Optics and Lasers in Engineering 37 (2002) 101114

Near- and mid-infrared laser-optical sensors for

gas analysis
Peter Werlea,*, Franz Slemra, Karl Maurera, Robert Kormannb,
c
.
Robert Mucke
, Bernd J.ankerd
a

Fraunhofer Institut, D-82467 Garmisch-Partenkirchen, Germany

b
Max-Planck Institut fur
. Chemie, D-55128 Mainz, Germany
c
Inneon Technologies, D-93049 Regensburg, Germany
d
Carl Zeiss, D-73446 Oberkochen, Germany
Received 15 April 2001; accepted 12 July 2001

Abstract
Semiconductor diode lasers were rst developed in the mid-1960s and found immediate
application as much needed tunable sources for high-resolution laser spectroscopy commonly
referred to as tunable diode laser absorption spectroscopy (TDLAS). In this paper, currently
available semiconductor lasers for spectroscopy in the near- and mid-infrared spectral region
based upon gallium arsenide, indium phosphite, antimonides and lead-salt containing compounds will be reviewed together with the main features of TDLAS. Room-temperature
measurements of atmospheric carbon dioxide near 2 mm will be discussed and recent results
obtained with a fast chemical sensor for methane ux measurements based on lead-salt diode
lasers operating near 7.8 mm will be presented. r 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Semiconductor lasers; Diode laser spectroscopy; Trace gas analysis; Carbon dioxide; Methane

1. Introduction
Laser-optical sensors are now at the threshold of routine applications in air
pollution monitoring and industrial process and gas analysis. The development of
this technology has been driven mainly by scientic questions, but increasingly these
sensors are transferred to industrial and other applications whenever sensitive,
selective and fast analysis is required. With the increasing complexity of processes,
*Corresponding author. Haidestr. 4, D-82438 Eschenlohe, Germany.
E-mail address: pwwerle@aol.com (P. Werle).
0143-8166/02/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 3 - 8 1 6 6 ( 0 1 ) 0 0 0 9 2 - 6

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online gas analysis is becoming a key issue in automated control of various industrial
applications, in combustion diagnostics, for investigations of aeroengines and
automobile exhaust measurements. Other challenges are online analysis of highpurity process gases, medical diagnostics and monitoring of agricultural and
industrial emissions. The need to meet increasingly stringent environmental and
legislative requirements has also led to the development of analyzers to measure the
concentrations of a variety of gases [1] based on near- and mid-infrared absorption
spectroscopy. After a brief review of currently available diode lasers for dierent
spectral regions we will describe a near-infrared trace-gas sensor for carbon dioxide
based on a room-temperature diode laser and a fast chemical mid-infrared sensor for
methane based on a lead-salt diode laser.

2. Semiconductor lasers
Semiconductor diode lasers play an important role in telecommunications and
consumer electronics in applications such as ber optical communications, laser
printers and CD players because of their small size, high reliability and ease of use.
As it can be seen from Fig. 1, the whole spectral range from the visible to the infrared
can be covered by semiconductor lasers of various compounds, which mainly are
gallium arsenide, indium phosphite, antimonides and lead salts. A drawback for
industrial applications of spectrometers based on semiconductor lasers is the lack of
high-quality, high-power laser diodes for many spectral regions of interest.
Gallium arsenide and indium phosphite lasers are commercially made from the III
V group of semiconductor materials. These diode lasers emit from the visible to nearinfrared wavelengths from 0.63 to 1.55 mm including the InGaAsP/InP 1.31.55 mm
optical communication lasers, as well as the GaAs/AlGaAs 0.78 and 0.83 mm lasers
found in compact disk players. The technology of near-IR 1.3 and 1.55 mm
InGaAsP/InP diode lasers developed for ber-optic communication can be extended
to fabricate lasers that emit anywhere in the wavelength interval of about 1.22 mm.
Near-infrared multiple-quantum-well distributed-feedback (DFB) lasers have the
advantages of single-mode outputs at milliwatt power and near-room-temperature
operation [2]. A drawback of these devices is that they are available only in narrow
spectral regions and only a limited number of molecular species have absorption
features in the spectral region covered by these lasers. Furthermore, near-IR
absorptions are overtone or combination bands that are typically one to several
orders of magnitude weaker than the IR-fundamental band, while many molecules
of interest have near-IR absorption bands that are strong enough for detection at
parts-per-million (ppm) and, in some cases, even parts-per-billion (ppb) levels [25].
Especially, the lasers for the visible/blue spectral range are of increasing importance
for element analysis based on atom absorption spectroscopy [6].
Antimonide lasers can be used for wavelengths longer than 1.8 mm and are based
on IIIV compounds such as AlGaAsSb, InGaAsSb, and InAsSbP. Room
temperature lasing from 2 to 2.4 mm has been reported from simple double
heterostructure antimonide diode lasers. As wavelength increases up to 3.7 mm, the

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103

Fig. 1. Spectral coverage of the visible to infrared region by dierent semiconductor laser materials: While
for pn-junction lasers room-temperature operation is only possible up to 23 mm for IIIV materials,
Quantum cascade lasers become a promising alternative to the cryogenic cooled IVVI lead-salt diode
lasers. Also shown are absorption cross sections for methane and interfering water vapor.

maximum operating temperature decreases as a result of increasing optical and

electrical losses. Laser devices based on InAsSb/ InAsSbP double heterostructure
devices were grown by liquid-phase epitaxy on InAs substrate and cover the spectral
range from 3 to 4 mm at LN2 temperatures. These devices are well suited, e.g. for the
detection of HCHO at 3.6 mm and CH4 at 3.26 mm [7]. For this spectral range also
spectroscopic sources based on frequency mixing techniques have been designed,
which allow room-temperature operation [8].
Lead-salt diode lasers are made from IVVI semiconductor materials and operate
in the 330 mm spectral region [9]. Therefore, they cover the IR fundamental bands
with strong absorption for the most atmospheric trace gases [1]. They are used
almost exclusively for spectroscopic applications [1014]. Since IVVI lasers and
their associated detectors operate at cryogenic temperatures, they are more expensive

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P. Werle et al. / Optics and Lasers in Engineering 37 (2002) 101114

and more cumbersome to use than IIIV devices [15]. In trace gas monitoring
applications, lead-salt laser instruments have routinely achieved parts-per-billion
detection levels of a number of important molecular species [1]. For unattended
industrial routine applications, however, the use of lead-salt diode lasers is limited by
the need of cryogenic cooling by LN2 or Stirling coolers (typ. 78120 K), occurrence
of multimode emission and power levels which are typically only several hundred
microwatts. Compared to GaAs lasers, lead-salt semiconductor lasers are at a
relatively early stage of their development due to a much smaller market.
Until recently, all semiconductor lasers, regardless of their operating wavelength,
relied upon direct band-to-band transitions in bulk material as shown in Fig. 1 (top
left). Rapid progress has been reported in mid-IR lasers based on new types of
transitions. The most notable example is the Quantum cascade (QC) lasers.
Although the basic concept was proposed as early as 1971, it took more than 20
years before an actual device was demonstrated in 1994 [16]. Quantum cascade lasers
are based on a completely dierent approach than the lasers described so far. In a
QC laser, electrons make transitions between bound states created by quantum
connement in ultra-thin alternating layers of semiconductor materials. Since these
ultra-thin layers, called quantum wells, have a size comparable to the electrons de
Broglie wavelength, they restrict the electron motion perpendicular to the plane of
the layer. Due to this eect called quantum connement, the electron can only jump
from one state to the other by discrete steps, emitting photons of light (Fig. 1 top
right). The spacing between the steps depends on the width of the well, and increases
as the well size is decreased. In a pictorial way, this laser is freed from bandgap
slavery, i.e. the emission wavelength depends now on the layer thickness and not on
the bandgap of the constituent materials. This has allowed, using the same base
semiconductors (InGaAs and AlInAs grown on InP), the manufacture of lasers with
an emission wavelength from 3.5 to 11.5 mm (recent work in Bell labs at Lucent
Technologies has pushed this limit to 17 mm). Compared to conventional (interband)
lasers, the quantum cascade laser has the following advantages: The same
semiconductor material whose technology is very well mastered can be used to
manufacture lasers operating across the whole mid-infrared (and potentially even
farther in the far-infrared). It is based on a cascade of identical stages (typically 20
70), allowing one electron to emit many photons, emitting more optical power. It is
intrinsically more robust (no interface recombination) and since the dominant nonradiative recombination mechanism is optical phonon emission and not Auger eect
(as it is the case in narrow-gap materials), it allows intrinsically higher operating
temperature. While these new types of lasers are still in the experimental stage, they
appear to oer the prospect of more robust construction and higher temperature
operation than is possible with the materials which have been used up to this point.
These devices are operated in pulsed mode at room temperature and allow
continuous wave operation only at lower temperatures. In the 58 mm wavelength
region, continuous wave operation at temperatures above 120 K generates
remarkable output powers of 220 mW and about 200 mW at 80 K [17], while in
comparison lead-salt diode lasers deliver only 200 mW at liquid nitrogen temperature.
With quantum cascade lasers already rst spectroscopic measurements have been

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105

reported [1820]. The commercial availability of these lasers might promote the
development of new operational systems that allow highly sensitive measurements
based on the strong fundamental IR transitions.

3. Diode laser spectroscopy

Semiconductor lasers were rst introduced in the mid-1960s and found immediate
application as much needed tunable sources for high-resolution infrared laser
absorption spectroscopy. The principal setup of an optical absorption spectrometer
is shown in Fig. 2a. All designs contain a radiation source, a detector and the species
under investigation in a closed absorption cell for the determination of gas
concentrations according to Beers law. Most systems also provide a modulation unit
to generate an AC signal. As a prerequisite to obtain the required specic
wavelength, selective elements have to be inserted into the optical path. GaslterCorrelator systems require a reference cell with a high concentration of the gas under
investigation. While for DOAS systems a monochromator is used, FTIR instruments
apply a Michelson interferometer as the selective element. Non-dispersive infrared
systems (NDIR) are based on gas selective devices. All instruments based on these
technologies meanwhile reached a high degree of complexity and sophistication. An
alternative approach is to insert the selective element directly into the radiation
sourceFthe laser. In principle, laser spectrometers allow less complex optomechanical designs than the current analytical instrumentation and with semiconductor

Fig. 2. (a) Principle setup of optical absorption spectroscopy, (b) direct absorption spectroscopy using a
tunable diode laser, (c) conventional wavelength modulation (kHz) spectroscopy and (d) high-frequency
modulation spectroscopy (MHz).

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P. Werle et al. / Optics and Lasers in Engineering 37 (2002) 101114

lasers even the required modulation can be implemented electronically. Therefore,

diode laser spectroscopy is an attractive and promising technique for analytical
instrumentation. The most important research applications of TDLs in atmospheric
eld measurements required long-path absorption cells to provide high-sensitivity
local measurements. In spectroscopy a single narrow laser line usually scans over an
isolated absorption line of the species under investigation (Fig. 2b). To achieve the
highest selectivity, analysis is made at low pressure, where the absorption lines are
not substantially broadened by pressure. This type of measurements has developed
into a very sensitive and general technique for monitoring most atmospheric trace
species [1]. The main requirement is that the molecule should have an infrared linespectrum which is resolvable at the Doppler limit, which in practice includes most
molecules with up to ve atoms together with some larger molecules. Since TDLAS
operates at reduced pressure it is not restricted in wavelength to the atmospheric
windows such as 3.45 and 813 mm.
Direct absorption measurements have to resolve small changes in a large signal. In
comparison with direct spectroscopy, the benets of modulation spectroscopy in
TDLAS are twofold. Firstly, it produces a dierence signal which is directly
proportional to the species concentration (zero baseline technique) and, secondly, it
allows the signal to be detected at a frequency at which the laser noise is signicantly
reduced. Wavelength modulation spectroscopy (WMS) has been used with tunable
diode laser sources since the early 1970s. The earliest TDL systems used a
modulation frequency in the lower kHz regime and second harmonic detection.
Today 50 kHz modulation with 100 kHz detection is quite usual and, consequently, it
is convenient to regard 100 kHz as a limit of conventional wavelength-modulated
TDLAS. Modulation spectroscopy is based on the ease with which diode lasers can
be modulated. In WMS with diode lasers, the injection current is modulated as the
laser wavelength is tuned repeatedly at about 100 Hz over the selected absorption
line and a computer-controlled signal-averager is used to accumulate the signal from
a lock-in amplier (Fig. 2c or d). This produces a harmonic spectrum of the line,
with an amplitude proportional to the species concentration. Scanning over the line
gives increased condence in the measurement because the characteristic feature of
the measured species is clearly seen and unwanted spectral features due to interfering
species or e! talon fringes can easily be identied.
While mid-infrared lasers operated at cryogenic temperatures cover the fundamental absorption bands required for ultra-sensitive gas analysis, near-infrared
room-temperature diode lasers give access mainly to signicantly weaker overtone
and combination bands. Therefore, the selection of the optimum operating
conditions for a gas analyzer is always a tradeo between the required sensitivity
and an operational system. By averaging over periods longer than 1 s or by using
longer path length the detection limits can be improved. While the predicted
sensitivities are based on known line strengths and the performance of a typical
TDLAS system, it is in the nature of eld measurements that optimum performance
is not always achieved due to drift eects and other interfering disturbances [21]. To
cope with these problems dierent approaches based upon signal processing [22] and
double modulation techniques [23] have been proposed and successfully applied.

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107

To illustrate the performance and operation of state-of-the-art near- and midinfrared spectrometers based on tunable diode lasers in the next section an example
of a near-infrared trace gas sensor for carbon dioxide based on a room-temperature
2 mm indium-phosphite-DFB-laser will be presented. Finally, a typical mid-infrared
spectrometer for methane detection based on a lead-salt diode laser operating at
7.8 mm at liquid nitrogen temperature will be described.
4. Near-infrared trace-gas sensor for carbon dioxide based on a room-temperature
diode laser
For many eld measurements or industrial applications the use of liquid nitrogen
must be avoided, only temperature stabilization by thermoelectrical elements is
acceptable. Therefore, in a fast CO2 sensor (Fig. 3a) we implemented InP-DFB-

Fig. 3. (a) Optical layout of a near-infrared spectrometer using an optical multipass cell (Herriott), (b)
typical mode map of an indium-phosphite-DFB-laser at 2 mm with 12 mW power, (c) measurements of
12
CO2 in ambient air at a pressure of 100 mbar and 100 m optical path length, (d) time series data recorded
from a 358 ppm 12CO2 calibration gas mixture and (e) identication of 12CO2 and 13CO2 absorption lines
around 2001.3 nm.

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P. Werle et al. / Optics and Lasers in Engineering 37 (2002) 101114

lasers from Sensors Unlimited Inc. (Princeton, NJ) with room-temperature singlemode emission at lE2 mm as shown in Fig. 3b. The components are mounted on a
60 cm
110 cm optical breadboard on top of a double 19 in rack. The DFB laser is
held inside a Peltier-cooled mount which is xed on an xyz-stage. The laser beam is
collimated by an o-axis parabola (OAP) with 10 mm diameter and 12 mm focal
length. The beam is focused by a spherical mirror (f 1 m) to the center of a
Herriott-type measurement cell. After 181 reections, corresponding to 100 m, the
beam exits the cell and is focused onto a temperature-stabilized extended InGaAs
detector (sensors unlimited) by another OAP. About 8% of the laser beam is coupled
o by a beam-splitter and directed through the 28 cm reference cell onto another
InGaAs detector. The whole system is pre-aligned by a visible diode laser, coupled
into the setup by a pellicle beam-splitter which has to be removed during the
measurements. In order to provide static as well as ux measurements at dened cell
pressures, the measurement cell is equipped with a pressure sensor and on/o-valves
(at inlet and outlet) as well as with a needle valve at the inlet and a throttle valve at
the outlet. The reference cellFlled with a high-concentration CO2 mixture and
sealed oFis connected to the measurement cell by a temperature bridge and a
dierential pressure sensor. With adjusted laser power and the right concentration in
the reference cell the signals from both detectors have identical shape and amplitude
and after system calibration using certied gas mixtures the reference signal can be
used as a secondary calibration standard. The signal processing schemes for singletone and two-tone FM spectroscopy can be found in detail in a recent review of
advances in semiconductor laser-based gas monitors [1].
The NIR system shown above has been applied for the detection of atmospheric
CO2. The DC current of the temperature-stabilized DFB laser is adjusted to the
selected absorption line. The laser is scanned over this line by a 1 kHz ramp and
additionally modulated by high frequency. In order to optimize the signal-to-noise
ratio and the system stability two dierent FM techniques (single-tone and two-tone)
have been implemented. Due to the limited detector bandwidth, frequencies up to
300 MHz are applied, corresponding to the line width of CO2 at a pressure of
100 mbar. Some FM signals from a near-infrared InP diode laser operating around
2 mm are shown in Fig. 3c when outdoor air has been pumped through the Herriott
cell and the ambient CO2 signal of 350 ppm was recorded at 2.004 mm. From the
weaker absorption lines of CO2 and H2O under high amplication a precision of up
to 104 has been estimated for 256 averages in less than 1 s. It is obvious that this
spectral region has a signicant advantage versus the 1.573 mm absorption band in
the NIR, where the line strength is about 2 orders of magnitude weaker. At 2 mm the
line strength is still weaker than in the fundamental band, but room-temperature
operation of diode lasers is still possible for cw applications [2]. Recording of
averaged spectra and calibration lead to time series data as shown in Fig. 3d for a
358 ppm CO2 calibration gas mixture. Besides ambient measurements another
possible application could be isotopic ratio measurements for medical diagnosis, e.g.
breath test.1 Therefore, 13CO2/12CO2 line pairs within the operation range of the
1

E.g. IRIS-infrared

13

C stable isotope analyser, www.wagner-bremen.de.

P. Werle et al. / Optics and Lasers in Engineering 37 (2002) 101114

109

tested 2 mm laser have been analyzed in the vicinity of 2000.8 and 2001.3 nm. The
latter line pair is partly inuenced by water vapor as displayed in Fig. 3e but one has
to consider that the CO2 absorption in expiration air is by a factor of 2030 higher
than the displayed ones. For medical applications the measuring instrument should
be able to determine the ratio of 13CO2 and 12CO2 with a resolution of at least 1%
[2], while the absolute CO2 concentration in human expiration air is 35%, with
100% relative humidity at body temperature. The natural ratio 13CO2 : 12CO2 is
1.09570.003%. Therefore, the instrument must be able to detect both isotopes with
a resolution of o103 unaected by water vapor. The measurement of the 13CO2
content in expiration air using the lines at 2000.8 and 2001.3 nm generates about the
same signal as 12CO2 in ambient atmospheric air masses at 2004 nm. Therefore,
equivalent detection limits are expected. For a typical required reproducibility of less
than 0.3 delta per mille for the determination of the 13C/12C ratio, the neighboring
12
CO2 lines, which are weaker by a factor of 4, dominate the sensitivity, but even at
absorption path lengths of less than 10 m clear signals are expected. The main
problem of accuracy is connected with temperature: the ratio of the line strength
must be kept constant, which means here that the temperature during the analysis
including calibration must be stable within 0.01 K, because the involved line
strengths show opposite temperature dependencies (at 2001.3 nm the ratio of the line
strengths changes from 5.4655 at 290 K to 4.081 at 300 K). A reliable measurement
of the 13CO2 : 12CO2 ratio using the 2000.8 and 2001.3 nm spectral regions is not easy
to perform, but feasible when using a small multipass cell. Nevertheless, the
utilization of line pairs with reduced sensitivity to temperature changes is
recommended. Therefore, the line pairs must be chosen in such a way that their
temperature coecients are low but also as close as possible to each other. However,
this measurement illustrates the principle and feasibility of isotopic measurements
using tunable diode laser absorption spectroscopy, but especially for 13CO2/12CO2
isotopic ratio analysis already commercially available competitive systems based on
non-dispersive infrared analyzers exist, which meet the requirements in terms of
sensitivity and time resolution (see footnote 1).

5. Fast chemical mid-infrared sensor for methane based on a lead-salt diode laser
A fast laser-optical sensor is the key issue for trace gas ux measurements based
on the so-called eddy correlation technique [1214]. As high time resolution and high
chemical resolution were the prerequisites for the success of the measurements, highfrequency modulation (FM) spectroscopy has been selected. In FM spectroscopy,
the laser is modulated at higher frequencies, typically in the radio frequency (rf)
region, thus allowing selective and fast scanning over an absorption line of a
molecule [1]. The layout of the detection electronics is shown in Fig. 4a. The system
can be run in either single-tone or two-tone mode and the optimum method can be
selected by the system operator from case to case depending on the experimental
conditions. The modulation section provides the required rf-modulation for the
laser. The laser beam is split into a sample and a reference path. Detector signals are

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P. Werle et al. / Optics and Lasers in Engineering 37 (2002) 101114

Fig. 4. (a) Setup of a mid-infrared (7.8 mm) high-frequency modulation spectrometer with a sample and a
reference cell, high-bandwidth HgCdTe detectors and subsequent phase-sensitive detection electronics, (b)
optical layout of the system with a small volume (0.3 l) Herriott cell, (c) photo of the fast chemical sensor
for eddy correlation trace gas ux measurements during a eld campaign in Italy [14], (d) typical mode
map of a lead-salt diode laser, (e) time series data of ambient methane concentrations with 10 Hz time
resolution to calculate the (f) methane ux from rice paddy elds over several days. Each point is based
upon 18,000 individual concentration measurements as shown in (e).

fed into a phase-sensitive detection electronics, which can be regarded as a highfrequency lock-in amplier. Both signals (sample and reference) are then digitized
and further processed by digital lters, line locking, normalization and calibration
procedures [22]. The reference beam goes through a reference cell, which provides a
high signal-to-noise ratio signal from the spectral feature under investigation. This
channel is used for line locking and online drift correction. A line locking procedure
monitors the deviation of the signal position from a given set-point and decides
whether a change in temperature or current has to be made to compensate for drifts.

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In order to compensate for fast and small uctuations the signals are online shifted
prior to signal averaging. These corrected signals are then fed into a digital lter
routine which removes the background and references the signal to a previously
stored calibration signal. All algorithms and procedures were implemented in a realtime parallel multi-processor system. The optical layout together with the external
control units of the system based on the detection scheme described above is shown
in Fig. 4b/c. For typical line strengths an ambient concentration of 1 ppbv produces
an absorption of only 1 part in 107 over a 10 cm path length. Conventional
absorption spectroscopy would not be able to measure such small absorptions.
TDLAS overcomes this problem by using a (White or Herriott) multi-pass cell with
eective path lengths of 100 m or more. All optomechanical components of the
spectrometer are mounted on a 50 cm
90 cm optical breadboard. The lead-salt
diode laser is mounted on a cold head within an LN2 dewar (Laser Photonics, Inc.,
Analytics Division, Andover, MA, Model L5736 Laser Dewar). The diverging laser
beam is collimated to a nearly parallel beam (1) by an o-axis parabola (OAP) and
passes through the beam steering optics, which focuses the beam at the center of a
commercial astigmatic Herriott cell (New Focus, Inc., Santa Clara, CA, Model 5611
Multipass cell) with a total path length of 18 m. This cell has a very small internal
volume of 0.3 l and is especially designed for applications requiring high time
resolution. The outcoming thin and nearly parallel beam (3) is then focused onto a
broadband HgCdTe measurement detector using a BaF2 planoconvex lens. The
reex of the cell inlet window is used as reference (2) after passing a small cell
containing pure methane gas. This reference beam is used, on the one hand, for the
reliable identication of the absorption features of the trace gas of interest, and, on
the other hand, for the active stabilization (line locking) of the spectrometer. A
visible (680 nm) diode laser is used to align the system. The beam splitter, which sets
the alignment beam onto the main light path, is removed during the measurement. A
.
rotary vacuum pump (Leybold AG, Koln,
Germany, Model SOGEVAC SV 65)
provides the gas ow of about 18 slm through the Herriott cell at a pressure of about
50 hPa. A dust lter is mounted at the inlet point of the measurement head to protect
the gas system and especially the mirrors of the Herriott cell from pollution. A newly
developed calibration system allowed programmed sequences of measurements of
background signals (N2), calibration gas and ambient air. The calibration system is
based on a dilution system and high-concentration calibration gas from steel
cylinders is diluted to ambient concentrations.
The key element of the fast chemical sensor is the laser diode. In the lower part of
Fig. 1 the absorption spectrum of methane is plotted together with atmospheric
water absorption versus wavelength. The near-IR absorption consists of overtone or
combination bands that are typically one to several orders of magnitude weaker than
the IR-fundamental band. Antimonide lasers [7] can be used for the detection of CH4
at 3.26 mm (n3 ) and for the 7.8 mm (n4 ) spectral region lead-salt diode lasers are the
optimum choice, as they cover the IR fundamental bands with strong absorption for
the most atmospheric trace gases. In trace gas monitoring applications, lead-salt
laser instruments have routinely achieved parts-per-billion detection levels of a
number of important molecular species. When starting to select a laser, the rst task

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P. Werle et al. / Optics and Lasers in Engineering 37 (2002) 101114

is to select from mode maps a combination of base temperature and drive current at
which the laser produces a strong, preferably single-mode emission, tuned to the
absorption line being monitored. After investigation of several antimonide and leadsalt diode lasers, the lead-salt device with the characteristics shown in Fig. 4d has
been selected. For injection currents between 400 and 600 mA at temperatures
ranging from 85 to 95 K single-mode operation with an average power level of
200 mW was ensured and isolated methane absorption lines could be reproducibly
selected for the measurements even after repetitive thermal cycling, which was an
important criterion for the planned eld measurements.
With this spectrometer ambient methane concentrations around 2 ppm can be
detected with a precision of about 1% at a 10 Hz repetition rate and a typical data set
of 18,000 individual concentration values is shown in Fig 4e. The data have been
collected during about half an hour of sampling at 10 Hz. Each concentration value
has been obtained by averaging individual spectra followed by a background
correction. Such fast response measurements of state variables generate time series of
data that can be statistically analyzed. As a result a set of ux data has been
obtained, which is shown in Fig 4f. Each data point shown represents a 30 min
average obtained from time series data as shown in Fig. 4e. From an intercomparison of these data with several other independent measurements based on gas
chromatography it was found that there is a bias of up to 70% between dierent ux
measurement methods [14]. This nding is important for atmospheric chemistry
research in the context of greenhouse gases. Such simultaneously fast and highly
sensitive measurements would not be possible with near-infrared systems due to the
lack of sensitivity and the results shown here demonstrate that tunable diode laser
absorption spectroscopy can be a valuable tool for quality assurance and quality
control.

6. Conclusion
The features of diode laser spectroscopy rendering it such a valuable technique for
gas analysis are given below. It is specic and as a high resolution spectroscopic
technique it is virtually immune to interference by other speciesFa problem that
plagues most competing methods. This ability to provide unambiguous measurements leads to the use of TDLAS as a reference technique against which other
methods are often compared. It is a technique universally applicable to all smaller
infrared active molecules and the same instrument can easily be converted from one
species to another by changing the laser and calibration gases. The time resolution of
TDLAS measurements can be traded o against sensitivity and this allows very fast
measurements with millisecond time resolution. In order to improve sensitivity
various types of modulation spectroscopy have been employed in which the diode
laser wavelength is modulated while being scanned across an absorption line. These
modulation techniques allow absorption as low as 1 part in 106 to be measured
within a 1 Hz bandwidth. In combination with optical multi-pass cells, this is
equivalent to detection limits of around 20 pptv for the most strongly absorbing

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113

species and better than 1 ppbv for almost all species of interest [1]. TDLAS has made
the transition from a technique mainly of interest to instrument developers into one
which produces results of real value to trace gas analysis and atmospheric chemistry
studies. However, it has yet to become an instrument suited to routine use by nonexpert operators, mainly due to the complex and sometimes unreproducible behavior
of the lasers. Further laser development is underway to remedy this and
semiconductor lasers are available meanwhile from the visible to the mid-infrared
and hopefully the spectral coverage is continuously increasing. Strong eort is
underway to further improve quantum cascade lasers as an alternative source of
infrared tunable radiation. Anyway, the near- and mid-infrared spectral regions will
provide complementary systems. For a certain limited number of species, where
ultrahigh sensitivity is not required, the near-infrared systems will provide
advantages of size, simplicity and cost. For other species requiring a more universal
and sensitive system, the mid-infrared diodes will continue to provide a superior and
highly specic measurement device.

References
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Acta A 1998;54:197238 with 183 references.
[2] Werle P, Mucke
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