- Laser absorption spectrometry
Laser absorption spectrometry (LAS) refers to techniques that utilize lasers to assess the concentration or amount of a species in gas phase by
It is well known that optical spectroscopic techniques in general and laser-based techniques in particular have a great potential for detection and monitoring of constituents in gas phase. They combine a number of important properties, e.g. a high sensitivity and a high selectivity with non-intrusive and remote sensing capabilities. Laser absorption spectrometry has become the foremost used technique for quantitative assessments of atoms and molecules in gas phase. It is also a widely used technique for a variety of other applications, e.g. within the field of optical frequency metrology or in studies of light matter interactions. The most common technique is
Tunable Diode Laser Absorption Spectrometry(TDLAS) which has become commercialized and is used for a variety of applications.
Direct Laser Absorption Spectrometry (DLAS)
The most appealing advantages of LAS is its ability to provide absolute quantitative assessments of species. [A. Fried and D. Richter: "Infrared absorption Spectroscopy", in "Analytical Techniques for Atmospheric Measurements" (Blackwell Publishing, 2006)] Its biggest disadvantage is that it relies on a measurement of a small change in power from a high level; any noise introduced by the light source or the transmission through the optical system will deteriorate the detectability of the technique. Direct laser absorption spectrometric (DLAS) techniques are therefore often limited to detection of absorbance ~10-3, which is far away from the theoretical shot noise level, which for a single pass DAS technique is in the 10-7 - 10-8 range. This detectability is insufficient for many types of applications.
There are basically three ways to improve on the situation:
# to reduce the noise;
# to address transitions with larger transitions strengths and
# to increase the interaction length; and. The first can be achieved by the use of a modulation technique; the second can be obtained by utilizing transitions in unconventional wavelength regions, whereas the third by using external cavities.
Modulated techniques – WMS and FMS – Tunable Diode Laser Absorption Spectrometry (TDLAS)
Modulation techniques make use of the fact that technical noise usually decreases with increasing frequency (often referred to as a 1/f noise) and improves on the signal contrast by encoding and detecting the absorption signal at a high frequency, where the noise level is low. The most common modulation techniques, wavelength modulation spectroscopy (WMS) [P. Kluczynski, J. Gustafsson, Å.M. Lindberg and O. Axner, Wavelength modulation absorption spectrometry - an extensive scrutiny of the generation of signals, "Spectrochimica Acta B" 56 1277-1354 (2001).] and frequency modulation spectroscopy (FMS), [G. C. Bjorklund, M. D. Levenson, W. Lenth, and C. Oritz, "Frequency Modulation (FM) Spectroscopy: theory of lineshapes and signal-to-noise analysis," "Appl. Phys. B" 32, 145-152 (1983).] achieve this by rapidly scanning the frequency of the light across the absorbing transition. Both techniques have the advantage that the demodulated signal is (ideally) zero in the absence of absorbers but they are also limited by residual amplitude modulation (RAM), either from the laser or from multiple reflections in the optical system (etalon effects). The most frequently used laser-based technique for environmental investigations and process control applications is based upon diode lasers and WMS and often referred to as
Tunable Diode Laser Absorption Spectroscopy(TDLAS). [D. T. Cassidy and J. Reid, "Atmospheric pressure monitoring of trace gases using tunable diode lasers," "Appl. Opt." 21 (7), 1185 - 1190 (1982).] [P. Werle, F. Slemr, K. Maurer, R. Kormann, R. Mucke, and B. Janker, "Near- and mid-infrared laser-optical sensors for gas analysis," "Opt. Las. Eng." 37 (2-3), 101-114 (2002).] The typical detectability of WMS and FMS techniques is in the 10-5 range.
Due to their good tunability and long lifetime (> 10 000 hours), most practical laser-based AS is today performed by distributed feedback (DFB) diode lasers. This gives rise to systems that can run unattended for thousands of hours, with a minimum of maintenance.
However, since these laser are mostly developed for the telecom industry, they emit in the near infrared (NIR) region, primarily in the 700 nm – 2 μm range. With light in this wavelength region, mostly only weak overtone transitions of molecules can be addressed. This limits the detectability of conventional TDLAS to detection of species down to the mid or high ppm m range (part-per-million concentrations times meter interaction lengths). This is still insufficient for a large range of applications, wherefore other actions have to be taken.
Laser absorption spectrometry utilizing fundamental vibrational or electronic transitions
The second way of improving the detectability of LAS is to employ transitions with larger linestrength, either in the fundamental vibrational band or electronic transitions. The former, which normally reside at ~5 μm, have linestrengths that are ~2-3 orders of magnitude higher than those of typical overtone transition. As an example, the figure ("to appear soon") shows the linestrengths for the second and first overtones in NO (at ~1.8 and 2.65 µm) as well as those for the fundamental vibrational transitions in the MIR region (around 5.3 µm). On the other hand, electronic transitions have often yet another 1-2 orders of magnitude larger linestrengths. The transitions strengths for the electronic transitions of NO, which are located in the UV range (at ~227 nm, not included in the figure) are ~2 orders of magnitude larger than those in the MIR region! If transitions with such large linestrengths can be used efficiently, a significant increase in detectability would result.
The recent development of quantum cascade lasers (QC) lasers working in the MIR region has opened up new possibilities for sensitive detection of molecular species on their fundamental vibrational bands. It is more difficult (although not impossible) to generate stable cw light addressing electronic transitions, since these often lie in the UV region. Despite the fact that transitions with larger transition strength can be reached by either MIR or UV emitting lasers, the limits of detection (LODs) of AS techniques utilizing these transitions have not yet been improved as much as has been anticipated. The reason is that these types of laser have a number of unique properties that limit their practical applicability. Their full potential can only be utilized whence these limitations have been circumvented. This is a rapidly developing but still only partly explored field of science that can help overcoming some of the present limitations of the AS technique.
Cavity Enhanced Absorption Spectrometry (CEAS)
The third way of improving the detectability of LAS is to extend the interaction length. This can be obtained by placing the species inside a cavity in which the light bounces back and forth many times, whereby the interaction length can be increased considerably. This has led to a group of techniques denoted as cavity enhanced AS (CEAS). The cavity can either be placed inside the laser, giving rise to intracavity AS, or outside, when it is referred to as an external cavity. Although the former technique can provide a high sensitivity, its practical applicability is limited because of all the non-linear processes involved.
External cavities can either be of multi-pass type, i.e. Herriott or White cells, or be of resonant type, most often working as a
Fabry-Perot(FP) etalon. Whereas the multi-pass cells typically can provide an enhanced interaction length of up to ~2 orders of magnitude, the resonant cavities can provide a much larger path length enhancement, in the order of the finesse of the cavity, "F", which for a balanced cavity with high reflecting mirrors with reflectivities of ~99.99-99.999% can be ~ 104 to 105. It should be clear that if all this increase in interaction length can be utilized efficiently, this vouches for a significant increase in detectability!
A problem with resonant cavities is though that a high finesse cavity has very narrow cavity modes, often in the low kHz range (the width of the cavity modes is given by FSR/F, where FSR is the free-spectral range of the cavity, which is given by "c"/2"L", where "c" is the speed of light and "L" is the cavity length). Since cw lasers often have free-running linewidths in the MHz range, and pulsed even larger, it is non-trivial to couple laser light effectively into a high finesse cavity. There are though a few ways this can be achieved.
Cavity Ring-Down Spectrometry (CRDS)
cavity ring-down spectrometry(CRDS) the mode-matching condition is circumvented by injecting a short light pulse in the cavity. The absorbance is assessed by comparing the cavity decay times of the pulse as it “leaks out” of the cavity on and off-resonance, respectively. While independent of laser amplitude noise, this technique is often limited by drifts in the system between two consecutive measurements and a low transmission through the cavity. Despite this, sensitivities in the ~10-7 range can routinely be obtained (although the most complex setups can reach below this). CRDS has therefore started to become a standard technique for sensitive trace gas analysis under a variety of conditions. [ B. A. Paldus and A. A. Kachanov, "An historical overview of cavity-enhanced methods," "Canadian Journal of Physics" 83 (10), 975-999 (2005).]
Integrated Cavity Output Spectroscopy (ICOS)
Integrated cavity output spectroscopy(ICOS) records the integrated absorption while the laser is repeatedly swept across one or several cavity modes. However, for high finesse cavities the ratio of “on” and “off” a cavity mode is small, given by the inverse of the finesse, whereby the transmission as well as the integrated absorption becomes small. Off-axis ICOS (OA-ICOS) improves on this by coupling the laser light into the cavity from an angle with respect to the main axis so as to interact with a high density of transverse modes, whose spacing is comparable to their widths. Although better than direct ICOS, the technique is, however, still limited by a low transmission and fluctuating incoupling efficiencies, and can again typically reach sensitivities ~10-7 (although again somewhat better results can be obtained using more complex systems).
Continuous wave Cavity Enhanced Absorption Spectrometry (cw-CEAS)
The group of CEAS techniques that has the largest potential to improve is that based on a continuous coupling of laser light into the cavity. This requires however an active locking the laser to one of the cavity modes. There are two ways in which this can be done, either by optical or electronic feedback,. Optical feedback (OF) locking, originally developed by Romanini et al. for cw-CRDS, [D. Romanini, A. A. Kachanav, J. Morville, and M. Chenevier, "Proc. SPIE EUROPTO (Ser. Environmental Sensing)" 3821 (8), 94 (1999)] utilizes the optical feedback from the cavity to lock the laser to the cavity while the laser is slowly scanned across the profile (OF-CEAS). In this case, the cavity needs to have a V-shape in order to avoid OF from the incoupling mirror. OF-CEAS is capable of reaching sensitivities ~10-8 range, limited by a fluctuating feedback efficiency. [J. Morville, S. Kassi, M. Chenevier, and D. Romanini, "Fast, low-noise, mode-by-mode, cavity-enhanced absorp-tion spectroscopy by diode-laser self-locking," "Applied Physics B-Lasers and Optics" 80 (8), 1027-1038 (2005] Electronic locking is usually realized with the Pound-Drever-Hall (PDH) technique, [R. W. P. Drever, J. L. Hall, F. V. Kowalski, J. Hough, G. M. Ford, A. J. Munley, and H. Ward, "Laser phase and frequency stabilization using an optical resonator," "Applied Physics B" 31 (2), 97-105 (1983] and is nowadays a well established technique, although it can be difficult to achieve for some types of lasers. [R. W. Fox, C. W. Oates, and L. W. Hollberg, "Stabilizing diode lasers to high finesse cavities," in Cavity-Enhanced Spectroscopies, R. D. van Zee and J. P. Looney, eds. (Elsevier Science, New York, 2002)] [J. L. Hall and T. W. Hansch, "External dye-laser frequency stabilizer," "Optics Letters" 9 (11), 502-504 (1984] It has been shown by that also electronically locked CEAS can be used for sensitive AS on overtone lines. [K. Nakagawa, T. Katsuda, A. S. Shelkovnikov, M. Delabachelerie, and M. Ohtsu, "Highly Sensitive Detection of Molecular Absorption Using a High Finesse Optical Cavity," "Optics Communications" 107 (5-6), 369-372 (1994)] [M. Delabachelerie, K. Nakagawa, and M. Ohtsu, "Ultranarrow (C2H2)-C-13 Saturated-Absorption Lines at 1.5 Mu-M," "Optics Letters" 19 (11), 840-842 (1994)] [G. Gagliardi, G. Rusciano, and L. Gianfrani, "Sub-Doppler spectroscopy of (H2O)-O-18 at 1.4 μm," "Applied Physics B-Lasers and Optics" 70 (6), 883-888 (2000)]
Noise-Immune Cavity-Enhanced Optical-Heterodyne Molecular Spectroscopy (NICE-OHMS)
However, all attempts to directly combine CEAS with a locking approach (DCEAS) have one thing in common; they do not manage to use the full power of the cavity, i.e. to reach LODs close to the (multi-pass) shot-noise level, which is roughly 2"F"/π times below that of DAS and can be down to ~10-13. The reason is two fold: (i) any remaining frequency noise of the laser relative to the cavity mode will, due to the narrow cavity mode, be directly converted to amplitude noise in the transmitted light, thereby impairing the detectability; and (ii) none of these techniques makes use of any modulation technique, wherefore they still suffers from the 1/f noise in the system. There is, however, one technique that so far has succeeded in making full use of the cavity by combining locked CEAS with FMS so as to circumvent both of these problems, and that is
Noise-Immune Cavity-Enhanced Optical-Heterodyne Molecular Spectroscopy( NICE-OHMS). The first and so far ultimate realization of this technique, performed for frequency standard applications, reached an astonishing LODs of 5•10-13 (1•10-14 cm-1). [L. S. Ma, J. Ye, P. Dube, and J. L. Hall, "Ultrasensitive frequency-modulation spectroscopy enhanced by a high-finesse optical cavity: theory and application to overtone transitions of C2H2 and C2HD," "Journal of the Optical Society of America B-Optical Physics" 16 (12), 2255-2268 (1999)] It is clear that this technique, correctly developed, has a larger potential than any other technique for trace gas analysis! [F. M. Schmidt, A. Foltynowicz, W. Ma, T. Lock, and O. Axner, "Doppler-broadened fiber-laser-based NICE-OHMS - Improved detectability," "Optics Express" 15 (17), 10822-10831 (2007).]
* Cavity Ring Down Spectroscopy (CRDS)
* Diode Lasers
Noise-Immune Cavity-Enhanced Optical-Heterodyne Molecular Spectroscopy( NICE-OHMS)
Tunable Diode Laser Absorption Spectroscopy
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