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'''Laser absorption spectrometry''' ('''LAS''') refers to techniques that use lasers to assess the concentration or amount of a species in gas phase by [[absorption spectrometry]] (AS).
'''Laser absorption spectrometry''' ('''LAS''') refers to techniques that use [[laser]]s to assess the concentration or amount of a [[species]] in gas phase by [[absorption spectrometry]] (AS).


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 spectroscopy]] (TDLAS) which has become commercialized and is used for a variety of applications.
[[Spectroscopy|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 spectroscopy]] (TDLAS) which has become commercialized and is used for a variety of applications.


== Direct laser absorption spectrometry ==
== Direct laser absorption spectrometry ==
The most appealing advantages of LAS is its ability to provide absolute quantitative assessments of species.<ref>A. Fried and D. Richter: ''Infrared absorption Spectroscopy'', in ''Analytical Techniques for Atmospheric Measurements'' (Blackwell Publishing, 2006)</ref> 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 sensitivity of the technique. Direct laser absorption spectrometric (DLAS) techniques are therefore often limited to detection of absorbance ~10<sup>−3</sup>, which is far away from the theoretical shot noise level, which for a single pass DAS technique is in the 10<sup>−7</sup> – 10<sup>−8</sup> range. This detection limit is insufficient for many types of applications.
The most appealing advantages of LAS is its ability to provide absolute [[Quantitative research|quantitative assessments]] of species.<ref>A. Fried and D. Richter: ''Infrared absorption Spectroscopy'', in ''Analytical Techniques for Atmospheric Measurements'' (Blackwell Publishing, 2006)</ref> 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 sensitivity of the technique. Direct laser absorption spectrometric (DLAS) techniques are therefore often limited to detection of absorbance ~10<sup>−3</sup>, which is far away from the theoretical [[shot noise]] level, which for a single pass DAS technique is in the 10<sup>−7</sup> – 10<sup>−8</sup> range. This detection limit is insufficient for many types of applications.


The detection limit can be improved by 1) reducing the noise, 2) using transitions with larger transitions strengths or 3) increasing the effective path length. The first can be achieved by the use of a modulation technique, the second can be obtained by using transitions in unconventional wavelength regions, whereas the third by using external cavities.
The detection limit can be improved by (1) reducing the noise, (2) using transitions with larger transition strengths or (3) increasing the effective path length. The first can be achieved by the use of a [[modulation]] technique, the second can be obtained by using transitions in unconventional [[wavelength]] regions, whereas the third by using external cavities.


== Modulated techniques ==
== Modulated techniques ==
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)<ref name="KluczynskiGustafsson2001">{{cite journal|last1=Kluczynski|first1=Pawel|last2=Gustafsson|first2=Jörgen|last3=Lindberg|first3=Åsa M.|last4=Axner|first4=Ove|title=Wavelength modulation absorption spectrometry — an extensive scrutiny of the generation of signals|journal=Spectrochimica Acta Part B: Atomic Spectroscopy|volume=56|issue=8|year=2001|pages=1277–1354|issn=05848547|doi=10.1016/S0584-8547(01)00248-8}}</ref> and frequency modulation spectroscopy (FMS),<ref name="BjorklundLevenson1983">{{cite journal|last1=Bjorklund|first1=G. C.|last2=Levenson|first2=M. D.|last3=Lenth|first3=W.|last4=Ortiz|first4=C.|title=Frequency modulation (FM) spectroscopy|journal=Applied Physics B Photophysics and Laser Chemistry|volume=32|issue=3|year=1983|pages=145–152|issn=0721-7269|doi=10.1007/BF00688820}}</ref> achieve this by rapidly scanning the frequency of the light across the absorbing transition. Both techniques have the advantage that the demodulated signal is low in the absence of absorbers but they are also limited by residual amplitude modulation, 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).<ref name="CassidyReid1982">{{cite journal|last1=Cassidy|first1=D. T.|last2=Reid|first2=J.|title=Atmospheric pressure monitoring of trace gases using tunable diode lasers|journal=Applied Optics|volume=21|issue=7|year=1982|pages=1185–90|issn=0003-6935|doi=10.1364/AO.21.001185|pmid=20389829}}</ref><ref>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).</ref> The typical sensitivity of WMS and FMS techniques is in the 10<sup>−5</sup> range.
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)<ref name="KluczynskiGustafsson2001">{{cite journal|last1=Kluczynski|first1=Pawel|last2=Gustafsson|first2=Jörgen|last3=Lindberg|first3=Åsa M.|last4=Axner|first4=Ove|title=Wavelength modulation absorption spectrometry — an extensive scrutiny of the generation of signals|journal=Spectrochimica Acta Part B: Atomic Spectroscopy|volume=56|issue=8|date=2001|pages=1277–1354|issn=0584-8547|doi=10.1016/S0584-8547(01)00248-8|bibcode=2001AcSpe..56.1277K}}</ref> and frequency modulation spectroscopy (FMS),<ref name="BjorklundLevenson1983">{{cite journal|last1=Bjorklund|first1=G. C.|last2=Levenson|first2=M. D.|last3=Lenth|first3=W.|last4=Ortiz|first4=C.|title=Frequency modulation (FM) spectroscopy|journal=Applied Physics B: Photophysics and Laser Chemistry|volume=32|issue=3|date=1983|pages=145–152|issn=0721-7269|doi=10.1007/BF00688820|bibcode=1983ApPhB..32..145B|hdl=10261/57307|s2cid=117556046}}</ref> achieve this by rapidly scanning the frequency of the light across the absorbing transition. Both techniques have the advantage that the demodulated signal is low in the absence of absorbers but they are also limited by residual amplitude modulation, either from the laser or from multiple reflections in the optical system ([[Fabry–Pérot interferometer|etalon]] effects). The most frequently used laser-based technique for environmental investigations and [[process control]] applications is based upon diode lasers and WMS (typically referred to as [[Tunable diode laser absorption spectroscopy|TDLAS]]).<ref name="CassidyReid1982">{{cite journal|last1=Cassidy|first1=D. T.|last2=Reid|first2=J.|title=Atmospheric pressure monitoring of trace gases using tunable diode lasers|journal=Applied Optics|volume=21|issue=7|date=1982|pages=1185–90|issn=0003-6935|doi=10.1364/AO.21.001185|pmid=20389829|bibcode=1982ApOpt..21.1185C}}</ref><ref>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).</ref> The typical sensitivity of WMS and FMS techniques is in the 10<sup>−5</sup> range.


Due to their good tunability and long lifetime (> 10,000 hours), most practical laser-based absorption spectroscopy is today performed by [[Distributed feedback laser|distributed feedback diode lasers]]. This gives rise to systems that can run unattended for thousands of hours, with a minimum of maintenance.
Due to their good tunability and long lifetime (> 10,000 hours), most practical laser-based absorption spectroscopy is performed today by [[Distributed feedback laser|distributed feedback diode lasers]] emitting in the 760&nbsp;[[Nanometre|nm]] – 16 [[Micrometre|μm]] range. This gives rise to systems that can run unattended for thousands of hours with minimum maintenance.

However, since these laser are mostly developed for the telecom industry, they emit in the near infrared (NIR) region, primarily in the 700&nbsp;nm – 2 μm range. With light in this wavelength region, mostly only weak overtone and combination band transitions of molecules can be addressed. This limits the sensitivity 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 using fundamental vibrational or electronic transitions ==
== Laser absorption spectrometry using fundamental vibrational or electronic transitions ==
The second way of improving the detection limit of LAS is to employ transitions with larger line strength, 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. On the other hand, electronic transitions have often yet another 1–2 orders of magnitude larger line strengths. The transitions strengths for the electronic transitions of NO, which are located in the UV range (at ~227&nbsp;nm) are ~2 orders of magnitude larger than those in the MIR region.{{citation needed|date=August 2013}}
The second way of improving the detection limit of LAS is to employ transitions with larger line strength, either in the fundamental vibrational band or electronic transitions. The former, which normally reside at ~5 μm, have line strengths that are ~2–3 orders of magnitude higher than those of typical overtone transition. On the other hand, electronic transitions have often yet another 1–2 orders of magnitude larger line strengths. The transitions strengths for the electronic transitions of NO{{Clarify|reason=What is this acronym?|date=March 2019}}, which are located in the [[Ultraviolet|UV]] range (at ~227&nbsp;nm) are ~2 orders of magnitude larger than those in the MIR region.{{citation needed|date=August 2013}}


The recent development of [[quantum cascade laser]]s (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 to generate stable cw light addressing electronic transitions, since these often lie in the UV region.
The recent development of [[quantum cascade lasers|quantum cascade]] (QC) lasers working in the MIR region has opened up new possibilities for sensitive detection of [[Molecule|molecular]] species on their fundamental vibrational bands. It is more difficult to generate stable cw light addressing electronic transitions, since these often lie in the UV region.


== Cavity enhanced absorption spectrometry ==
== Cavity enhanced absorption spectrometry ==
The third way of improving the sensitivity of LAS is to increase the path 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 by non-linear processes.
The third way of improving the sensitivity of LAS is to increase the path 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 by non-linear processes.


External cavities can either be of [[Multipass spectroscopic absorption cells|multi-pass type]], i.e. [[Herriott cell|Herriott]] or [[White cell (spectroscopy)|White cells]], or be of resonant type, most often working as a [[Fabry–Pérot etalon|Fabry–Pérot (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 ~ 10<sup>4</sup> to 10<sup>5</sup>.
External cavities can either be of [[Multipass spectroscopic absorption cells|multi-pass type]], i.e. [[Herriott cell|Herriott]] or [[White cell (spectroscopy)|White cells]], or be of resonant type, most often working as a [[Fabry–Pérot etalon|Fabry–Pérot (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 ~10<sup>4</sup> to 10<sup>5</sup>.


A problem with resonant cavities is though that a high finesse cavity has narrow [[Longitudinal mode|cavity modes]], often in the low kHz range. Since cw lasers often have free-running linewidths in the MHz range, and pulsed even larger, it is difficult to couple laser light effectively into a high finesse cavity. There are though a few ways this can be achieved.
A problem with resonant cavities is that a high finesse cavity has narrow [[Longitudinal mode|cavity modes]], often in the low [[Hertz|kHz]] range. Since cw lasers often have free-running line-widths in the MHz range, and pulsed even larger, it is difficult to couple laser light effectively into a high finesse cavity. However, there are a few ways this can be achieved. One such method is [[Vernier Spectroscopy]], which employs a frequency comb laser to excite many cavity modes simultaneously and allows for a highly parallel measurement of [[Trace gas|trace gases]].


=== Cavity ring-down spectroscopy ===
=== Cavity ring-down spectroscopy ===
In [[cavity ring-down spectroscopy]] (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<sup>−7</sup> range can routinely be obtained (although the most complex setups can reach below this~10<sup>−9</sup>). CRDS has therefore started to become a standard technique for sensitive trace gas analysis under a variety of conditions.Also CRDS is now an effective method for different physical parameters (such as temperature,pressure,strain) sensing.<ref name="PaldusKachanov2005">{{cite journal|last1=Paldus|first1=Barbara A|last2=Kachanov|first2=Alexander A|title=An historical overview of cavity-enhanced methods|journal=Canadian Journal of Physics|volume=83|issue=10|year=2005|pages=975–999|issn=0008-4204|doi=10.1139/p05-054}}</ref>
In [[cavity ring-down spectroscopy]] (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<sup>−7</sup> range can routinely be obtained (although the most complex setups can reach below this~10<sup>−9</sup>). CRDS has therefore started to become a standard technique for sensitive trace gas analysis under a variety of conditions. In addition, CRDS is now an effective method for different physical parameters (such as temperature, pressure, strain) sensing.<ref name="PaldusKachanov2005">{{cite journal|last1=Paldus|first1=Barbara A|last2=Kachanov|first2=Alexander A|title=An historical overview of cavity-enhanced methods|journal=Canadian Journal of Physics|volume=83|issue=10|date=2005|pages=975–999|issn=0008-4204|doi=10.1139/p05-054|bibcode=2005CaJPh..83..975P}}</ref>


=== Integrated cavity output spectroscopy ===
=== Integrated cavity output spectroscopy ===
Integrated cavity output spectroscopy (ICOS) sometimes called as cavity-enhanced absorption spectroscopy (CEAS) records the integrated intensity behind one of the cavity mirrors, while the laser is repeatedly swept across one or several cavity modes.{{citation needed|date=July 2013}} 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 do not interact with a high density of transverse modes. Although intensity fluctuations are lower than direct on-axis ICOS, the technique is, however, still limited by a low transmission and intensity fluctuations due to partly excitation of high order transverse modes, and can again typically reach sensitivities ~10<sup>−7</sup> .
Integrated cavity output spectroscopy (ICOS) sometimes called as cavity-enhanced absorption spectroscopy (CEAS) records the integrated intensity behind one of the cavity mirrors, while the laser is repeatedly swept across one or several cavity modes.{{citation needed|date=July 2013}} 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 not interact with a high density of transverse modes. Although intensity fluctuations are lower than direct on-axis ICOS, the technique is, however, still limited by a low transmission and intensity fluctuations due to partly excitation of high order transverse modes, and can again typically reach sensitivities ~10<sup>−7</sup> .


=== Continuous wave cavity enhanced absorption spectrometry ===
=== Continuous wave cavity enhanced absorption spectrometry ===
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,<ref>D. Romanini, A. A. Kachanav, J. Morville, and M. Chenevier, ''Proc. SPIE EUROPTO (Ser. Environmental Sensing)'' '''3821''' (8), 94 (1999)</ref> uses 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<sup>−8</sup> range, limited by a fluctuating feedback efficiency.<ref>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)</ref> Electronic locking is usually realized with the Pound-Drever-Hall (PDH) technique,<ref>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)</ref> and is nowadays a well established technique, although it can be difficult to achieve for some types of lasers.<ref>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)</ref><ref>J. L. Hall and T. W. Hansch, "External dye-laser frequency stabilizer," ''Optics Letters''''' 9''' (11), 502–504 (1984</ref> It has been shown by that also electronically locked CEAS can be used for sensitive AS on overtone lines.<ref>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)</ref><ref>M. Delabachelerie, K. Nakagawa, and M. Ohtsu, "Ultranarrow (C<sub>2</sub>H<sub>2</sub>)-C-13 Saturated-Absorption Lines at 1.5 Mu-M," ''Optics Letters'' '''19''' (11), 840–842 (1994)</ref><ref>G. Gagliardi, G. Rusciano, and L. Gianfrani, "Sub-Doppler spectroscopy of (H<sub>2</sub>O)-O-18 at 1.4 μm," ''Applied Physics B-Lasers and Optics'' '''70''' (6), 883–888 (2000)</ref>
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 of 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,<ref>D. Romanini, A. A. Kachanav, J. Morville, and M. Chenevier, ''Proc. SPIE EUROPTO (Ser. Environmental Sensing)'' '''3821''' (8), 94 (1999)</ref> uses 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<sup>−8</sup> range, limited by a fluctuating feedback efficiency.<ref>{{cite journal | last1=Morville | first1=J. | last2=Kassi | first2=S. | last3=Chenevier | first3=M. | last4=Romanini | first4=D. | title=Fast, low-noise, mode-by-mode, cavity-enhanced absorption spectroscopy by diode-laser self-locking | journal=Applied Physics B: Lasers and Optics | volume=80 | issue=8 | pages=1027–1038 | date=2005 | doi=10.1007/s00340-005-1828-z | url=https://www.researchgate.net/publication/225831931}}</ref> Electronic locking is usually realized with the [[Pound–Drever–Hall technique|Pound-Drever-Hall]] (PDH) technique,<ref>{{cite journal | last=Drever | first=R. W. P. | last2=Hall | first2=J. L. | last3=Kowalski | first3=F. V. | last4=Hough | first4=J. | last5=Ford | first5=G. M. | last6=Munley | first6=A. J. | last7=Ward | first7=H. | title=Laser phase and frequency stabilization using an optical resonator | journal=Applied Physics B: Photophysics and Laser Chemistry | volume=31 | issue=2 | pages=97–105 | date=1983 | doi=10.1007/BF00702605 | url = https://www.researchgate.net/publication/222714969}}</ref> and is nowadays a well established technique, although it can be difficult to achieve for some types of lasers.<ref>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)</ref><ref>{{cite journal | last1=Hall | first1=J. L. | last2=Hänsch | first2=T. W. | title=External dye-laser frequency stabilizer | journal=Optics Letters | volume=9 | issue=11 | pages=502–504 | date=1984 | doi=10.1364/OL.9.000502 }}</ref> It has been shown by that also electronically locked CEAS can be used for sensitive AS on overtone lines.<ref>{{cite journal | last1=Nakagawa | first1=K. | last2=Katsuda | first2=T. | last3=Shelkovnikov | first3=A.S. | last4=de Labachelerie | first4=M. | last5=Ohtsu | first5=M. | title=Highly sensitive detection of molecular absorption using a high finesse optical cavity | journal=Optics Communications | volume=107 | issue=5-6 | pages=369–372| date=1994 | doi=10.1016/0030-4018(94)90349-2 }}</ref><ref>{{cite journal | last1=de Labachelerie | first1=M. | last2=Nakagawa | first2=K. | last3=Ohtsu | first3=M. | title=Ultranarrow <sup>13</sup>C<sub>2</sub>H<sub>2</sub> saturated-absorption lines at 15 μm | journal=Optics Letters | volume=19 | issue=11 | page=840–842 | date=June 1, 1994 | doi=10.1364/OL.19.000840}}</ref><ref>{{cite journal | last1=Gagliardi | first1=G. | last2=Rusciano | first2=G. | last3=Gianfrani | first3=L. | title=Sub-Doppler spectroscopy of H<sub>2</sub><sup>18</sup>O at 1.4 μm: | journal=Applied Physics B: Lasers and Optics | volume=70 | issue=6 | pages=883–888 | date=2000 | doi=10.1007/PL00021149 }}</ref>


=== Noise-immune cavity-enhanced optical-heterodyne molecular spectroscopy===
=== Noise-immune cavity-enhanced optical-heterodyne molecular spectroscopy===
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<sup>−13</sup>. The reason is twofold: (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 sensitivity; 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<sup>−13</sup> (1•10<sup>−14</sup> cm<sup>−1</sup>).<ref>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 C<sub>2</sub>H<sub>2</sub> and C<sub>2</sub>HD," ''Journal of the Optical Society of America B-Optical Physics'' '''16''' (12), 2255–2268 (1999)</ref> It is clear that this technique, correctly developed, has a larger potential than any other technique for trace gas analysis!<ref>A. Foltynowicz, F. M. Schmidt, W. Ma, and O. Axner, "Noise-immune cavity-enhanced optical heterodyne molecular spectrometry: Current status and future potential," ''Applied Physics B'' '''92''', 313–326 (2008).</ref>
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<sup>−13</sup>. The reason is twofold: (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 sensitivity; and (ii) none of these techniques makes use of any modulation technique, wherefore they still suffer 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: [[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<sup>−13</sup> (1•10<sup>−14</sup> cm<sup>−1</sup>).<ref>{{cite journal| title=Ultrasensitive frequency-modulation spectroscopy enhanced by a high-finesse optical cavity: theory and application to overtone transitions of C<sub>2</sub>H<sub>2</sub> and C<sub>2</sub>HD| date=1999| last1=Ma| first1=Long-Sheng| last2=Ye| first2=Jun| last3=Dubé| first3=Pierre| last4=Hall| first4=John L.| journal=Journal of the Optical Society of America B| volume=16| issue=12| pages=2255–2268| bibcode=1999JOSAB..16.2255M| doi=10.1364/JOSAB.16.002255| url=https://www.researchgate.net/publication/263769800}}
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 C<sub>2</sub>H<sub>2</sub> and C<sub>2</sub>HD", ''Journal of the Optical Society of America B-Optical Physics'' '''16''' (12), 2255–2268 (1999)</ref> It is clear that this technique, correctly developed, has a larger potential than any other technique for trace gas analysis.<ref>{{cite journal| title=Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy: Current status and future potential| date=2008| last1=Foltynowicz| first1=A.| last2=Schmidt| first2=F.M.| last3=Ma| first3=W.| last4=Axner| first4=O.| journal=Applied Physics B| volume=92| issue=3| page=313–326| bibcode=2008ApPhB..92..313F| doi=10.1007/s00340-008-3126-z}}</ref>


==References==
==References==
{{reflist}}
{{reflist}}

==External links==
* Zeller, W.; Naehle, L.; Fuchs, P.; Gerschuetz, F.; Hildebrandt, L.; Koeth, J. [https://www.mdpi.com/1424-8220/10/4/2492/ DFB Lasers Between 760 nm and 16 μm for Sensing Applications.] Sensors 2010, 10, 2492–2510. MDPI {{open access}}


{{lasers}}
{{lasers}}


[[Category:Spectroscopy]]
[[Category:Absorption spectroscopy]]

Latest revision as of 17:54, 26 July 2024

Laser absorption spectrometry (LAS) refers to techniques that use lasers to assess the concentration or amount of a species in gas phase by absorption spectrometry (AS).

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 spectroscopy (TDLAS) which has become commercialized and is used for a variety of applications.

Direct laser absorption spectrometry

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The most appealing advantages of LAS is its ability to provide absolute quantitative assessments of species.[1] 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 sensitivity 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 detection limit is insufficient for many types of applications.

The detection limit can be improved by (1) reducing the noise, (2) using transitions with larger transition strengths or (3) increasing the effective path length. The first can be achieved by the use of a modulation technique, the second can be obtained by using transitions in unconventional wavelength regions, whereas the third by using external cavities.

Modulated techniques

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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)[2] and frequency modulation spectroscopy (FMS),[3] achieve this by rapidly scanning the frequency of the light across the absorbing transition. Both techniques have the advantage that the demodulated signal is low in the absence of absorbers but they are also limited by residual amplitude modulation, 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 (typically referred to as TDLAS).[4][5] The typical sensitivity 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 absorption spectroscopy is performed today by distributed feedback diode lasers emitting in the 760 nm – 16 μm range. This gives rise to systems that can run unattended for thousands of hours with minimum maintenance.

Laser absorption spectrometry using fundamental vibrational or electronic transitions

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The second way of improving the detection limit of LAS is to employ transitions with larger line strength, either in the fundamental vibrational band or electronic transitions. The former, which normally reside at ~5 μm, have line strengths that are ~2–3 orders of magnitude higher than those of typical overtone transition. On the other hand, electronic transitions have often yet another 1–2 orders of magnitude larger line strengths. The transitions strengths for the electronic transitions of NO[clarification needed], which are located in the UV range (at ~227 nm) are ~2 orders of magnitude larger than those in the MIR region.[citation needed]

The recent development of quantum cascade (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 to generate stable cw light addressing electronic transitions, since these often lie in the UV region.

Cavity enhanced absorption spectrometry

[edit]

The third way of improving the sensitivity of LAS is to increase the path 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 by non-linear processes.

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–Pérot (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.

A problem with resonant cavities is that a high finesse cavity has narrow cavity modes, often in the low kHz range. Since cw lasers often have free-running line-widths in the MHz range, and pulsed even larger, it is difficult to couple laser light effectively into a high finesse cavity. However, there are a few ways this can be achieved. One such method is Vernier Spectroscopy, which employs a frequency comb laser to excite many cavity modes simultaneously and allows for a highly parallel measurement of trace gases.

Cavity ring-down spectroscopy

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In cavity ring-down spectroscopy (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~10−9). CRDS has therefore started to become a standard technique for sensitive trace gas analysis under a variety of conditions. In addition, CRDS is now an effective method for different physical parameters (such as temperature, pressure, strain) sensing.[6]

Integrated cavity output spectroscopy

[edit]

Integrated cavity output spectroscopy (ICOS) sometimes called as cavity-enhanced absorption spectroscopy (CEAS) records the integrated intensity behind one of the cavity mirrors, while the laser is repeatedly swept across one or several cavity modes.[citation needed] 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 not interact with a high density of transverse modes. Although intensity fluctuations are lower than direct on-axis ICOS, the technique is, however, still limited by a low transmission and intensity fluctuations due to partly excitation of high order transverse modes, and can again typically reach sensitivities ~10−7 .

Continuous wave cavity enhanced absorption spectrometry

[edit]

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 of 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,[7] uses 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.[8] Electronic locking is usually realized with the Pound-Drever-Hall (PDH) technique,[9] and is nowadays a well established technique, although it can be difficult to achieve for some types of lasers.[10][11] It has been shown by that also electronically locked CEAS can be used for sensitive AS on overtone lines.[12][13][14]

Noise-immune cavity-enhanced optical-heterodyne molecular spectroscopy

[edit]

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 2F/π times below that of DAS and can be down to ~10−13. The reason is twofold: (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 sensitivity; and (ii) none of these techniques makes use of any modulation technique, wherefore they still suffer 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: 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).[15] It is clear that this technique, correctly developed, has a larger potential than any other technique for trace gas analysis.[16]

References

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  1. ^ A. Fried and D. Richter: Infrared absorption Spectroscopy, in Analytical Techniques for Atmospheric Measurements (Blackwell Publishing, 2006)
  2. ^ Kluczynski, Pawel; Gustafsson, Jörgen; Lindberg, Åsa M.; Axner, Ove (2001). "Wavelength modulation absorption spectrometry — an extensive scrutiny of the generation of signals". Spectrochimica Acta Part B: Atomic Spectroscopy. 56 (8): 1277–1354. Bibcode:2001AcSpe..56.1277K. doi:10.1016/S0584-8547(01)00248-8. ISSN 0584-8547.
  3. ^ Bjorklund, G. C.; Levenson, M. D.; Lenth, W.; Ortiz, C. (1983). "Frequency modulation (FM) spectroscopy". Applied Physics B: Photophysics and Laser Chemistry. 32 (3): 145–152. Bibcode:1983ApPhB..32..145B. doi:10.1007/BF00688820. hdl:10261/57307. ISSN 0721-7269. S2CID 117556046.
  4. ^ Cassidy, D. T.; Reid, J. (1982). "Atmospheric pressure monitoring of trace gases using tunable diode lasers". Applied Optics. 21 (7): 1185–90. Bibcode:1982ApOpt..21.1185C. doi:10.1364/AO.21.001185. ISSN 0003-6935. PMID 20389829.
  5. ^ 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).
  6. ^ Paldus, Barbara A; Kachanov, Alexander A (2005). "An historical overview of cavity-enhanced methods". Canadian Journal of Physics. 83 (10): 975–999. Bibcode:2005CaJPh..83..975P. doi:10.1139/p05-054. ISSN 0008-4204.
  7. ^ D. Romanini, A. A. Kachanav, J. Morville, and M. Chenevier, Proc. SPIE EUROPTO (Ser. Environmental Sensing) 3821 (8), 94 (1999)
  8. ^ Morville, J.; Kassi, S.; Chenevier, M.; Romanini, D. (2005). "Fast, low-noise, mode-by-mode, cavity-enhanced absorption spectroscopy by diode-laser self-locking". Applied Physics B: Lasers and Optics. 80 (8): 1027–1038. doi:10.1007/s00340-005-1828-z.
  9. ^ Drever, R. W. P.; Hall, J. L.; Kowalski, F. V.; Hough, J.; Ford, G. M.; Munley, A. J.; Ward, H. (1983). "Laser phase and frequency stabilization using an optical resonator". Applied Physics B: Photophysics and Laser Chemistry. 31 (2): 97–105. doi:10.1007/BF00702605.
  10. ^ 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)
  11. ^ Hall, J. L.; Hänsch, T. W. (1984). "External dye-laser frequency stabilizer". Optics Letters. 9 (11): 502–504. doi:10.1364/OL.9.000502.
  12. ^ Nakagawa, K.; Katsuda, T.; Shelkovnikov, A.S.; de Labachelerie, M.; Ohtsu, M. (1994). "Highly sensitive detection of molecular absorption using a high finesse optical cavity". Optics Communications. 107 (5–6): 369–372. doi:10.1016/0030-4018(94)90349-2.
  13. ^ de Labachelerie, M.; Nakagawa, K.; Ohtsu, M. (June 1, 1994). "Ultranarrow 13C2H2 saturated-absorption lines at 15 μm". Optics Letters. 19 (11): 840–842. doi:10.1364/OL.19.000840.
  14. ^ Gagliardi, G.; Rusciano, G.; Gianfrani, L. (2000). "Sub-Doppler spectroscopy of H218O at 1.4 μm:". Applied Physics B: Lasers and Optics. 70 (6): 883–888. doi:10.1007/PL00021149.
  15. ^ Ma, Long-Sheng; Ye, Jun; Dubé, Pierre; Hall, John L. (1999). "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. 16 (12): 2255–2268. Bibcode:1999JOSAB..16.2255M. doi:10.1364/JOSAB.16.002255. 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)
  16. ^ Foltynowicz, A.; Schmidt, F.M.; Ma, W.; Axner, O. (2008). "Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy: Current status and future potential". Applied Physics B. 92 (3): 313–326. Bibcode:2008ApPhB..92..313F. doi:10.1007/s00340-008-3126-z.
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