stable species not consumed in the flame. The most sensitive parameter is the temperature both in the flame and outside the flame. Simulations allow the selection of the best spectroscopic transitions for a given flame (i.e. a given temperature profile), ensuring the weakest influence of the inaccuracy affecting the temperature determination. High quantum states belonging to the A–X (0–1) band of NO have been found to be the most valuable and have led to a NO mole fraction determination with an accuracy of ±13%. NO absorption in the flame was completely masked using the A–X (0–0) band. Finally, the prompt-NO mole fraction formed in a methane/air flame stabilized at 33 Torr is obtained by combining CRDS and laser induced fluorescence techniques. Received: 12 October / Revised version: 1 February 2002 / Published online: 14 March 2002     

Spectroscopic diagnostics of chemical processes: applications of tunable optical parametric oscillators

Optical parametric oscillator (OPO) and amplifier (OPA) devices are useful for spectroscopic sensing of chemical processes in laboratory, industrial, and environmental settings. This is particularly true of nanosecond-pulsed, continuously tunable OPO/OPA systems, for which we survey a variety of instrumental strategies, together with actual spectroscopic measurements. The relative merits of OPO wavelength control by intracavity gratings and by injection seeding are considered. A major innovation comprises an OPO with a ring cavity based on periodically poled lithium niobate (PPLN) and injection-seeded by a single-mode tunable diode laser (TDL). Active cavity control by an ‘intensity dip’ method yields an optical bandwidth ≤0.005 cm^-1 (150 MHz), which compares favourably with the performance of advanced grating-tuned OPO/OPA systems. A novel adaptation of this TDL-seeded PPLN OPO employs a compact, inexpensive multimode pump laser, with which it is still possible to obtain continuously tunable single-mode signal output. Cavity ringdown (CRD) spectroscopy also figures prominently, with infrared (IR) CRD spectra from both grating-scanned and TDL-seeded OPOs reported. Finally, a tunable ultraviolet (UV) source, combining a TDL-seeded passive-cavity OPO and a sum-frequency generation stage, is developed for measurements of time-resolved IR-UV double resonance spectra of acetylene and UV laser-induced fluorescence spectra of nitric oxide. Received: 28 March 2000 / Published online: 13 September 2000     

Application of mid-infrared cavity-ringdown spectroscopy to trace explosives vapor detection using a broadly tunable (6–8 μm) optical parametric oscillator

A novel instrument, based on cavity-ringdown spectroscopy (CRDS), has been developed for trace gas detection. The new instrument utilizes a widely tunable optical parametric oscillator (OPO), which incorporates a zinc–germanium–phosphide (ZGP) crystal that is pumped at 2.8 μm by a 25-Hz Er,Cr:YSGG laser. The resultant mid-IR beam profile is nearly Gaussian, with energies exceeding 200 μJ/pulse between 6 and 8 μm, corresponding to a quantum conversion efficiency of approximately 35%. Vapor-phase mid-infrared spectra of common explosives (TNT, TATP, RDX, PETN and Tetryl) were acquired using the CRDS technique. Parts-per-billion concentration levels were readily detected with no sample preconcentration. A collection/flash-heating sequence was implemented in order to enhance detection limits for ambient air sampling. Detection limits as low as 75 ppt for TNT are expected, with similar concentration levels for the other explosives. Received: 1 April 2002 / Revised version: 13 June 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-408/524-0551, E-mail: mtodd@picarro.com     

Signal-to-noise enhancement techniques for quantum cascade absorption spectrometers employing optimal filtering and other approaches

Optical feedback to the laser source in tunable diode laser spectroscopy (TDLS) is known to create intensity modulation noise due to elatoning and optical feedback (i.e. multiplicative technical noise) that usually limits spectral signal-to-noise (S/N). The large technical noise often limits absorption spectroscopy to noise floors 100-fold greater than the Poisson shot noise limit due to fluctuations in the laser intensity. The high output powers generated from quantum cascade (QC) lasers, along with their high gain, makes these injection laser systems especially susceptible to technical noise. In this article we discuss a method of using optimal filtering to reduce technical noise. We have observed S/N enhancements ranging from ∼20% to a factor of ∼50. The degree to which optimal filtering enhances S/N depends on the similarity between the Fourier components of the technical noise and those of the signal, with lower S/N enhancements observed for more similar Fourier decompositions of the signal and technical noise. We also examine the linearity of optimal filtered spectra in both time and intensity. This was accomplished by creating a synthetic spectrum for the species being studied (CH₄, N₂O, CO₂ and H₂O in ambient air) utilizing line positions and linewidths with an assumed Voigt profile from a commercial database (HITRAN). Agreement better than 0.036% in wavenumber and 1.64% in intensity (up to a 260-fold intensity ratio employed) was observed. Our results suggest that rapid ex post facto digital optimal filtering can be used to enhance S/N for routine trace gas detection. Received: 1 April 2002 / Revised version: 7 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-509/376-6066, E-mail: robert.disselkamp@pnl.gov     

A pulsed optical parametric oscillator, based on periodically poled lithium niobate (PPLN), for high-resolution spectroscopy

-1 ), approaching the limit imposed by the Fourier transform of the pulse duration. Received: 31 August 1998     

Cavity-enhanced absorption spectroscopy with a rapidly swept diode laser

Cavity-enhanced absorption spectroscopy is explained in terms of the transmission function of a rapidly swept interferometer, and the integrated transmission is shown to be proportional to the cavity ringdown time. The technique is demonstrated on the b¹Σ_g ⁺-X³Σ_g ^-  (1,0) band in molecular oxygen at 687 nm using a tunable diode laser and a relative-ly high-Q optical cavity (finesse ≈4000). A detection limit of 3×10^-8 cm^-1 s^1/2 is achieved for a 0.8 cm^-1 scanning range. Received: 24 June 2002 / Revised version: 5 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: peverall@physchem.ox.ac.uk     

Atomic and molecular spectroscopy with a continuous-wave, doubly resonant, monolithic optical parametric oscillator

Doppler-broadened atomic and molecular spectra were observed with a one octave tunable, continuous-wave, doubly resonant, monolithic optical parametric oscillator (OPO) using 5% MgO-doped LiNbO₃ as a non-linear crystal with a birefringent phase-matching configuration. By tuning the frequency of a pump laser, longitudinal mode selection over 20 successive modes, corresponding to a 60 GHz span, was possible, owing to the simple structure of the monolithic OPO. Continuous frequency tuning was achieved using an external waveguide-type electrooptic phase modulator (EOM). By changing the modulation frequency of the EOM, frequency tuning of the optical sidebands over 12 GHz was possible, which is larger than the one free spectral range of the monolithic cavity of 3 GHz. We could observe the Cs-D₁ (894 nm), Cs-D₂ (852 nm), Rb-D₁ (795 nm), acetylene R9 (1520 nm) and P9 (1530 nm) transitions with the single monolithic OPO.     

Open-path trace gas detection of ammonia based on cavity-enhanced absorption spectroscopy

A compact open-path optical ammonia detector is developed. A tunable external-cavity diode laser operating at 1.5 μm is used to probe absorptions of ammonia via the cavity-enhanced absorption (CEA) technique. The detector is tested in a climate chamber. The sensitivity and linearity of this system are studied for ammonia and water at atmospheric pressure. A cluster of closely spaced rovibrational overtone and combination band transitions, observed as one broad absorption feature, is used for the detection of ammonia. On these molecular transitions a detection limit of 100 ppb (1 s) is determined. The ammonia measurements are calibrated independently with a chemiluminescence monitor. Compared to other optical open-path detection methods in the 1–2 μm region, the present result shows an improved sensitivity for contactless ammonia detection by over one order of magnitude. Using the same set-up, a detection limit of 100 ppm (1 s) is determined for the detection of water at atmospheric pressure. Received: 19 January 2000 / Revised version: 6 March 2000 / Published online: 7 June 2000     

Sensitive detection of ammonia and ethylene with a pulsed quantum cascade laser using intra and interpulse spectroscopic techniques

Spectroscopic concentration measurements of ammonia and ethylene were done with a pulsed, distributed feedback (DFB) quantum cascade (QC) laser centered at 970 cm⁻¹. An astigmatic Herriot cell with 150 m path length was employed, and we compare the results from experiments using inter- and intrapulse techniques, respectively. The measurements include the detection of ammonia in breath with these methodologies. In the interpulse technique, the laser was excited with short current pulses (5–10 ns), and the pulse amplitude was modulated with an external current ramp resulting in a ∼0.3 cm⁻¹ frequency scan. A standard amplitude demodulation technique was implemented for extracting the absorption line, thus avoiding the need for a fast digitizer or a gated integrator. In the intrapulse technique, a linear frequency down-chirp is used for sweeping across the absorption line. A 200 ns long current pulse was used for these measurements which resulted in a spectral window of ∼1.74 cm⁻¹ during the down-chirp. The use of a room temperature mercury-cadmium-telluride detector resulted in a completely cryogen free spectrometer. We demonstrate detection limits of ∼3 ppb for ammonia and ∼5 ppb for ethylene with less than 10 s averaging time with the intrapulse method and ∼4 ppb for ammonia and ∼7 ppb for ethylene with the interpulse technique with an integration time of ∼5 s.     

Remote sensing of volcanic gases with a DFB-laser-based fiber spectrometer

We demonstrate monitoring of H₂O and CO₂ emitted in a volcanic area, using a spectrometer equipped with two distributed feedback (DFB) semiconductor diode lasers. Each laser is resonant with a molecular species and is fiber-coupled to allow remote operation of the spectrometer. Recordings of H₂O and CO₂ lines made at the Solfatara volcano, in southern Italy, are shown, and the application of such a spectrometer as a new tool for the continuous monitoring and surveillance of volcanoes is discussed. Received: 28 June 1999 / Revised version: 20 December 1999 / Published online: 23 February 2000     

Cavity ring-down spectroscopy of molecularly thin iodine layers

Cavity ring-down spectroscopy (CRDS) has so far mostly been used for measurements in the gas phase. Only in 1999 was a first spectrum of condensed phase published. This spectrum was measured by using a coated plate between the cavity mirrors. Rather than using this method, our measurements were made using the cavity mirrors as a substrate. This way, the scattering losses could be reduced by approximately a factor of 100. In our measurements we investigated molecularly thin layers of iodine. The iodine spectra were taken in the frequency range from 16200 to 17200 cm^-1 using pulsed CRDS. Received: 14 April 2000 / Revised version: 26 July 2000 / Published online: 22 November 2000     

Tuning and stability of a continuous-wave mid-infrared high-power single resonant optical parametric oscillator

A 2.2-W continuous-wave, continuously tunable, single-frequency OPO has been developed in the 3.0–3.8 μm wavelength range for the detection of molecular trace gasses. The oscillation threshold, output power and stability of the single resonant OPO were improved by optimizing pump beam waist and OPO cavity length. Both air-spaced and solid etalons were tested to frequency stabilize and tune the OPO, from which the solid etalon gave a better performance. Temperature oscillations in the PPLN crystal caused oscillations in the idler wavelength of less than 200 MHz over 300 s; the short-term stability was less than 3 MHz over 1 s. The high laser power, in combination with photoacoustic spectroscopy, achieved a detection limit of 10 parts-per-trillion for ethane in nitrogen. Received: 9 April 2002 / Revised version: 14 June 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax:+31-24/3653311, E-Mail: maartenh@sci.kun.nl     

500-Hz two-photon Ramsey fringes with a SF6 beam: towards a new frequency standard in the 30-THz spectral region

A two-photon Ramsey-fringe experiment with a supersonic beam of SF₆ has been performed with an interzone distance of up to 50 cm. Using a He-seeded beam with 50% of SF₆, the two-photon transition P(4)E⁰ in the 2ν₃ band reveals its magnetic hyperfine structure and the periodicity of the fringes is 500 Hz. The strength of the central fringe of the main hyperfine component corresponds to a flux of 10¹⁰–10¹¹useful molecules/s, which is very promising for a new frequency standard in the 30-THz spectral region. Received: 27 April 2001 / Revised version: 18 June 2001 / Published online: 18 July 2001     

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     

Observation of iodine transitions using the second and third harmonics of a 1.5-μm laser

This paper presents spectroscopic measurements of iodine at 778 nm and 518 nm performed by second and third harmonics of a 1.5-μm diode laser, generated by quasi-phase matching in a periodically poled lithium niobate waveguide. Sub-Doppler spectroscopy by a 780-nm source was also demonstrated, and shows the potential of the system to reach high levels of frequency stability by locking the laser to the iodine transitions. The suggested method significantly improves the number of frequency references available for stabilizing 1550-nm lasers. Received: 4 February 2002 / Revised version: 14 May 2002 / Published online: 8 August 2002