Optical-feedback cavity-enhanced absorption spectroscopy with a quantum cascade laser

Optical-feedback cavity-enhanced absorption spectroscopy is demonstrated in the mid-IR by using a quantum cascade laser (emitting at 4.46 μm). The laser linewidth reduction and frequency locking by selective optical feedback from the resonant cavity field turns out to be particularly advantageous in this spectral range: It allows strong cavity transmission, which compensates for low light sensitivity, especially when using room-temperature detectors. We obtain a noise equivalent absorption coefficient of 3 × 10(-9)/cm for 1 s averaging of spectra composed by 100 independent points. At 4.46 μm, this yields a detection limit of 35 parts in 10(12) by volume for N(2)O at 50 mbar, corresponding to 4 × 10(7) molecules/cm(3), or still to 1 fmol in the sample volume.     

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     

Simultaneous cavity-enhanced and cavity ringdown absorption spectroscopy using optical feedback

We present a scheme of optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) including a fast optical switch to produce cavity ringdown spectra (OF-CRDS) simultaneously. This also works as a dynamically adjustable variable attenuator allowing to compensate for reduced signal levels in correspondence with absorption lines. For this, an acousto-optic deflector is used in a double-pass configuration to eliminate the single-pass frequency shift, which is incompatible with optical feedback. This is probably the most effective device providing the required fast response and the high extinction ratio necessary to perform clean ringdown measurements. The resulting direct comparison of OF-CEAS and OF-CRDS shows that these produce almost equivalent spectral data, with 0.3 % maximal difference at the top of an absorption line having a signal-to-noise ratio (S/N) of 3,300. OF-CEAS is largely winning on the short-term noise level while OF-CRDS appears to be more immune from interference fringes, delivering cleaner spectra after longer averaging.     

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     

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.     

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) in a ring cavity

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) has been demonstrated by coupling a distributed feedback diode laser to a ring cavity. Frequency-selected light decaying from the ring cavity is retro-reflected, inducing a counter-propagating intra-cavity beam, and providing optical feedback to the laser. At specific laser-to-cavity distances, all cavity mode frequencies return to the diode laser with the same phase, allowing spectra to be accumulated across the range of frequencies of the current-tuned laser. OF-CEAS has been used to measure very weak oxygen isotopologue (¹⁶O¹⁸O and ¹⁶O¹⁷O) absorptions in ambient air at wavelengths near 762 nm using the electric-dipole forbidden O₂ A-band. A bandwidth reduced minimum detectable absorption coefficient of 2.2×10⁻⁹ cm⁻¹ Hz^−1/2 is demonstrated.     

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     

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.     

Near-confocal cavity-enhanced Raman spectroscopy for multitrace-gas detection

Simultaneous detection of multitrace gas is still a challenge. Near-confocal cavity-enhanced Raman spectroscopy is proposed and demonstrated for simultaneous detection of multitracegas. With a 200 mW incident laser, the excitation power of >9 W forms at two foci of the near-confocal cavity owing to the beam being reflected 50 times. High-power excitation light greatly enhances the detection sensitivity of the Raman system. Using this cavity-enhancing technique, high-sensitivity detection of the mixture of eight gases with same volume ratio has been achieved. This technique may be applied for detecting multitrace gas in many areas.     

Sub-ppb NO2 detection by optical feedback cavity-enhanced absorption spectroscopy with a blue diode laser

We report preliminary results on the first application of optical feedback cavity-enhanced absorption spectroscopy with a blue (411 nm) extended cavity diode laser (ECDL) for NO₂ detection. While this technique was originally developed to operate with distributed feedback diode lasers in the near infrared, it is here extended to ECDLs and applied to the blue spectral region. With a simple and compact optical setup, we demonstrate from the baseline noise a minimum detectable NO₂ concentration of 6×10⁹ molecules/cm³ for a single laser scan (70 ms), which extrapolated under atmospheric conditions corresponds to 200 pptv. Signal averaging should allow further lowering of this limit. Observed absorption spectra display more structure than previous spectra obtained at lower resolution by Fourier-transform spectroscopy at the same wavelength. PACS 07.88.+y; 42.55.Px; 42.62.Fi     

Characterisation of the potential of frequency modulation and optical feedback locking for cavity-enhanced absorption spectroscopy

A combination of optical feedback self-locking of a continuous-wave distributed feedback diode laser to a V-shaped high finesse cavity, laser phase modulation at a frequency equal to the free spectral range of the V-cavity and detection of the transmitted laser beam at this high modulation frequency is described for the possible application in cavity-enhanced absorption spectroscopy. In order to estimate the noise level of an absorbance baseline, the triplet of frequency modulated light, i.e. the central laser frequency and the two sidebands, were transmitted through both the V-cavity in open air and a 1.5-cm long optical cell placed behind the cavity output mirror and filled with acetylene (C₂H₂) at low pressure. The performance of the setup was evaluated from the measured relative intensity noise on the cavity output (normalised by the bandwidth) and the frequency modulation absorption signals induced by C₂H₂ absorption in the 1.5-cm cell. From these data, we estimate that the noise-equivalent absorption sensitivity of 2.1 × 10^?11 cm^?1 Hz^?1/2—by a factor of 11.7 above the shot-noise limit—can be achieved for C₂H₂ absorption spectra extracted from the heterodyne beat signals recorded at the transmission maxima intensity peaks of the successive TEM₀₀ resonances.     

Effects of modulation on signals obtained in saturated absorption spectroscopy experiments

An analysis of the useful signals detected in saturated absorption spectroscopy experiments is given. Both Gaussian and plane-wave fields are considered. The various cases of unmodulated, square-wave modulated and sinusoidally modulated saturating beams are examined. It is found that square-wave and sinusoidal modulations give different results. The first is identical to no modulation, and detection at the fundamental frequency records a fraction of the total signal which is also a square wave. The second gives fundamental or higher-harmonic signals each with a very different dependence on the saturation parameter. The signal at the fundamental saturates faster and more completely than that for square-wave modulation. The results suggest experimental methods for the determination of the absolute value of the saturation parameter.     

The near infrared cavity-enhanced absorption spectrum of methyl cyanide

The absorption spectrum of methyl cyanide (CH₃CN) has been measured in the near IR between 6000 and 8000 cm^?1 with a resolution of 0.12 cm^?1 using Fourier transform incoherent broadband cavity-enhanced absorption spectroscopy. The spectrum contains several weakly perturbed spectral regions; potential vibrational combination bands contributing to the spectrum are outlined. Line positions and cross-sections of CH₃CN between 6814 and 7067 cm^?1 have been measured at high-resolution of 0.001 cm^?1 using diode laser based off-axis cavity-enhanced absorption spectroscopy. A total of 4630 new absorption lines of CH₃CN are identified in this region. A value for the self-broadening coefficient has determined to be (3.3±0.2)×10^?3 cm^?1 mbar^?1 for one isolated line at 7034.171 cm^?1. Several line series have been identified in these regions and an autocorrelation analysis performed with a view to aiding future assignments of the rotational-vibrational transitions.     

Lineshape effects in atomic absorption spectroscopy

Deviations from Beer's Law caused by the relative lineshape functions of source and absorber in atomic absorption experiments are considered. The validity of using a modified form of the law incorporating a correction factor γ, which is particularly convenient in time-resolved atomic absorption experiments, to account for these deviations, has been critically examined for a wide range of source and absorber lineshapes using numerical evaluation of the transmission integrals involved. It is concluded that there is, in general, no theoretical justification for the use of such a γ factor, except in the case of large source linewidth/absorber linewidth ratios when the line broadening in the absorber involves a significant homogeneous (Lorentzian) contribution. The use of empirically determined γ factors, much different from unity to analyse experimental data, should be viewed with suspicion unless direct evidence is presented to show that under the experimental conditions γ happens to be constant or slowly varying.     

Quantitative detection of singlet O2 by cavity-enhanced absorption

A method for the practical determination of the absolute concentration of single (a1delta(g)) oxygen is discussed. The method is based on sensitive off-axis integrated-cavity-output spectroscopy (ICOS). Off-axis ICOS allows narrowband, continuous-wave lasers to be used in conjunction with optical cavities to record sensitive absorption measurements. The details of the method as well as spectroscopic data confirming the first observation of the (1, 0) band of the b1sigma(g)(+) - a1delta(g) Noxon system are presented. The absolute transition probabilities for the b1sigma(g)(+) - a1delta(g) Noxon system, which are not known precisely from experiments, are determined by quantum chemistry theory.     

In situ measurements of atmospheric NO2 using incoherent broadband cavity-enhanced absorption spectroscopy with a blue light-emitting diode

We describe the application of incoherent broadband cavity-enhanced absorption spectroscopy(IBBCEAS) for in situ measurements of atmospheric NO2 using a blue light-emitting diode.The mirror reflectivity is determined by the transmitted intensity variation through the cavity caused by Rayleigh scattering.Concentrations of atmospheric NO2(1 to 35 ppbv) during the seven-day period are retrieved from the absorption spectra.The IBBCEAS measurement data are compared with those of a commercial long path differential optical absorption spectroscopy.The linear regression has a correlation coefficient and a slope     

Characterization of lineshape structure by wavelength modulation spectroscopy

Wavelength Modulation Spectroscopy (WMS) is performed in the oxygen A-band at different harmonics for different modulation indices and optical pathlengths. The experimental data is compared to two models with different absorption profiles: one assuming a Lorentzian lineshape function and the other with a Voigt lineshape function. We show that the larger amount of structure in higher harmonic signals provides greater sensitivity to the type of lineshape profile utilized for modeling. A useful new feature explored in this work is optical path length saturation in WMS that was described for the first time in a recent paper from our group. We discuss the role of such saturation and how it can be utilized as a diagnostic to probe lineshape. We also address the effect of the ever present modulation broadening. Results of experiments in which sets of nine scans (direct absorption, 1f, 2f,??,8f; i.e., detection harmonic N=0,1,2,3,??,8) were made simultaneously are described and discussed. Finally, the role that increased structure plays??as a result of increasing order of detection, N, as well as from the modification of the signal profile with increasing optical thickness??is outlined from the perspective of classical information theory.