Deep-ultraviolet cavity ringdown spectroscopy

The sensitive optical detection technique of cavity ringdown spectroscopy is extended to the wavelength range 197-204 nm. A novel design narrowband Fourier-transform-limited laser is used, and the technique is applied to gas-phase extinction measurements in CO2, SF6, and O2. Further demonstration of the system capabilities is given in high-resolution recordings of the Schumann-Runge (0, 0), (1,0), and (2, 0) bands in O2.     

Frequency-switched heterodyne cavity ringdown spectroscopy

When the frequency of light coupled into a cavity is suddenly shifted, the radiation emanating from the input port of the previously excited cavity can beat with the reflection of the frequency-shifted input on the surface of a photodetector. When the beat frequency is stable, the time decay of the resulting optical heterodyne signal can be used to measure intracavity absorption spectra with near quantum-limited sensitivity.     

Two schemes for trace detection using cavity ringdown spectroscopy

We describe and compare two schemes of high-sensitivity cavity ringdown spectroscopy (CRDS), both functioning with telecom diode lasers. The first (cw-CRDS) gives high spectral resolution, which is useful for low-pressure trace detection or for laboratory spectroscopy applications. We present a compact prototype partly based on fiber technology. The second scheme exploits optical feedback (of-CRDS) and results in a much simpler setup, more appropriate for realizing low-cost trace-detection devices. PACS 42.62.Fi; 87.64.Ni; 42.68.Ca; 82.80.Gk     

Bending loss measurement using a fiber cavity ringdown scheme

A novel sensitive technique for the determination of losses in fiber cavities is presented. The method is based on the cavity ringdown scheme implemented in silica-based single-mode fibers. Bending losses of fiber cavities of different lengths have been measured showing all an oscillating behavior with respect to the curvature radius of the fiber as predicted by a theoretical model. The best minimum detectable absorbance per cavity pass achieved by this new method is 1.72×10⁻³ dB within a 10 m-long cavity. This limit suffices well for an accurate determination of optical bending losses even in bend-insensitive fibers. Furthermore, the comparison of the measured bending losses with a theoretical model allows the extraction of different fiber parameters. Good agreement has been found between the experimentally derived parameters and literature data.     

Velocity measurements by cavity ringdown spectroscopy

We demonstrate velocity measurements of gas-phase particles by using cavity ringdown spectroscopy (CRDS). Velocity information is inferred from the Doppler-shift contributions to the measured absorption line shape. Because in CRDS the laser beam propagates back and forth within the optical cavity, a measured absorption feature is both upshifted and downshifted; i.e., it is split by the velocity component parallel to the optical axis. The splitting of the absorption features allows direct velocity measurements to be made without requiring an external frequency reference. The CRDS velocity measurement approach is demonstrated for sputtered molybdenum atoms in a low-pressure (collisionless) environment.     

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.     

High-precision pressure shifting measurement technique using frequency-stabilized cavity ring-down spectroscopy

We describe a high-precision method for measuring pressure shifting of absorption lines. The technique involves the acquisition of high-resolution spectra using a cavity ring-down spectrometer whose length is continuously locked to a frequency-stabilized reference laser over a range of sample pressures. We discuss a relatively large correction arising from the pressure-dependence of dispersion in the cavity modes, and we demonstrate pressure shifting measurements in air for transitions in the ¹⁶O₂A-band. Pressure shifts in the range -0.011 to are reported. We measured relative positions of line centers to within 70 kHz and determined pressure shifting coefficients over a 5 kPa pressure range with relative uncertainties approximately equal to 1.0%, which constitutes a five-fold improvement over previous measurements.     

Mode-by-mode optical feedback: cavity ringdown spectroscopy

We describe a new continuous wave cavity ringdown spectroscopy (cw-CRDS) approach using an extended cavity diode laser (ECDL) optically self-locked to a high finesse cavity including an intracavity glass plate under the Brewster angle. Low noise, mode-by-mode absorption spectra are recorded at a high acquisition rate (laser frequency scan greater than 400 GHz/s) and covering four orders of magnitude in absorption coefficient. Sampling spectra with the fixed high finesse cavity frequency comb provides high precision frequency markers. An original scheme for the laser beam shut-down, based on signal shape analysis and the diode laser injection current control, is presented. This scheme avoids any supplementary switching device. To retrieve ringdown processing at a kilohertz rate several exponential decay fit algorithms are compared. Performances of this new scheme are demonstrated with the observation of very weak lines of the oxygen B-band around 680 nm. Atmospheric spectra of isolated lines averaged for less than 10 s show a baseline noise of 5×10^-10 cm^-1 and a single point minimum detectable absorption loss over a one-second measurement interval of 2×10^-10 cm/ is obtained. PACS 07.88.+y; 42.55.Px; 42.62.Fi     

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     

Measurement of CrO in flames by cavity ringdown spectroscopy

CrO is an important intermediate in the high temperature oxidation chemistry of chromium containing species. This work reports the first detection of CrO in a flame. The B⁵-X⁵ electronic transition was probed by cavity ringdown spectroscopy (CRDS) in a lean (=0.38), low-pressure, flat, laminar hydrogen-oxygen-argon flame seeded with Cr(CO)₆. The previous B⁵-X⁵ CrO spectrum of Hocking et al. (605.0 nm-606.5 nm) is extended from the band head located at 605.6 nm to 614.4 nm. The temperature profiles of the doped and undoped flames were obtained from measurements of OH laser- induced fluorescence. Seeding the flame with Cr(CO)₆ increased the flame temperature by approximately 150 K. The concentration profile of CrO was measured as a function of height above the burner. CrO absorption signals were converted to concentration using the measured temperature profile and absorption cross-section calculated from lifetimes by Hedgecock et al. A lower limit peak CrO concentration of 1.6 ppb was found in the flame. Some uncertainty in the cross-section remains. Comparisons to calculations using STANJAN indicate that CrO is present in flames at super equilibrium concentrations. PACS 82.33.Vx; 42.62.Fi     

Cavity ringdown spectroscopy using mid-infrared quantum-cascade lasers

Cavity ringdown spectra of ammonia at 10 parts in 10(9) by volume (ppbv) and higher concentrations were recorded by use of a 16-mW continuous-wave quantum-casacde distributed-feedback laser at 8.5 mum whose wavelength was continuously temperature tuned over 15 nm. A sensitivity (noise-equivalent absorbance) of 3.4x10(-9) cm(-1) Hz(-1/2) was achieved for ammonia in nitrogen at standard temperature and pressure, which corresponds to a detection limit of 0.25 ppbv.     

Rapid measurement of cavity ringdown absorption spectra with a swept-frequency laser

A novel cavity ringdown spectrometer, incorporating a miniature continuous-wave swept-frequency laser that is widely tunable, requires less than 1 s to record wide-ranging absorption spectra with high sensitivity in a single rapid sweep of the laser frequency. The free spectral range of the ringdown cavity defines a sampling grid to measure absorbance-dependent ringdown times at successive cavity-resonance frequencies. The spectrometer has a single-ended transmitter-receiver configuration based on retro-reflected optical-heterodyne detection and exploiting fibre-optical telecommunications components. This swept-frequency approach to cavity ringdown spectroscopy yields a simple, low-cost, compact, rugged, versatile instrument for efficient sensing of gases. The performance of the spectrometer is demonstrated by measuring weak near-infrared rovibrational spectra of carbon dioxide gas within the 1.5–1.6 m wavelength range. PACS 42.62.Fi; 07.57.Ty; 07.07.Df     

Near-infrared laser based cavity ringdown spectroscopy for applications in petrochemical industry

A simple, economic diode laser based cavity ringdown system for trace-gas applications in the petrochemical industry is presented. As acetylene (C₂H₂) is sometimes present as an interfering contaminant in the gas flow of ethylene (ethene, C₂H₄) in a polyethylene production process, an on-line monitoring of such traces is essential. We investigated C₂H₂–C₂H₄ mixtures in a gas-flow configuration in real time. The experimental setup consists of a near-infrared external cavity diode laser with an output power of a few mW, standard telecommunication fibers and a home-made gas cell providing a user-friendly cavity alignment. A noise-equivalent detection sensitivity of 4.5×10^-8 cm^-1 Hz^-1/2 was achieved, corresponding to a detection limit of 20 ppbV C₂H₂ in synthetic air at 100 mbar. In an actual C₂H₂–C₂H₄ gas-flow measurement the minimum detectable concentration of C₂H₂ added to the C₂H₄ gas stream (which may already contain an unknown C₂H₂ contamination) increased to 160 ppbV. Moreover, stepwise C₂H₂ concentration increments of 500 ppbV were resolved with a 1-min time resolution and an excellent linear relationship between the absorption coefficient and the concentration was found. PACS 07.07.Df; 42.62.Fi; 82.80.Gk     

Theoretical analysis on the dynamic absorption saturation in pulsed cavity ringdown spectroscopy

We perform a theoretical analysis on the transient dynamics of absorption saturation in pulsed cavity ringdown spectroscopy. Based on a coupled rate equation approach, modelling of the dynamic saturation is carried out to account for time-evolving intracavity photon density and absorbing population. Master equations are derived in terms of normalized system parameters, which enables one to systematically study the non-exponential feature of saturated cavity ringdown signals. Erroneous quantification of sample absorbance by the conventional ringdown time analysis is numerically simulated, and the saturated spectral feature showing a Lamb dip is obtained for a Doppler broadened sample. Finally a novel numerical recipe is proposed to handle saturated ringdown signals and retrieve unsaturated spectra, allowing relevant absorption parameters without degrading the measurement signal-to-noise ratio. PACS PACS 42.62.Fi; 42.60.Da     

Infrared cavity ringdown laser absorption spectroscopy (IR-CRLAS) in low pressure flames

-5 fractional absorption) and generality of IR-CRLAS for combustion studies is demonstrated for low pressure laminar flames and is shown to be robust even in sooting environments with high temperature gradients. The ability to obtain (1-D) spatially resolved spectra of both reactants and products within a narrow spectral region is also demonstrated. In these initial flame studies, two information rich mid-infrared spectral regions are probed at Doppler-limited resolution, centered about 1.5 μm and 3.3 μm. Received: 30 August 1996     

A study of OH radicals in an atmospheric AC discharge plasma using near infrared diode laser cavity ringdown spectroscopy combined with optical emission spectroscopy

Simultaneous measurements of absolute concentrations of H₂O and OH radicals in an atmospheric AC discharge using continuous wave cavity ringdown spectroscopy (cw-CRDS) are reported. Formation of OH radicals and plasma temperatures are characterized by optical emission spectroscopy. The concentration of OH radical at the edge of the discharge plume at 380 K is measured by the cw-CRDS technique to be 1.1 ×10¹⁵ molecule cm^-3. Ringdown measurements of the H₂O (120-000) band and the OH first overtone around 1515 nm enable us to determine an OH generation yield, , to be 4.8 ×10^-3, where N_OH and are the number densities of OH and H₂O, respectively. The minimum detectable absorption coefficient of the cw-CRDS system is 8.9 ×10^-9  cm^-1, which corresponds to a 1σ detection limit of OH number density of 1.2 ×10¹³ molecule cm^-3 in the discharge. This experimental approach is demonstrated for the first time ever in an AC discharge, and can be applied in general to a variety of atmospheric plasmas to help study OH formation mechanisms and OH-related plasma applications.     

Theoretical investigation on the intracavity Doppler effect in continuous wave swept-cavity ringdown spectroscopy

We theoretically investigate the spectral measurement errors that are apt to occur in continuous wave (CW) cavity ringdown (CRD) techniques suffering intracavity Doppler shifts. In the typical CW CRD scheme based on a cavity sweep operation for the resonant coupling of a probe laser into a ringdown cavity, the intracavity probe light detunes gradually over time, carrying time-dependent loss information of an absorption feature. Frequency-drifting ringdown signals are theoretically modelled and found to result in erroneous absorption spectra that exhibit the frequency shift of absorption profiles as well as linewidth broadening. PACS 42.62.Fi; 42.60.Da; 42.25.BS     

Detection of trace gases by rapidly-swept continuous-wave cavity ringdown spectroscopy: pushing the limits of sensitivity

Cavity ringdown (CRD) absorption spectroscopy enables spectroscopic sensing of gases with a high sensitivity and accuracy. Instrumental improvements result in a new high-performance continuous-wave (cw) CRD spectrometer using a rapidly-swept cavity of simple design. It employs efficient data-acquisition procedures, high-reflectivity mirrors, a low-adsorption flow cell, and various compact fibre-optical components in a single-ended transmitter-receiver configuration suitable for remote sensing. Baseline noise levels in our latest cw-CRD experiments yield a competitive noise-equivalent absorption limit of ∼5×10^-10 cm^-1Hz^-1/2, independent of whatever molecules are to be detected. Measurements in the near-infrared wavelength range of 1.51–1.56 μm yield sub-ppmv (i.e., ppbv or better) sensitivity in the gas phase for several representative molecules (notably CO₂, CO, H₂O, NH₃, C₂H₂, and other hydrocarbons). By measuring spectroscopic features in the 1.525 μm band of C₂H₂ gas, we realise detection limits of 19 nTorr (2.5×10^-11 atm) of neat C₂H₂ (Doppler-limited at low pressure) and 0.37 ppbv of C₂H₂ in air (pressure-broadened at 1 atm). Our cw-CRD spectrometer is a high-performance sensor in a relatively simple, low-cost, compact instrument that is amenable to chemical analysis of trace gases in medicine, agriculture, industry, and the environment. PACS 07.07.Df; 07.57.Ty; 42.62.Fi     

Optical absorption spectrum of gold atoms deposited on SiO(2) from cavity ringdown spectroscopy

The optical properties of gold atoms supported on amorphous silica (alpha-SiO2) were studied experimentally and theoretically in the visible range. Samples were prepared in situ by depositing Au atoms at low coverages (5 x 10(12) cm(-2)) in UHV, and the optical absorption spectra were recorded by cavity ringdown spectroscopy. The atomic absorption bands can be attributed to gold atoms trapped at [triple bond] Si-O(.-) and [triple bond]Si-O(-) defect sites. The absence of optical transitions typical for Au(2) shows that the atoms are efficiently anchored at these defect sites, preventing diffusion and aggregation. Furthermore, these experimental results reveal that it is now possible to study optical properties of well-defined nanostructures at surface coverages as low as 5 x 10(11) cm(-2).