Metrological use of intracavity laser spectroscopy

Measurement Techniques -     

Trace methane gas detection by wavelength modulated off-axis integrated cavity output spectroscopy

An instrument based on wavelength modulation off-axis integrated cavity output spectroscopy (WM-OA-ICOS) was developed for detection of trace methane (CH₄) gas. The wavelength modulation technique was employed to obtain the second harmonic of the CH₄ absorption signal. The modulation parameters were optimized to obtain a maximum second harmonic signal. A noise-equivalent absorption sensitivity of 9.4 × 10^?11 cm^?1 Hz^?1/2 (corresponding to a detection limit of 28.9 ppbv for CH₄ at this wavelength) was achieved using 2f detection. Compared with the traditional off-axis integrated cavity output spectroscopy (OA-ICOS) technique, WM-OA-ICOS provided an 8-fold improvement in detection sensitivity. CH4 concentration measurements were also achieved by normalization of second harmonic signal to first harmonic signal (2f/1f). The dynamic range and linearity of WM-OA-ICOS for both 2f method and 2f/1f method were investigated. The result showed that the 2f/1f method exhibited better linearity than 2f method.     

Wavelet denoising for infrared laser spectroscopy and gas detection

After a brief introduction to wavelet theory, this paper discusses the critical parameters to be considered in wavelet denoising for infrared laser spectroscopy. In particular, it is shown that measurement dispersion as well as sensibility can be dramatically improved when using wavelet denoising for gas detection by infrared laser absorption spectroscopy.     

Visible intracavity laser spectroscopy with a step-scan Fourier-transform interferometer

A Fourier-transform spectrometer has been used in a step-scan mode to make time-resolved measurements of the evolving laser pulse in intracavity laser spectroscopy (ILS) experiments. Spectra of broadband dye laser pulses at approximately 615 nm were recorded at relatively high spectral (0.5-cm(-1)) and temporal (as high as 5-mus) resolution. In the absence of an absorber, the height of the pulse is shown to be proportional to t(g)(0.57) (where t(g) is the generation time) for generation times as high as 500 mus. The system was constructed for feasibility studies of future use at infrared and near-infrared wavelengths where conventional ILS that uses diode arrays would be either expensive or simply not possible. The CH(4) overtone transition at 619.68 nm was used to test the linearity and sensitivity of the system. Comparable performance to conventional ILS systems was demonstrated, as were the advantages of the present system for studies of laser and absorption dynamics.     

Infrared intracavity laser absorption spectroscopy with a continuous-scan Fourier-transform interferometer

High-quality broadband infrared high-resolution spectra were obtained by use of the intracavity laser absorption spectroscopy technique with a Ti:sapphire laser in combination with a continuous-scan Fourier-transform (FT) interferometer. With electronic filtering used to smooth out the fluctuations of the laser power, the absorption of atmospheric water vapor in the range of 12,450-12,700 cm(-1) was recorded at a resolution of 0.05 cm(-1). A signal-to-noise ratio of greater than 300 was observed in this spectrum, corresponding to a minimum detectable absorption of approximately 2 x 10(-9) cm(-1). Comparison with previous measurements by use of a conventional FT technique shows that this method gives absorption spectra with highly accurate line positions along with reasonable line intensities. Investigation of the evolution of intracavity laser absorption spectra with the generation time is also shown to be possible with a continuous-scan FT spectrometer by use of the interleave rapid-scan method.     

Trace detection of explosives with low vapor emissions by laser surface photofragmentation-fragment detection spectroscopy with an improved ionization probe

Trace explosive residues are measured in real time by surface laser photofragmentation-fragment detection (SPF-FD) spectroscopy at ambient conditions. A 248-nm laser photofragments the target residue on a substrate, and a 226-nm laser ionizes the resulting NO fragment by resonance-enhanced multiphoton ionization by means of its A-X (0, 0) transitions near 226 nm. We tested two probes on selected explosives and modeled their electric field in the presence of a substrate with an ion optics simulation program. The limits of detection range from 1 to 15 ng/cm2 (signal-to-noise ratio of 3) at 1 atm and 298 K and depend on the electrode orientation and mechanism for NO formation.     

Ammonia detection by using quantum-cascade laser photoacoustic spectroscopy

A pulsed quantum-cascade distributed-feedback laser, temperature tunable from -41 degrees C to +31.6 degrees C, and a resonant differential photoacoustic detector are used to measure trace-gas concentrations to as low as 66 parts per 10(9) by volume (ppbv) ammonia at a low laser power of 2 mW. Good agreement between the experimental spectrum and the simulated HITRAN spectrum of NH3 is found in the spectral range between 1046 and 1052 cm(-1). A detection limit of 30 ppbv ammonia at a signal-to-noise ratio of 1 was obtained with the quantum-cascade laser (QCL) photoacoustic (PA) setup. Concentration changes of approximately 50 ppbv were detectable with this compact and versatile QCL-based PA detection system. The performance of the PA detector, characterized by the product of the incident laser power and the minimum detectable absorption coefficient, was 4.7 x 10-9 W cm(-1).     

Real-time, ultralow concentration detection of analytes in solution by infrared intracavity laser absorption

Two intracavity laser absorption techniques for ultralow concentration detection of chemicals in solution are compared. The first consists of a laser diode in a grating extended cavity, which produces a linear calibration curve for parts in 10(9) (ppb) concentrations corresponding to 17 nM. By replacing the grating with a highly reflective mirror, parts in 10(12) (ppt) concentration detection is achieved, which corresponds to 340 pM. We report, to our knowledge for the first time, ppt detection of analyte concentration in liquid solution demonstrating good agreement between theory and experiment.     

Helium detection in gas mixtures by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) has been evaluated as a tool for monitoring trace levels of helium in gas mixtures consisting mostly of hydrogen. Calibration data for helium in hydrogen was investigated at different helium concentration levels. At high concentrations of helium (>7.25%), the LIBS signal is quenched due to Penning ionization. The hydrogen alpha line (656.28 nm) was observed to broaden as the concentration of helium impurities in the hydrogen gas mixture increased. The helium line at 587.56 nm was selected as the analyte line for helium impurity detection. The effects of laser energy, the delay time between the laser pulse and data acquisition, and the gas pressure on the LIBS signal of helium were investigated to determine the optimum conditions for helium detection. The LIBS signal from the helium line at 587.56 nm shows good linear correlation with helium concentration for He concentrations below 1%. Thus, LIBS can be reliably used to detect the low levels of helium. The limit of detection for helium was found to be 78 ppm.     

Mid-infrared photothermal heterodyne spectroscopy in a liquid crystal using a quantum cascade laser

We report a technique to measure the mid-infrared photothermal response induced by a tunable quantum cascade laser in the neat liquid crystal 4-octyl-4'-cyanobiphenyl (8CB), without any intercalated dye. Heterodyne detection using a Ti:sapphire laser of the response in the solid, smectic, nematic and isotropic liquid crystal phases allows direct detection of a weak mid-infrared normal mode absorption using an inexpensive photodetector. At high pump power in the nematic phase, we observe an interesting peak splitting in the photothermal response. Tunable lasers that can access still stronger modes will facilitate photothermal heterodyne mid-infrared vibrational spectroscopy.     

Trace moisture detection using continuous-wave cavity ring-down spectroscopy

We have developed an instrument to measure trace concentrations of small hydride species in gases using continuous-wave cavity ring-down spectroscopy with near-infrared diode laser excitation. An rms baseline equivalent absorbance of 9.2 x 10(-11) cm(-1)/square root(n) is found, where n is the number of ring-down transients. When the 1396.376-nm absorption line of water is used, this corresponds to a noise equivalent moisture concentration in nitrogen gas of 68 pptv/square root(n). Water vapor concentration is detected over a range extending from 3 to 1000 ppbv and found to depend linearly on the concentration as determined by a calibrated commercial moisture sensor.     

Gas detection by correlation spectroscopy employing a multimode diode laser

A gas sensor based on the gas-correlation technique has been developed using a multimode diode laser (MDL) in a dual-beam detection scheme. Measurement of CO(2) mixed with CO as an interfering gas is successfully demonstrated using a 1570 nm tunable MDL. Despite overlapping absorption spectra and occasional mode hops, the interfering signals can be effectively excluded by a statistical procedure including correlation analysis and outlier identification. The gas concentration is retrieved from several pair-correlated signals by a linear-regression scheme, yielding a reliable and accurate measurement. This demonstrates the utility of the unsophisticated MDLs as novel light sources for gas detection applications.     

Quasi-phase-matched intracavity laser frequency summation

The work presents a theoretical analysis of quasi-phase-matched intracavity interaction in the constant-intensity approximation at frequencies summing with simultaneous regard for the losses and phases of interacting waves. An analytical expression for optimum correlation between interacting waves has been received. It is shown that, by the choice of optimum values of phase mismatch, pump intensity, and phase relationship, it is possible considerably to increase conversion efficiency in comparison with the noncavity case. The numerical estimation of expected conversion efficacy in conditions of an experiment is presented.     

Multiline absorption spectroscopy for methane gas detection

A multiline absorption spectroscopy technique was investigated based on the single-line absorption spectroscopy technique. An open-path methane-detecting system was designed. An LED was used as a broadband source, and a Fabry-Perot interferometer whose transmission peaks matched the methane R-branch absorption lines was used to enhance the detectable sensitivity. We demonstrate a minimum-detectable concentration of 7600 +/- 10% ppm (parts per million) with a multiline differential absorption spectroscopy technique and a concentration of 1000 +/- 10% ppm with a multiline wavelength modulation spectroscopy technique.     

Detection of photothermal effect by laser speckle strain gauge

A new method for simple and sensitive detection of photothermal strain caused by laser irradiation of plastic plates has been proposed. In-plane strain of the surface is detected directly by optoelectronic detection of speckle displacements at two symmetrical positions about a probe beam. The initial bending of the plate owing to the temperature gradient along the plate thickness is measured and shows good agreement with one-dimensional calculations.