Optoelectronic system for NO2 detection

Zbigniew Bielecki*1, Piotr Pręgowski2, Jacek Wojtas1

1)
Military University of Technology, 2 Kaliski Str. 00-908 Warsaw - Poland
2)
PIRS Pregowski Infrared Services, 36 Zachodzącego Słońca Str. 01-495 Warsaw-Poland

ABSTRACT

This paper presents application of Cavity Ring-Down Spectroscopy (CRDS) and Cavity Enhanced Spectroscopic
(CEAS) techniques with blue laser diodes-based system for nitrogen dioxide (NO2) detection. CES technique bases on
integration of the light from a resonator. Since the integrated intensity is proportional to the decay time, the experimental
signal can be related to the absorption process. The minimum detectable concentration of the absorber for a specific
transition is inversely proportional to the effective sample-path length, and directly proportional to the minimum
intensity fluctuation detected by a receiving system. In the presented system, the blue laser diode was mounted in a
temperature-controlled housing. The light transmitted through the cavity was focused onto a PMT of H5783-03 type. The
detector signal enters a lock-in amplifier and next a computer with a 16-bit data acquisition board.

Keywords: Cavity Ring-Down Spectroscopy, detection of NO2.

1. INTRODUCTION

Cavity Ring-Down Spectroscopy has become a widely used technique in the optical absorption analysis of atoms,
molecules, and optical components. The technique allows the determination of total optical losses within a closed cavity
comprised of two or more mirrors. CRDS is a technique capable of making quantitative diagnostic of trace species in a
gaseous environment [1,2].
The method of CRDS is based on measurement of the time rate decay of a pulse of light trapped in a high
reflectance optical cavity. A laser pulse is injected into an optical cavity that is formed by two highly reflective mirrors.
Particularly when cavity mirrors of extreme reflectivity (i.e. more 99.99%) are available, the sensitivity limit for
detecting absorption is dramatically improved [3-5]. Here we will describe an experiment on detection of nitrogen
dioxide in free air using CRDS method.

2. ANALYSIS OF THE CRDS METHOD

The principle of CRDS method is based upon a measurement of the rate of decay of an optical resonator with a high
quality factor. It is schematically illustrated in Fig.1.

A laser pulse of about 30 ns duration is coupled into cavity, consisting of two highly reflecting (R>99.995%) mirrors. At
each mirror a small part (1-R) of the circulating power will be coupled out, while the remaining part is reflected back in
the cavity (Fig 2).

Pulsed _____ ______ __________________________ ______

[ laser [ Optics ] Et Optical resonator ]1
[Photoreceivej
Fig. 1. Scheme representation of the CRDS method

Detectors and Associated Signal Processing II, edited by Jean-Pierre Chatard, Peter N. J. Dennis,
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 L

12

R R
I-
1(T)
Mirror 1 Mirror2 TtSI
Fig. 2. Idea of CRDS operation

A small fraction of this light transmits through each mirror with each pass. This light is detected at the output mirror with
a photo multiplier and is monitored on a digital oscilloscope as a function of time. Figure 3 shows the detected light at
the output mirror. If an absorbing species is placed in the cavity the ring-down time will be shortened at that wavelength
where absorption occurs. The ring-down time is indirectly proportional to the absorbing coefficient of the species [6].

4%

'4,,
4%,
4%.

44,

x1
4,-.
-.4 4-.

I ftts]

Fig. 3. The detected light at the output mirror, where λ1 is the wavelength of the absorbance of the gas

If there is additional loss inside the cavity due the presence of absorbing and light scattering species, the light intensity
inside the cavity will still decay exponentially in time provided the absorption follows Beer‫׳‬s law
dI ⎛ c(1 − R) ⎞
= I⎜ + αc ⎟, (1)
dt ⎝ L ⎠
where L is the cavity length, R is the reflectivity coefficient of the mirror, c is the light velocity and α is the absorption
coefficient at the laser wavelength.

Solving equation (1) we obtain

⎡ c [(1− R )+αL ] ⎤
−⎢ ⎥t
I (t ) = I o e ⎣ L ⎦
= I o e −t / τ . (2)
where Io is the magnitude of the introduced light, τ is the cavity ring down time.

The cavity ring-down time is given by

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 L
τ= . (3)
c[(1 − R ) + αL ]

When the cavity is empty (α=0) the determining ring down-time is given by the reflectivity (R) of the cavity mirrors and
the cavity length (L)
L
τo = . (4)
c(1 − R )

By combining equation (3) and (4) we obtain [7]

L⎛ 1 1 ⎞
α (λ ) = ⎜⎜ − ⎟. (5)
c ⎝ τ (λ ) τ 0 (λ ) ⎟⎠

CRDS method is based on the determination of a time constant of the exponential decay of the laser light leaking out of a
optical cavity. Knowledge of the time constants of the empty cavity τo(λ) and the cavity filled with absorbing gases τ (λ)
respectively, allows the determination of the optical extinction.

Detection limit in the CRDS method dependence on the laser beam quality, the optical alignment, the mechanical and
thermal stabilities, aerosols and Rayleigh scattering and the mirrors contamination.

It is possible to use the measured absorption strength to estimate the concentration (N) of NO2 because

α =σ ⋅N , (6)
where σ is the absorption cross section.

From (5) and (6) we obtain the detectable concentration limit

L ⎛1 1 ⎞ L ⎛ τ 0 −τ ⎞
N= ⎜⎜ − ⎟⎟ = ⎜⎜ ⎟⎟, (7)
σ c ⎝ τ τ 0 ⎠ σ cτ ⎝ τ0 ⎠

where γ equals to (τ0 –τ)/τ0 is the relative precision of the CRDS time determination.

Assuming that relative precision of the CRDS time determination is equal γ, one achieves that detectable concentration
limit NLimit is described by the formula

γ
N Limit = . (8)
cσ (λ )τ 0

Figure 4 presents dependence detectable concentration limit NLimit and decay time τ on length of cavity L for the mirror
reflectivity equal to 0.99998 and the NO2 concentration equal to 50 ppm.

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 Fig. 4. Curve of dependence decay time τ and detectable concentration limit NLimit on cavity length L

Cavity Enhanced Absorption Spectroscopy (CEAS), modification of CRDS technique, is based on off-axis arrangement
of the optical cavity. In this configuration, the light is repeatedly reflected by the mirrors (like in multipass cells),
however, the reflection points are spatially separated. The off-axis design eliminates optical feedback from the cavity to
the light source. Moreover, in these configurations the light is many times reflected by the mirrors and it fills the whole
volume of the cavity. In comparison with ordinary CDRS, the integrating spectroscopy with off-axis cavity adjusting is
much less sensitive for the cavity misalignment caused, e.g., by the refractive index fluctuations due to turbulences or
small mechanical instabilities.

3. EXPERIMENTAL RESULTS

We used the experimental setup presented in Fig. 5. The optical resonator consisted of two concave mirrors which
reflectivity reached value of 0.99998 at the wavelength of interest (Fig. 6). Since the length of the cavity was about 60
cm it allows to observe the decay time even to 25 µs.

Gas inlet Gas outlet

1' 1k

Fig. 5. Experimental system

As a light source a 50 mW pulsed laser was used. It was working at 414 nm (Fig. 7) with 1kHz repetition rate and 30 ns
pulse duration. The laser radiation was directed to the cavity using the two mirrors.

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 0.00€ I I I I I

0.005

:: ::??::::::::::
400 410
X[nm]
420 430

Fig. 6. Mirrors characteristic curve

Due to pulsed character of the radiation used one can avoid various problem with the light modulation and the laser –
cavity mode coupling. The cavity is equipped with gas inlet and outlet, which were connected with the gas mixing
system. The system allows for precision gas mixing and establishing ordered NO2 concentration.

600E-'-03
500E+03 —4—4-—
co 4.OOE-'-03
:iy : : :

300E+03 .--L---- -- _J___!__i__J_

LL
:: "
200E+03

380 400 420 440 460 480

X[nm]
Fig 7. Laser diode spectrum

The output signal was detected with a photomultiplier of H5783-03 type equipped with the spectral filter eliminated
interferences. The signal was observed and recoreded with fast digital oscilloscope and the NO2 concentration can be
determined using Eq. (7). In order to achieve high precision of the decay time determination, the proper adjustment of
the cavity is necessary. Assuming 10% precision of the decay time determination the detection limit better than 10 ppb
was obtained. We were able to register 13 ppb of NO2 in the lab air. We expect that precision of the decay time
measurement can be increased in about one order of magnitude.

CONCLUSIONS

Spectroscopy is widely used for monitoring of pollutant gases in the atmosphere. Nitrogen dioxide is one of the most
important factor of atmospheric quality. Usually NO2 is detected by using the methods based on chemiluminescence,
which sensitivity reaches level of single ppb. Recent development of GaN (in Unipress – Poland) and InGaN laser diodes
provides opportunity to construct fully optoelectronic detector of this compound.
We found that the spectroscopic techniques based on CRDS can be easily applied for construction of fully
optoelectronic, portable NO2 detector which detection limit is comparable with detection limits of chemical detectors.

ACKNOWLEDGEMENTS

This article draws upon the work of colleagues at the Warsaw University and Institute of Applied Optics in Warsaw, and
we are particulary grateful for the contribution from Professor T. Stacewicz and dr. A. Czyzewski.

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* zbielecki@wat.edu.pl

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