Cavity-enhanced absorption: detection of nitrogen dioxide and iodine monoxide using a violet laser diode

We present an application of cavity-enhanced absorption spectroscopy with an off-axis alignment of the cavity formed by two spherical mirrors and with time integration of the cavity-output intensity for detection of nitrogen dioxide (NO₂) and iodine monoxide (IO) radicals using a violet laser diode at λ=404.278 nm. A noise-equivalent (1σ≡ root-mean-square variation of the signal) fractional absorption for one optical pass of 4.5×10^-8 was demonstrated with a mirror reflectivity of ∼0.99925, a cavity length of 0.22 m and a lock-in-amplifier time constant of 3 s. Noise-equivalent detection sensitivities towards nitrogen dioxide of 1.8×10¹⁰ molecule cm^-3 and towards the IO radical of 3.3×10⁹ molecule cm^-3 were achieved in flow tubes with an inner diameter of 4 cm for a lock-in-amplifier time constant of 3 s. Alkyl peroxy radicals were detected using chemical titration with excess nitric oxide (RO₂+NO→RO+NO₂). Measurement of oxygen-atom concentrations was accomplished by determining the depletion of NO₂ in the reaction NO₂+O→NO+O₂. Noise-equivalent concentrations of alkyl peroxy radicals and oxygen atoms were 3×10¹⁰ molecule cm^-3 in the discharge-flow-tube experiments. Received: 4 February 2003 / Revised version: 10 March 2003 / Published online: 12 May 2003 RID="*" ID="*"Corresponding author. Fax: +44-1865/275-410, E-mail: vlk@physchem.ox.ac.uk     

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     

Wavelength-modulation spectroscopy using a frequency-doubled current-modulated diode laser

We have studied atomic absorption in an argon discharge by wavelength-modulation spectroscopy with a frequency-doubled diode laser. The tunable wavelength-modulated radiation at 430 nm was generated by frequency doubling a current-modulated 860-nm diode laser in a KNbO₃ crystal. 2f-, 4f- and 6f-harmonic spectra as a function of diode laser modulation depth were measured on a Doppler-broadened sample of excited argon atoms produced in a capacitively coupled plasma chamber. Characterisation of the harmonic signals was accomplished. Minimum detectable absorbances of 7.7×10^-5 and 1.9×10^-4 based on a 3σ criterion (σ being the standard deviation of the noise) were estimated for 2f- and 4f-harmonic detection of the frequency-doubled radiation with a time constant of 0.1 s. The concentrations of argon in the 1s₄ state were found to be in the range of 3×10⁸ to 1.2×10¹¹ cm^-3 for the experimental conditions studied. Received: 25 February 2002 / Revised version: 4 April 2002 / Published online: 14 May 2002     

All-diode-laser ultraviolet absorption spectroscopy for sulfur dioxide detection

Ultraviolet radiation around 302 nm was produced by sum-frequency generation in beta-barium borate employing a blue and a near-infrared diode laser. The diode-laser-based spectrometer has a mode-hop-free tuning range of 50 GHz and was used for high-resolution spectroscopic detection of sulfur dioxide. Differential measurements of several gas concentrations, at low pressure as well as at ambient atmospheric pressure, were demonstrated. The detection limit in the first implementation of the instrument was about 20 ppm m at atmospheric pressure, essentially limited by interference fringes. Methods for greatly improving this limit are suggested.     

Resonant photoacoustic simultaneous detection of methane and ethylene by means. of a 1.63-μm diode laser

A compact multi-component trace-gas detector based on the resonant photoacoustic technique and a NIR external cavity diode laser has been developed. It has been characterized using a mixture of ethylene and methane diluted in ambient air. A spectroscopic investigation of combination bands and overtones between 5900 and 6250 cm^-1, obtained with an IR pulsed laser photoacoustic spectrometer, allowed us to find a wavelength region where the 2ν₃ overtone of CH₄ and the ν₅+ν₉ combination band of C₂H₄ show uncongested rotational lines. Using a single-mode scan of the diode laser in this region, around 6150 cm^-1, the sensitivity for the simultaneous detection of ethylene and methane is 8 ppm/mW and 40 ppm/mW respectively. Factors affecting the sensitivity and selectivity of the detection system and possible improvements suitable to reach the sub-ppm detection limit are discussed. Received: 1 August 2001 / Revised version: 28 November 2001 / Published online: 7 February 2002 An erratum to this article is available at .     

Laser intracavity absorption spectroscopy

Emission spectra of multimode lasers are very sensitive to spectrally selective extinction in their cavity. This phenomenon allows the quantitative measurement of absorption. The sensitivity of measurements of intracavity absorption grows with the laser pulse duration. The ultimate sensitivity obtained with a cw laser is set by various perturbations of the light coherence, such as quantum noise, Rayleigh scattering, four-wave mixing by population pulsations, and stimulated Brillouin scattering. It depends on the particular laser type used, and on its operative parameters, for example pump power, cavity loss, cavity length, and length of the gain medium. Nonlinear mode-coupling dominates the dynamics of lasers that feature a thin gain medium, such as dye lasers, whereas Rayleigh scattering is more important in lasers with a long gain medium, such as doped fibre lasers, or the Ti:sapphire laser. The highest sensitivity so far has been obtained with a cw dye laser. It corresponds to 70000 km effective length of the absorption path. The ultimate spectral resolution is determined by the spectral width of mode emission, which is 0.7 Hz in this dye laser. High sensitivity and high temporal and spectral resolution allow various practical applications of laser intracavity spectroscopy, such as measurements and simulations of atmospheric absorption, molecular and atomic spectroscopy, process control, isotope separation, study of free radicals and chemical reactions, combustion diagnostics, spectroscopy of excited states and nonlinear processes, measurements of gain and of spectrally narrow light emission. Intracavity absorption in single-mode lasers shows enhanced sensitivity as well, although not as high as in multimode lasers. Received: 10 May 1999 / Published online: 29 July 1999     

Simultaneous detection of methane, oxygen and water vapour utilising near-infrared diode lasers in conjunction with difference-frequency generation

An all-diode-laser-based spectrometer is used for the simultaneous detection of methane, oxygen and water vapour. This is accomplished using a 760-nm diode laser and a 980-nm diode laser in conjunction with difference-frequency generation to 3.4 μm in a periodically poled lithium niobate crystal. Each of the output wavelengths is resonant with one of the molecular species. Simultaneous recordings over a 15-m open path of laboratory air are demonstrated. The recording scheme shows the wide applicability of a diode-laser-based difference-frequency spectrometer for the detection of molecular species in different wavelength ranges. By increasing the frequency of the 760-nm diode laser and decreasing the frequency of the 980-nm diode laser, a maximum continuous tuning range in the mid infrared of 3.6 cm^-1 is achieved. This enables the recording of several methane lines at atmospheric pressure. Pressure-dependence studies of methane lineshapes are also performed in an absorption cell. An indoor-air methane background level of 3 ppm is measured. The signal-to-noise ratio in the recorded methane spectra indicates that sub-ppm detection of methane at atmospheric pressure is feasible. Received: 6 March 2000 / Revised version: 19 June 2000 / Published online: 11 October 2000     

Intracavity photoacoustic gas detection with an external cavity diode laser

The first use of an external cavity diode-laser light source in combination with a photoacoustic detector for high-sensitivity gas detection is described. This combined system is applicable for detecting gases with absorption coefficients as low as 5 x 10^–8 cm^–1 by operating the photoacoustic cell in an intracavity mode. Measurements were made on the 1.13 m absorption lines of water vapour. For quantitative measurements, it was found to be necessary to introduce a reference cell into the system.     

Sensitive birefringence measurement in a high-finesse resonator using diode laser optical self-locking

We demonstrate a new method to measure weak birefringence of dielectric mirrors with excellent spatial resolution and sensitivity (<10^-7 radians). We exploit a well-known optical feedback scheme for line-width narrowing and frequency locking of a diode laser to a high-finesse cavity. Feedback comes from the intracavity field which builds up at resonance, selected by its change in polarization with respect to the incident field. This change, due to the residual birefringence of the cavity mirror coatings, was already exploited for birefringence measurements using an active laser-locking scheme. Here we measure the optical feedback rate as a function of rotation angle of one of the cavity mirrors (around the cavity axis). A stable feedback signal is obtained since the laser, as soon as it locks to a cavity resonance, effectively behaves as a monochromatic source. By fitting the data with a theoretical expression, we determine quantitatively the local birefringence vectors of both mirrors, which are around 10^-6 radians. Our scheme is simple, works with cavities of very high finesse (F∼10⁵), and is promising for measuring birefringence in gases induced by external fields. Received: 18 July 2001 / Final version: 14 March 2002 / Published online: 8 May 2002     

Pulsed cavity ring-down spectroscopy of NO and NO2 in the exhaust of a diesel engine

The application of pulsed cavity ring-down spectroscopy has been demonstrated for the in situ quantitative determination of NO and NO₂ in the exhaust of a diesel engine. NO absorption has been monitored at the transition from the Χ²Π ground state to the A²Σ⁺ state at 226 nm. For NO₂, absorption bands in the spectral region from 438 nm to 450 nm were used. At the selected engine conditions, concentrations of 212±22 ppm and 29±4 ppm have been measured for NO and NO₂, respectively, in good agreement with separate chemical exhaust gas analysis. The method is sensitive enough to meet the European Euro V standard directive on NO_x emissions. This communication discusses the relatively simple setup needed for this type of measurement, the problems encountered, as well as the prospects for single-stroke, simultaneous measurements of both NO and NO₂ at the sub-ppm level. Received: 30 November 2001 / Revised version: 18 February 2002 / Published online: 14 March 2002     

Spectroscopic trace-gas sensor with rapidly scanned wavelengths of a pulsed quantum cascade laser for in situ NO monitoring of industrial exhaust systems

Development of a pulsed quantum cascade laser (QCL)-based spectroscopic trace-gas sensor for sub-part-per-million detection of nitric oxide (NO) and capable of monitoring other molecular species such as CO₂, H₂O, and NH₃ in industrial combustion exhaust systems is reported. Rapid frequency modulation is applied to the QCL to minimize the influence of fluctuating non-selective absorption. A novel method utilizes only a few laser pulses within a single wavelength scan to probe an absorption spectrum at precisely selected optical frequencies. A high-temperature gas cell was used for laboratory evaluation of the NO sensor performance. A noise-equivalent sensitivity (1) of 100 ppb × m/ at room temperature and 200 ppb × m/ at 630 K was achieved by measuring the NO R(6.5) absorption doublet at 1900.075 cm^–1.     

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.     

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     

A tunable diode laser system for the remote sensing of on-road vehicle emissions

2 O, and NO₂ emissions have been measured with this instrument. The system is also capable of measuring CO, NH₃, H₂CO, CH₃OH, and other small molecules in vehicle exhaust. Received: 18 May 1998/Revised version: 1 July 1998     

Cavity ring-down spectroscopy for atmospheric trace gas detection: application to the nitrate radical (NO3)

Cavity ring-down spectroscopy is a relatively new and quite sensitive technique for the measurement of gas-phase optical extinction. It holds the potential for simple, direct and sensitive measurement of the concentrations of a variety of trace gases in the atmosphere. For example, detection of the nitrate radical, NO₃, and its companion, dinitrogen pentoxide, N₂O₅, has been demonstrated with a sensitivity of 0.25 pptv (1σ). This paper considers several of the requirements for the application of cavity ring-down spectroscopy to concentration measurements of trace gases in ambient air. These include detection sensitivity, measurement of an accurate zero in the presence of competing absorbers, cavity stability and mirror cleanliness, laser line-width effects, saturation effects, Rayleigh scattering, the influence of atmospheric aerosols and sampling issues for reactive species. Examples drawn from our work on NO₃ and N₂O₅ detection in the field illustrate these considerations. Received: 1 April 2002 / Revised version: 5 June 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-303/497-5822, E-mail: sbrown@al.noaa.gov     

Fast, low-noise, mode-by-mode, cavity-enhanced absorption spectroscopy by diode-laser self-locking

A new technique of cavity enhanced absorption spectroscopy is described. Molecular absorption spectra are obtained by recording the transmission maxima of the successive TEM_oo resonances of a high-finesse optical cavity when a Distributed Feedback Diode Laser is tuned across them. A noisy cavity output is usually observed in such a measurement since the resonances are spectrally narrower than the laser. We show that a folded (V-shaped) cavity can be used to obtain selective optical feedback from the intracavity field which builds up at resonance. This induces laser linewidth reduction and frequency locking. The linewidth narrowing eliminates the noisy cavity output, and allows measuring the maximum mode transmissions accurately. The frequency locking permits the laser to scan stepwise through the successive cavity modes. Frequency tuning is thus tightly optimized for cavity mode injection. Our setup for this technique of Optical-Feedback Cavity-Enhanced Absorption Spectroscopy (OF-CEAS) includes a 50 cm folded cavity with finesse ∼20 000 (ringdown time ∼20 μs) and allows recording spectra of up to 200 cavity modes (2 cm⁻¹) using 100 ms laser scans. We obtain a noise equivalent absorption coefficient of ∼5×10⁻¹⁰ cm⁻¹ for 1 s averaging over scans, with a dynamic range of four orders of magnitude.     

High efficiency second harmonic generation with a low power diode laser

\valunit{8}{mW} ( corrected for the output mirror reflection) of the cw coherent blue light around by frequency doubling of only from a diode laser. With IR power of we reach the doubling efficiency of . The overall conversion efficiency from the electrical power into the blue light is . By the way of careful analysis of the Blue Light Induced IR Absorption (BLIIRA) in the potassium niobate based external doubling cavity we obtain good agreement with the theoretical conversion efficiency. Received: 29 November 1996     

Detection of argon and krypton traces in noble gases by diode laser absorption spectrometry

Wavelength modulation, diode laser atomic absorption spectrometry is applied to measure traces of argon and krypton in other noble gases. Strong transitions from long-lived metastable levels highly populated in a low-pressure dc discharge are induced with a standard diode laser in the spectral range around 811 nm. The detection limits achieved are in the lower ppbv range, and the residual concentrations of Kr and Ar traces in the utilized high-purity noble gases are measured. Received: 2 October 2000 / Final version: 3 May 2001 / Published online: 7 June 2001     

Wide-bandwidth frequency locking of a 1083-nm extended-cavity DBR diode laser to a high-finesse Fabry–Pérot resonator

Received: 28 July 1997/Revised version: 27 November 1997     

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