Optics and Lasers in Engineering 37 (2002) 533551

Tunable diode lasers and two-tone frequency

modulation spectroscopy applied to atmospheric
gas analysis
F. DAmatoa,*, M. De Rosab
a
SIT Srl, Via Masaccio 116, 50132 Firenze, Italy
b
European Laboratory for Non Linear Spectroscopy, LENS, Largo E. Fermi 1, 50125 Firenze, Italy

Abstract

In this paper, we discuss the main features of a class of gas analyzers based on spectroscopic
techniques with the aim of realizing fully automated systems which can be used for practical
purposes. The technique we deal with is based on semiconductor diode laser as sources,
emitting in the near infrared region of the electromagnetic spectrum, and the two-tone
frequency modulation spectroscopy as the detection technique. We will describe the main
features of a typical device and two particular apparata for industrial and biological
applications. r 2002 Elsevier Science Ltd. All rights reserved.

PACS: 42.55.P; 39.30.+w; 07.88

Keywords: Diode lasers; Spectroscopic techniques; Gas analyzers

1. Introduction

Molecular spectroscopy is a powerful tool for both fundamental physics

investigations and for practical applications. Knowledge about the molecular
absorption spectra [1,2] can be used for the realization of gas analyzers based on the
dierent techniques. As the molecular transition bands of the great part of the
molecules are in the infrared (IR) region of the electromagnetic spectrum, absorption
of IR radiation by molecular species is the basic process for a large number of
techniques aimed at the measurements of small concentrations of gases [3]. There are
two leading ideas in the development of optical analyzers. One idea is that of

*Corresponding author. URL: http://www.scintec.it.

E-mail address: francesco.damato@frascati.enea.it (F. DAmato).

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 8 9 - 6
534 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551

measuring as many gases as possible contemporarily, by using Fourier transform

spectrometers. Such instruments already exist on the market. They are quite
expensive, slow, and they cannot work in the most favorable conditions for all the
target molecules, so that their average sensitivity is not very high. The other idea is
that of developing techniques which give the best results for one molecule at a time.
Here, we restrict our attention to one of these techniques, that seems to be very
promising for the realization of practical instruments, with high sensitivity and
selectivity, along with ease of operation and economicity. The technique we deal with
is based on the selective absorption, by the investigated molecule, of IR radiation
emitted by a semiconductor diode laser source, and on a detection scheme developed
to reduce the noise aecting the measurement. The main advantages of this
technique rely on the fact that diode lasers can be selectively and continuously tuned
on a particular molecular transition by changing their temperature and injection
current; this property allows the adoption of very eective noise reduction detection
schemes based on frequency modulation of the source. Diode lasers emitting in the
mid IR region (220 mm) would be preferable, as the fundamental ro-vibrational
bands occurring there are the most intense for each molecule. Unfortunately, diode
laser currently available, emitting in that region, have to operate at liquid nitrogen
temperature or below, and this is a drawback when maintenance should be as rare as
possible, as in an industrial application. Many scientic apparata have been
developed, based on these sources [35], and several eorts are in progress to obtain
practical room temperature sources in this electromagnetic region [68]. Until these
eorts come to new commercial sources, diode lasers emitting in the near IR region
must be used, even if some orders of magnitude are loss in the intensity of the
absorptions. The lost in intensity can be compensated by increasing the absorption
pathlength and reducing the level of noise aecting the measurements. This can be
attained in dierent ways, namely, by adopting high sensitivity detection schemes [9
14], with a careful design of the optical line to reduce interference fringes and
increase the absorption pathlength [1517], and with special algorithms that process
the acquired signals [1820].
In the following, we discuss the main features of a gas analyzer based on diode
lasers, with particular emphasis on the possibility of realizing an instrument that is
suitable for the market, with a good compromise between performances, simplicity
and costs, and that can be used by non-expert people in disparate environmental
conditions, when robustness and ease of operation and maintenance are required.
Gas analyzers with very high sensitivity or resolution have been realized [21,22], but
their complexity is such that they are still far from mass production. Also, we present
two examples of such analyzers, that were designed for an industrial application such
as monitoring of emissions, and for entomological studies.

2. Scheme

The setup of the instrument includes some compulsory parts and some optional
parts. The compulsory parts are the diode laser with collimating optics; laser current
 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551 535

supply and temperature stabilizer; a detector; a device for the analysis of the signal;
the driving computer and the software. The optional devices are an absorption cell
(single- or multi-pass), a reference cell with its reference detector. The reference arm
is required each time the target molecule is usually not present in the environment
(such as HCl in the example presented later) or its concentration undergoes changes
over orders of magnitudes, like methane in leak nders. Of course, dierent mirrors
or lenses are required according to the particular geometry. Two examples of actual
setups will be shown in Sections 8.1 and 8.2.
Here, we examine in detail the dierent features of the instrument.

3. Sources

The ideal laser source should fulll two dierent groups of requirements: from the
physical point of view it must be tunable, single mode, and it must be possible to
modulate its emission frequency up to a few GHz; from the practical point of view
the laser should be small, simple to handle (this includes room temperature
operation), reliable and, possibly, cheap. As for the single mode operation, some
further considerations are needed. We usually investigate absorption lines of rather
light molecules at room temperature and pressure, so that linewidths are BGHz.
Unless we measure heavy molecules in the upper troposphere, even a laser linewidth
of 100 MHz would be acceptable. What is never acceptable is a multimode emission,
as the dierent modes have a spacing up to several GHz and there is a power
competition among them.
In the mid infrared, no laser source satises all the conditions. Lead salts lasers
are hard to handle due to cooling. They are multimode, apart in small emission
regions when specially selected, and in this case, they are very expensive. Moreover,
their emission is not continuous in frequency. Dierence frequency generation sources
[6] are complicated and expensive. Quantum Cascade sources [7,8] are a very
promising tool, as they emit single-mode in the best frequency region with a high
power, but they still require to be cooled outside the possibilities of Peltier systems.
In the near infrared, there are several choices. All diode lasers work at room
temperature (0401C). FabryPerot lasers have a multimode emission, and can be
used only in the extended cavity conguration [23]. This means that part of the laser
beam is reected back inside the laser by a mirror or a grating. This optical element
must be carefully aligned. Moreover, its position must be changed during the
frequency sweeps of the laser in order to maintain the best emission conditions. This
is usually obtained by means of piezo-electrical elements. The advantages of this
system are that the laser is rather cheap and the tunability is quite wide (more than
20 nm). These devices are commercially available at quite a high price (about 15.000
USD). As a matter of fact, an instrument which measures only one absorption line
does not require a wide tunability. As for the price, the cost of all the additional
optical components and the complication of the system nd a good motivation if the
laser lifetime is small compared to that of the whole device. If the laser lifetime is the
same as that of the instrument, like in a compact disk player, a simple source is to be
preferred.
536 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551

Table 1
Comparison among the main features of DFBs and VCSELs

Parameter Units DFB VCSEL

Emission range mm 0.82 0.71

Maximum current mA 100 10
Current tunability GHz/mA 1 180
Temperature tunability nm/K 0.1 0.05
Output power mW 10 1
Beam symmetry F Elliptical Circular
Price USD 6000 200

The sources we have chosen are distributed feed-back (DFB) and distributed
Bragg reector (DBR) lasers. In these lasers the active medium is grown on a
longitudinal diraction grating (DFB [24]) or is closed by two Bragg mirrors made
by a series of dielectric layers (DBR [25]). Presently, the commercial DBR lasers are
represented mostly by the vertical cavity surface emitting lasers (VCSEL [26]).
We have summarized the features of these two kinds of lasers in Table 1. In
practice, it is compulsory to use DFB at wavelengths above 1 mm. In any case, the
laser must be temperature stabilized, within 1 mK, and driven with a low noise
current generator. The emitted bandwidth is within 30 MHz.

4. Detection technique

The range of the absorbances in the near IR, per unit length, of the atmospheric
molecular transitions is very wide. For instance, water and CO2 give in 10 m so large
absorbances that even direct absorption is sucient to yield a good S/N.
Unfortunately most molecules, like CO, NH3 ; CH4 ; H2 S, HCl, HF, NO, etc. can
yield absorbances down to 10
6 after 100 m. In order to increase the number of
possible target molecules, very sensitive techniques must be adopted.
Harmonic detection seems to be a suitable technique for achieving an eective
reduction of the noise level which aects the measurements. In this case, the laser
frequency n0 is modulated at a frequency n1 ; and the laser eld can be described by [9]
E1 t E0 1 M sino1 t ceio0 tb sin o1 t
XN
E0 t rn exp ino1 t;
n
N

where oi 2pni : The rn coecients are

X
1
rn b; M; c ak M; cJn
k b; 1
k
1

where b and M are the frequency and amplitude modulation indices, c the relative
phase shift, a0 1; a71 7
iM=2exp7ic; and Jn b is the nth Bessels
 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551 537

function. A comb of sideband emissions is generated, symmetrical with respect to n0

and with a constant spacing n1 : The signal onto the detector is the sum of the beat
notes of all the couples of emissions. Typically, the laser noise has a 1=f behavior up
to 0.11 MHz, then the noise level is quite constant up to several GHz, where
internal relaxation eects dominate. In order to understand how eective the noise
reduction is, we must compare n1 with the width of 1=f laser noise and with nL ; the
absorption linewidth (FWHM).
Of course, the best situation is when n1 is greater than both the 1=f distribution
and nL ; which means usually above 1 GHz. This is the so-called frequency modulation
(FM). In this case, the signal is essentially the sum of only two beat notes. When the
rst sideband is at the line center, n0 is still out of the line, so the contrast is
maximum. The disadvantage is that the demodulation at n1 requires very fast
detectors, which must be very small, thus so leading to serious alignment problems,
and a carefully designed electronics, which is usually quite expensive.
At the opposite end, there is the case in which n1 is smaller than both the 1=f
distribution and nL ; say E100 kHz. In this case, we speak of derivative detection
(DD). The laser excess noise is only slightly reduced and the contrast is lower than in
FM, unless the comb of emissions extends for the entire absorption linewidth (this
would require a very large M). On the other side, the detector can be quite large and
the electronics is simpler and cheaper.
In the middle, we have the wavelength modulation (WM), in which n1 (E10 MHz)
is outside the 1=f distribution but is still much lower than the absorption linewidth.
We have a better noise reduction with respect to DD, but alignment and electronics
are still simple.
The two-tone frequency modulation (TTFM) is a mixing of FM and WM.
In this case, two frequencies n1 and n2 are added to n0 ; with the following
conditions:
n1 n2
nm XnL ;
2
7n1
n2 7 O{nL :
We can assume that the modulation indexes and the phase shift are the same for both
frequencies, so that the electric eld can be written as
X
E2 t E0 t rn rm expi2pnn1 mn2 t: 2
n;m

In this case, we have two couples of sidebands, in which the two emissions of the
same couple suer practically the same absorption. The Fourier component of the
detector photocurrent at the frequency O is proportional to
c X
IO t 7E0 t72 2M 2 cos2pOt * r*
rn rm rn
1 m1
8p n;m

exp
2an0 n mnm 
c
 7E0 t72 2 cos2pOtQa M 2 : 3
8p
538 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551

Here, an is the absorption line shape. In case of no absorption, Qa 0; so we

have
c
IO t 7E0 t72 2M 2 cos2pOt: 4
8p
This means that we have a non-zero background signal, due to residual amplitude
modulation (RAM), which limits the amplication of the demodulation chain. The
simplest way to avoid this problem is to split the laser beam into two arms. Only one
arm undergoes absorption. In the absence of absorbing gas, the signals of the two
photodetectors, one for each arm, are summed with a p phase shift and balanced to
give a zero sum. This balanced detection also eliminates the laser 1=f noise and the
optical noise before the beam splitter, a characteristic which is valid for the other
modulation techniques as well. Another possibility is that of demodulating the
detector signal at a frequency nO; with n integer greater than one [13]. In the case of
small absorption, and with the approximation M; b{1; Eq. (3) becomes:
c
IO t 7E0 t72 2M 2 cosOt
8p
2M 2 2a0 b2
M 2

a b2 2Mb sin c M 2

a
b2
2Mb sin c M 2 : 5

As a matter of fact, the condition b{1 is not always veried in TTFM, but Eq. (5)
gives, anyway, a good representation of the signal shape: a constant level (RAM),
plus a positive (negative) peak at o0 ; plus two negative (positive) peaks at o0 7om :
Once om XoL ; the contrast is the same as that of FM. For room temperature diode
lasers O in the range 510 MHz is enough to make the 1=f laser noise negligible, yet
keeping at a very low level the requirements over detector and electronic chain. So,
for TTFM the main limiting feature is RAM. We have decided to avoid the
introduction of a balancing arm for RAM suppression for two main reasons: it leads
to a complication of the systems and the balancing of the two signals is very dicult
to be maintained in eld conditions, where temperature excursion and vibrations can
make the compensation of the signal to fail. The demodulation at harmonics of O is
under consideration, but not yet implemented.

5. Electronics

The fundamental elements of the electronics are the laser driver, the TTFM
frequency generation board, the detector(s) preamplier(s), the demodulation board,
and the computer. The electronics setup is shown in Fig. 1. For TTFM, two
frequencies B1 GHz must be sent to the laser and their dierence must be used as a
local oscillator in the demodulation board. We have chosen this system: the
demodulation frequency oD is generated inside the demodulation board. This signal
is sent in part through a phase shifter to the nal mixer. The other part is frequency
 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551 539

Fig. 1. Electronics setup. FGB: Frequency Generation Board; PA: Pre Amplier; PS: Phase Shifter; Dx :
Detector.

divided by two and sent to the frequency generation board. Here, o1 and o2 are
generated by mixing a carrier oC (see below) with oD =2; yielding o1;2 oC 7oD =2:
The laser driver (LD) includes both the temperature stabilizer and the current
generator. The requirements for these two sections are easily quantied: the short-
term frequency uctuations induced by temperature/current uctuations must be less
than the frequency step of the laser scan. So, for a DFB, for a scan of 3 GHz in 100
steps, the frequency uctuation must be B10 MHz, which turns into maximum
uctuations of 10 mA and 0.1 mK. In the case of a VCSEL, the current stability must
be higher, while the temperature stability is not so critical. On the other side, as the
maximum current for a VCSEL is much lower than for a DFB laser, the requirement
on current noise can be met without serious diculties. The long-term uctuations
are corrected by an active, software-driven line locking. Both current and
temperature have a manual coarse set and a computer-driven ne adjustment. The
current sweep necessary for the measurements is obtained through this ne
adjustment.
540 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551

The TTFM frequency generation board (FGB) hosts a voltage controlled oscillator
(VCO) which generates oC ; the mixer for the production of o1;2 ; and all the circuitry
to safely feed low and high frequency signals into the laser. Here we want to remark
about a particular feature of TTFM: a high frequency signal is necessary for the right
frequency spacing of the sidebands, but this signal is necessary only at the laser
entrance, and nowhere else. So the VCO is placed just near the laser current pin. In
this way, it must run only a few cm on a printed board, and not meters in cables and
connectors.
The detector(s) preamplier(s) has nothing special, except for the fact that the
preamplier of the main detector has two outputs, one for the oD signal and one for
the low-frequency dc signal derived from the laser output power change during the
current ramp. This latter signal is used for the normalization of the acquired
waveforms with respect to the total incident power. In this way, we can get rid of
problems related to uctuation in the transmission of the sample, not related to
variations of the concentration of the target molecule.
The demodulation board (DB) generates oD ; sends to the FGB oD /2 and processes
the signal coming from the main detector. This signal is ltered, amplied by a
variable gain amplier and sent to a mixer. The other input of the mixer is oD
through a variable phase shifter. Both the amplier and the phase shifter are driven
by the computer via the DAC board.
For the computer, we have adopted the PC-104 industrial standard. The computer
is made of several boards (with standard dimensions 10 cm 10 cm 2.5 cm) stacked
through a connector which reproduces an AT bus. Our computers include four
boards: a CPU, DX 100 MHz; a VGA; an ADC, 16 inputs; a DAC, 8 outputs. With
this conguration, also 40 digital I/O lines are available. The acquisition boards are
connected through an analogical bus to LD and DB. The computer performs all the
tasks of the instrument, acquires, stores and delivers the results.

6. Software

The software has the task of driving all the instrumental activities (start-up,
diagnostics, current sweeps, data acquisitions, calibration) and of processing the
acquired signals in such a way as to give the nal results of the measurement. This
last feature deserves particular attention, as the available computers and data
acquisition systems allow real time digital processing of signals which can further
enhance the sensitivity of the analyzers. In most cases, the signal related to an
absorption is deterministic. The shape of an absorption signal depends on the
particular technique adopted for the detection: so, while a direct absorption has a
typical bell shape, for wavelength modulation techniques, the shape of the signal is
similar to dierent derivatives of the original bell shape, depending on the
demodulation frequency. However, apart from the shape, the signal has a typical
width which depends on the conditions of the sample, e.g. temperature, pressure, and
on the parameters of the detection, e.g. the modulation frequency and amplitude
index involved in the particular FM technique. We can write the signal st as a sum
 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551 541

of the contribution at due to the absorption from the molecules, and the noise nt
which unavoidably aect the measurements,
st at nt: 6
The intensity of the signal depends linearly on the density of the absorbing species in
the sample, this is true for small absorbances, when the BeerLambert law for
absorption can be well approximated by a linear dependence, as
T exp
an 1
an; an{1: 7
To be correct, the intensity of the signal had to be meant in the sense of the integral
area, however, if we assume both that the conditions of the sample are constant, and
that the parameters of the detection are optimized and kept xed, then peak-to-peak
intensity can be considered in place of integral intensity. According to these
assumptions, Eq. (6) can be write as
st kut nt; 8
where ut is the shape of the unit absorption signal, corresponding to an arbitrary
unit of absorption, and k is the intensity of a given absorption with respect to the
chosen unit. These features are the basis for the implementation of matched digital
lters and least-square t algorithms, which can enhance the sensitivity of the
analyzer of almost an order of magnitude [20]. Here, we are concerned with ltering
in the Fourier domain, when the whole acquired signal is Fourier transformed, by
means of a fast Fourier transform (FFT) algorithm, multiplied by a lter response
function Hf ; and nally transformed back to the time domain. The lter response
Hf is chosen in order to emphasize the frequencies for which the signal dominates
and reducing the frequencies for which the noise dominates. Then, a least-squares t
of the ltered signal can be used for extracting the nal information on the intensity
of the signal and thus of the concentration of the target molecules. An example of
this procedure is shown in Fig. 2. After this step, the signal level is obtained, for
instance, by taking the dierence between the central positive peak and the average
of the lateral negative peaks, possibly by tting the ltered signal with a proper
function. From the practical point of view, the signal shape can be determined easily
by measuring a high concentration sample of the target molecule, in the same
conditions as that of the routine operation, having optimized all the parameters of
the measurements; thus, its Fourier spectrum can be easily determined and as a
consequence, the Fourier harmonics which greatly contribute to the signal.
Comparing this spectrum with the spectrum of the signal when no absorbing
molecule is present, i.e., the noise spectrum, one can determine the frequencies that
can be eliminated, i.e., the frequency response Hf of the lter. However, we remark
that information on the intensity of the signal is kept in its counterpart in the Fourier
domain. Indeed, the Fourier transform of the signal of Eq. (8) can be written in a
similar form,
Sf kUf Nf ;
where capital letters are used for Fourier transform of the corresponding
components in time domain. The information on the intensity is maintained in the
542 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551

Fig. 2. Noisy signal before (a) and after (b) digital ltering.

same way for each frequency and is still linear, because of the well known linearity of
the Fourier transform operator. This simple feature suggests that the measurement
of intensity does not necessarily require the second inverse transform for returning in
the time domain. In fact, once the harmonics of the absorption signal are known, one
can directly measure the intensity of one or more of them, avoiding a second FFT
and further processing. An example of the procedure is shown in Fig. 3. In the upper
side, four noisy signals are plotted in the time domain as they are acquired, whose
intensities of the absorption are in the ratios: 0.2 : 0.5 : 1 : 2; in the center we plotted
the corresponding FFT plus the one of noise without any signal; while in the bottom
we plotted the intensity of the most intense harmonics (here the 5th), after
subtraction of the corresponding background, versus the original signal intensities,
showing how the original ratios are linearly retrieved in the transforms. In this case,
it can be noticed that the main part of the noise, due to fringes, is concentrated
between the 15th and 20th harmonics, well separated from the signal harmonics
(below the 10th). Apart from fringes, we have white noise as well, which is
homogeneously distributed all over the spectrum, and only that part lying in the
same interval of harmonics of the signal still aects the nal measurements.
In order to optimize the implementation of this method, we rst of all subtract
from the signal its average, so that the zeroth harmonic is zero. We also nd that
there is an optimal value for the amplitude of the frequency sweep of the laser, in
order to have the best S/N ratio. Of course, with this kind of signal analysis, it is
possible to perform only relative measurements, as the information about the
absolute strength of the absorption is lost. In order to overcome this limitation, some
other data are necessary. The results are normalized with respect to the light power
on the detector and the comparison with a known gas mixture gives the nal value.
This method permits to increase the signal-to-noise ratio even up to one order of
magnitude respect to the measurements on the raw acquired signal, as other digital
ltering techniques do, but in our case, the processing is less time consuming,
because a second FFT for returning in the time domain and other least squares t are
avoidedFso very high acquisition rates can be achieved.
 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551 543

Fig. 3. Test of the method: four noisy signals (top), their Fourier transforms with the transform of noise
without signal (center), and plot of the transformed signal intensities versus original intensities (bottom).

7. Calibration

The calibration procedure is a critical point of all instruments of this kind. The
ideal procedure should be fast and automatic, without requiring sample mixtures,
and performed without conditioning the external environment. As an example of the
last requirement, we can consider an analyzer measuring along the chimney of an
industrial plant, as the one described in the next section. It is obvious that the
calibration cannot require the plant to be turned o. We try to match as close as
possible these requirements.
First of all, we assume that the instrumental response linearly follows the gas
concentration along the whole measurement range. This is well satised because, as
said above, we usually work with maximum absorbances which are below 1%.
Moreover, the entire processing of the acquired data relies on linear algorithms.
From this consideration, we can conclude that only two measurements, one at zero
concentration level and one at full scale level, are sucient to fully characterize the
behavior of the instrument.
544 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551

The measurement at zero level is made by moving the central frequency o0 of the
sweep far from absorptions. For this purpose, the laser temperature is changed.
Then, the laser frequency is set again to the line center. A short, sealed optical cell
(B1 cm) is placed across the laser beam. This cell is lled with a known mixture of
the target molecule with an inert gas, at such pressures to reproduce at the best the
same lineshape conditions of the measurement.
Let us examine this aspect in some detail. From the theory of absorptions, it
descends that, for a given line and a given length, the integral of absorbance versus
frequency is a function of concentration only. Moreover, the shape of the line
(Doppler, Lorentz, Voigt) depends only on the ratio between the Doppler and the
Lorentz widths. So, we use a buer gas in order to obtain the right Lorentz width,
and this ensures that all the other line parameters are correct. In order to obtain the
equivalent concentration, we rst need to know the linewidth in the real
measurement conditions and the line broadening coecient for a suitable buer
gas. Then, we ll the cell with the target molecule and the buer gas with partial
pressures such that they give the right Lorentz broadening. The equivalent
concentration is the partial pressure of the target molecule in the cell divided by
the pressure of the atmosphere in the experimental conditions, scaled for the inverse
of the optical paths. If necessary, the temperature must also be taken into account,
due to the change in the linestrength. The concentration in the cell must be such as to
reproduce the right concentration along the real measurement path. For instance, if
the detection is performed inside a multipass cell with 30 m optical path, the
concentration in a 1 cm long calibration cell will be 30.000 times that of full scale.
This usually leads to calibration concentrations that are very easy to obtain in a
reliable way. The buer gas is usually argon or nitrogen, whose foreign broadening
coecients are very often higher than that of air. This procedure nd its explanation
in the fact that the use of a single bottle of buer gas is more safe and reliable than
the use of, for instance, synthetic air. In the case of NO, the oxygen of the air would
destroy the sample in the cell. Moreover, it is easier to seal cells with inner pressure
below room pressure.
Coming back to calibration, the increase of the instrumental signal for unit increase
of concentration is determined by the increase in the signal due to the insertion of the
cell along the optical path. In this way, this coecient can be obtained also if the
concentration of the target molecule during calibration is not zero.

8. Two applications

In this section, we briey present two examples of how the previous discussion has
been translated in practical instruments.

8.1. HCl in industrial emission

One of the molecules to be monitored in industrial emissions is HCl. This gas can
be either a prime material or, most frequently, a by-product of the industrial process.
 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551 545

Incinerator plants are a typical example, due to the combustion of plastic. Rules
about polluting emissions are becoming more and more severe, and we could arrive
at a point that the detection limits of the present analyzers could become
unsucient. So, a dierent approach should be adopted for this measurement.
Moreover, the optical techniques like those described here can be more simple than
the present ones, as they do not require one to sample the exhaust gases and to carry
them some tens of meters apart from the chimney. So we developed a rst prototype
of HCl analyzer to be mounted directly on the chimney. A schematical drawing of
the instrumental setup is shown in Fig. 4. The device is formed by two parts, to be
mounted on the opposite ends of a diameter of the chimney, where two holes allow
the laser beam to cross the stack. The optics were protected against the exhaust gases
by two heat-resistant glasses placed just outside the holes. The launching optics box
contains the laser, the reference arm of the analyzer and a visible optical line for
the eld alignment. The receiving optics is formed by two mirrors and the main
detector.
We performed some tests on the molecule of HCl in the laboratory [27,28] and we
prepared a reference and a calibration cell. While for the reference cell, there are no
problems for the preparation of the mixture, serious problems exist for the
calibration cell, due to the reactivity of HCl and to the particular measurement
conditions to be simulated. The exhaust gases of an incinerator chimney contain a
large amount of CO2 and water (about 15% for each gas), at the temperature of
1801C for the plant at which we performed the test. While it is relatively simple to
verify the eects of CO2 on the width and position of the absorption lines of HCl, it
is impossible to do the same with water. So we decided to simulate the linewidth in
air at the right temperature, and to verify on the eld the validity of this

Fig. 4. Scheme of the instrument for the monitoring of HCl concentration in industrial emissions: LB
Launching Box; RB Receiving Box; ML Measurement Laser; AL Alignment Laser; Dx Detector; M
Mirror; BS Beam Splitter; RC Reference Cell.
546 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551

approximation. The concentration in the calibration cell has been chosen such as to
give an absorbance of about 1%. In this way, we could verify by direct absorption
that the cell did really contain the correct amount of HCl. A recording of the
instrument is shown in Fig. 5. The laser power has been recorded in order to
understand its eect on the performances of the analyzer. There was no wind during
measurements, and no gas came out through the holes. So the actual absorption path
was the inner bore of the chimney, 86 cm. The spikes before 12:00 are due to the
setting of the instrument. The disturbance at 4 p.m. was due to powder emitted in
one of the burners of the plant during a maintenance operation. It was necessary to

Fig. 5. Measurement of HCl concentration in the chimney versus time. Up: readings of HCC-01 and of
the conventional instrument; Down: laser power onto the detector.
 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551 547

clean the protecting glasses after this event. It can be seen that the readings of our
instrument agree with those from the conventional instrument apart from a factor of
about 2. This feature is common to the measurements of other days. We have
investigated the reasons for this discrepancy, and found that, as expected, they lie in
the calibration cell. The registered waveforms dier from the expected ones. So we
are planning a spectroscopical measurement directly on the chimney in order to get
the right line prole.
The detection limit of this prototype is 1 mg/nm3 m (the longer the detection path,
the lower the limit). For conventional instruments, the detection limit is not aected
by the diameter of the chimney. On the contrary, instruments like the one described
can take advantage of wider bores, and the optical setup can realize a round-trip or
even a three-pass conguration for the beam. Of course, a standard technique for the
separation of the optical components from the inner part of the chimney must be
adopted. By taking into account the results of the present tests and the foreseen
improvements in the various features of the analyzer we expect to reach a detection
limit of 0.3 mg/nm3 m.

8.2. Entomological application

The metabolism of insects, particularly during their metamorphosis phases, can be

studied through the quantitative analysis of the CO2 that they produce. The amount
of carbon dioxide released per unit time is very small and the emission occurs either
continuously or in bursts, so a suitable sensitivity and an integration time of a few
seconds are required. The insect is placed inside a sealed optical cell, whose CO2
concentration is monitored through the absorption of a laser beam around 2 mm. The
sensitivity is related to the volume of the cell. In order to perform measurement over
some days, before suering the eects of a very high absorbance, the cell volume was
chosen to be 500 cm3 ; which leads to a required sensitivity of B1 ppm. A scheme of
the instrument is shown in Fig. 6. The total path of the laser beam is 115 cm, of
which 98 are in the sealed cell. For CO2 ; a reference arm is not necessary, as the
normal concentration of this gas in the ambient air is such that the system can nd
and lock to the absorption line without problems. As for the previous case, we
performed preliminary spectroscopical analysis [29,30], and prepared a calibration
cell for the characterization of the instrument. For this operation, no insect was
inside the absorption cell, and the room was kept closed during the whole
measurement. After some hours, the room concentration reached stability. In Fig. 7,
the results of these characterizations are shown. During the two hours before
opening the room the concentration was stable within 0.9 ppm. The integration
time is 10 s, corresponding to an average over 60 acquisitions. An example of an
actual measurement is shown in Fig. 8. A female Osmia Cornuta within its
cocoon was put inside the cell. The insect was in the latest phase of its
metamorphosis. The CO2 emission can be observed, which proceeds by bursts,
and not continuously. The rst signicant scientic results of this activity have been
presented in Ref. [31].
548 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551

Fig. 6. Scheme of the instrument for the monitoring of CO2 production by insects.

Fig. 7. Test of the stability of the instrument. For details, see text.

9. Conclusions

We have described the core structure of our instruments and some of the obtained
results. We want to stress again that we know that a further decrease of the
instrumental noise level would be possible, for instance by using optical insulators at
the laser output or by adding a measurement arm for a better subtraction of the laser
noise. Unfortunately, this would make the systems more complicated and expensive,
 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551 549

Fig. 8. Example of results obtained with the instrument. For details, see text.

and this is beyond of our philosophy. On the contrary, in the near future, we are
going to test some hardware improvements, which will make the electronics faster
and smaller.

Acknowledgements

Many thanks are due to all the people who in dierent ways contributed to the
development of these instruments: Prof. M. Inguscio and Prof. M. Rosa-Clot for
helpful discussions; Dr. C. Corsi, Dr. G. Modugno and Dr. M. Gabrysch for the
development of the TTFM technique; Dr. C. Piccolo and Dr. C. Nardini for the
spectroscopical measurements, Prof. R. Amendolia, Dr. A. Tozzi, Mr. M. Giuntini
and Mr. M. De Pas for the electronics.
550 F. DAmato, M. De Rosa / Optics and Lasers in Engineering 37 (2002) 533551

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