Appl. Phys.

B 78, 103109 (2004)

Applied Physics B

DOI: 10.1007/s00340-003-1342-0

Lasers and Optics

a. zybin1,u
y.a. kuritsyn2
v.r. mironenko2
k. niemax1

Cavity enhanced wavelength modulation

spectrometry for application in chemical
analysis
1 Institute of

Spectrochemistry and Applied Spectroscopy (ISAS), Bunsen-Kirchhoff-Strasse 11,

44139 Dortmund, Germany
2 Institute of Spectroscopy, Russian Academy of Sciences, 142190 Troitzk, Moscow reg., Russian Federation

Received: 30 April 2003/Revised version: 10 September 2003

Published online: 13 November 2003 Springer-Verlag 2003

A simple and robust absorption technique is developed which combines cavity enhanced absorption spectroscopy and wavelength modulation spectroscopy and measures the integrated output of unlocked cavities. The detection
power of the technique is affected by peculiarities of the laser injection into a cavity causing excess noise which exceeds the shot
noise. The noise and ways for its reduction are discussed. The
new method is demonstrated by absorption measurements of excited carbon atoms in a microwave induced plasma. Preliminary
detection limits equivalent to optical depths below 106 were
obtained.

ABSTRACT

PACS 42.55.Px;

42.62.Fi; 42.60.Mi

Introduction

Absorption techniques are of great interest for

spectral analysis of elements and molecular species, since
they are known to be robust in respect to chemical and
physical effects which affect the accuracy of the analysis.
Recently, the development of new and more powerful absorption methods was particularly stimulated by the use of
diode lasers which are compact, simple to operate and whose
wavelength can be easily and rapidly tuned in wavelength.
Different modulation techniques have been developed which
allow absorption measurements near to the shot noise limit.
The present paper reports on a new approach where the diode
laser wavelength modulation (WM) method is combined with
cavity enhanced absorption spectroscopy. The new technique
has the advantage of being relatively simple and suitable also
for strong absorption transitions which tend to show optical
saturation inside cavities. This is, in particular, important for
extreme trace analysis of element where the strongest optical
transitions are selected for analysis to be able to measure the
lowest possible concentration of atoms in the absorption path.
In cavity enhanced absorption spectroscopy an absorption cell is integrated into a resonance cavity with a high
finesse F . Photons in the cavity pass through the absorption media many times. As a result, the effective absorption
u Fax: +49-231/1392-120, E-mail: zybin@isas-dortmund.de

length increases by a factor of F/ as compared to the cavity length. The cavity enhanced absorption methods are, e.g.
integrated cavity enhanced spectroscopy [1, 2] or cavity ringdown spectroscopy [3], etc. Below we consider the methods
based on the measurement of the integrated cavity transmission spectrum.
It is well known that the transmission curve of a Fabry
Perot cavity consists of a series of peaks at the resonance
frequencies of the cavity. To perform the absorption measurements it is desirable to have a flat transmission baseline.
This can be done in two ways. The first approach implies that
the cavity is actively locked to the laser wavelength (further
laser-locked spectroscopy (LLS)). The cavity mode (and, consequently, the laser wavelength) tunes over the line profile and
a weak absorption line can be measured. The enhancement of
the absorption is a factor of 2F/ . Cavities with commercially
available mirrors can reach a finesse of F 105. By combining this technique with diode laser frequency modulation
technique and heterodyne detection a relative absorption below 1012 s1/2 can be measured [4], which corresponds to the
shot-noise limited detection combined with cavity enhanced
absorption length. However, it should be noted that the experimental arrangement for LLS is complex, expensive and
not stable enough for routine application inside or outside of
chemical laboratories.
A substantially simpler way is to use an unstabilized cavity and averaging procedures. Here, the laser wavelength is
scanned over the absorption lines while there is no locking of
laser and cavity. The coupling occurs only if the laser wavelength coincides with the cavity modes. To overcome large
fluctuations of the baseline the cavity length is modulated applying a piezo-transducer [1, 2, 5, 6]. Since the cavity is not
stabilized and its length varies from scan to scan, the cavity transmission spectrum is well averaged during multiple
line scans, and the absorption line shape and intensity can be
measured. This technique is usually referred to as cavity enhanced absorption spectroscopy (CEAS).
An analogous method is the integrated cavity output spectroscopy (ICOS), developed by OKeefe et al. [7]. This approach implies that the wavelength of the diode laser can be
modulated with a much higher frequency than the cavity by
piezo-modulation. Thus, one can obtain a flat transmission
baseline even during one scan.

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Applied Physics B Lasers and Optics

It should be noted that the noise characteristics of the baseline in both methods have not yet been discussed in detail.
At first glance it seems that shot noise limits the method.
Unfortunately, this is not the case, since there are substantial intensity fluctuations caused by the random character of
the injection of laser power into the cavity. These fluctuations
cause a noise which exceeds the shot noise by orders of magnitude. In a recently published paper [8] these fluctuations
are well explained and investigated. A model for quantitative
characterization was developed. Below we will discuss the
impact of this noise on the detection power of the integrated
cavity methods (see Sect. 2.3).
If methods are applied which are based on multiple wavelength scanning full spectroscopic information on the scan
range can be obtained. For analytical applications, however,
only the absorption at one point, namely at the center of the
analytical line, is of importance. This allows one to apply
the wavelength modulation (WM) technique, which is simple and widely used by trace analysis. Here, the wavelength
of a diode laser is tuned to the center of the absorption line
and then modulated over the absorption line profile with relatively high frequencies with a modulation amplitude comparable to the width of the absorption line. The absorption
signal can be measured on the modulation frequency or its
harmonics by a phase-sensitive technique. The detection limit
of the method is determined by the noise of the Fourier components of the light. In the most favorable case, it is possible
to measure the laser shot-noise-limited absorption of about
107. The WM is often used for the detection of a low concentration of atoms and molecules using tunable diode lasers
(DL) [912].
It should be noted, that the classical ICOS and CEAS
methods are comparable with the WM method from the viewpoint of detection power. By appropriate signal treatment and
when the repetition rate of scanning is equal to that of WM, the
detection limits of both methods are comparable. However,
the WM-technique is simpler. On the other hand, it is easier to
increase the WM frequency than the scanning repetition rate.
As we show later (see Sect. 2.3) this plays an important role
for noise reduction.
A condition for an effective enhancement in a cavity is
that non-selective absorption does not lower the finesse of
the cavity. Unfortunately, this condition is not fulfilled by
two established and often used atomizers in atomic absorption spectrometry (AAS), the analytical flame and the graphite
tube furnace. However, low-pressure plasmas, such as a lowpressure microwave induced plasma (MIP), can be adequate
atomizers for intra-cavity measurements since background
absorption can be neglected. Here, absorption spectrometry
with a diode laser can measure not only elements from its
ground states but also electronically excited atoms. For example, it was shown that elements such as hydrogen, oxygen
or halogen elements could be measured with high detection
sensitivity by WM-absorption spectroscopy, in particular, if
they are measured in long-lived and metastable levels [13, 14].
A further possible improvement of the detection power of
the element-selective diode laser absorption techniques in low
pressure plasmas by wavelength modulation integrated cavity output spectrometry (WM-ICOS) is the motivation of the
present paper.

2
2.1

Theory
Spectrally integrated cavity transmission and
enhancement

A simple description of the ICOS can be done in

terms of photon fluxes reflecting in or passing through the
cavity. A more strict description of the integrated cavity transmission is given in the Appendix.
Let us suppose that it is possible to neglect the interference
of light. A photon flux with power P0 passes the entrance mirror and is reflected repeatedly between the cavity mirrors. It
is gradually weakened on each round trip by small radiation
losses due to the mirrors transmission. Adding the intensities
of the beams passing the output mirror at a given time, one get
the power of the transmitted photon flux



P0 T 2
Ptr = P0 T 2 1 + R2 + R4 + . . . =
,
1 R2

(1)

where T and R are the transmittance and reflectivity of the

mirrors, respectively.
For a high finesse cavity 1 R2 2(1 R) and Ptr
P0 T/2.
If there is line absorption inside the resonator the transmitted power can be written as
P0 T 2 e()l
P0 T 2



R2
1 R2e2()l
(1 R2) 1 + 2()l 1R
2


R2
P0 T 2

1 2()l
,
1 R2
1 R2

Pt =

(2)

where () is the absorption coefficient at frequency , l is the

R2
length of absorbing media and 2()l 1R
2  1.
Equation 2 shows that multiple passing of the light through
absorbing media in a high-finesse cavity enlarges the absorp2R2
tion pass by a factor of G = 1R
2 and the effective length l eff
2

2R
becomes leff = 1R
2 l . For 1 R  1 the effective enhance1
and
ment factor is approximately equal to 1R

leff =

l
= c,
1 R

(3)

l
is the cavity ring-down time. It should be
where = c(1R)
mentioned that the enhancement by ICOS is a half of that obtained by laser-locked measurements [8].
Using (1) the efficiency of coupling of the diode laser radiation with the spatial modes of the cavity can be estimated.
Taking into account losses, (1) has to be modified:

Ptr = P0

T2
,
1 R2

(4)

Introducing 1 R2 2(1 R) which is valid for high finesse

mirrors
(1 R) 2Tcav
=
,
(5)
T2
where Tcav = Ptr /P0 is the integrated cavity transmission
which can be found experimentally.
In the present experiments the measured value = 0.75
which is an adequate value taking into account that no laser
beam correction was applied.

ZYBIN et al.

Detection limit comparison of ICOS and

cavity-locked absorption measurements

Taking into account the reduction of the integrated

power for ICOS Ptr = P0 T/2 one can estimate that in the case
of shot noise limitation the detection limit improvement B is
proportional to the square root of the signal enhancement G .
For ideal mirrors (T = 1 R)


B = G T/2 = G/2.
(6)
Note that the improvement of the detection limit would
be proportional to G if the laser was locked to the cavity
provided that the input power is the same. This is significantly better than in ICOS. However, the useful power is often
limited by optical saturation of the transition, in particular,
in atomic spectrometry. In this case one has to take into account that by the same input power the integrated intracavity
power for the ICOS is a factor of G lower than in a measurement with a locked cavity. Therefore, the input power in ICOS
can be increased by the factor G before a comparable saturation is achieved. The corresponding increase of the output
power reduces the relative shot noise and the detection limits should be of the same order of magnitude in both cases
considered. However, it should be stressed that this consideration is only valid when the lines are pressure broadened
and the mode intervals are smaller than the line width, so that
the power in each cavity mode is distributed over the mode
interval. Furthermore, the tuning time of the laser between
two neighboring cavity modes has to be smaller than the ringdown time.
In the present experiment no optical saturation was observed up to an intra-cavity power of 1 mW and a transmitted power of about 60 nW. In contrast to that, an essential
saturation was observed at an intra-cavity power of 0.01 mW
in [15]. Taking into account the G value of about 105 in [15]
this corresponds to an output power less than 0.1 nW.
2.3

Mode injection excess noise

By the calculation of the detection limit improvement for ICOS in Sect. 2.1 the enhanced signal was related
to the shot noise. However, in measurements by ICOS and
CEAS the noise equivalent absorption is usually substantially
higher than expected taking into account the shot noise limitation only. As was already mentioned in the Introduction, this
discrepancy is obviously due to excess fluctuations caused by
laser phase noise. The mechanism of this noise is well analyzed in [8]. Its origin can intuitively be understood by considering fast random fluctuations of the optical frequency of the
laser radiation inside the laser line width ( 2 MHz for a free
running laser, 100 kHz for a laser with external cavity [8]).
Such fluctuations produce a constructive intracavity interference (which manifests itself as an effective injection) only if
the instantaneous frequency falls inside the cavity mode. By
scanning the laser line over a spectral cavity mode the effective injection only occurs at a random part of the overlapping
time of both (laser and cavity) line profiles. This time can be
shorter or longer that causes fluctuations of injected power by
each injection act. Figure 1 illustrates these fluctuations by
one scan over seven cavity modes.

105

0,0

photomultiplier signal, arb. units

2.2

Cavity enhanced wavelength modulation spectrometry for application in chemical analysis

-0,2

2
1
-0,4

5
-0,6

6
0

40

80

time, s

120

160

FIGURE 1 Fluctuation of the injected power obtained by one scan of the

laser wavelength over seven TEM00 modes (fsr 0.08 cm1 )

Following the model developed by [8] one can estimate

the value of excess noise by WM-ICOS. The signal of a photodetector during the integration time T consists of K = TN
peaks were N is the quantity of interactions of laser radiation with cavity modes per second. In the case of modulation
at a frequency of f over n modes N = 2 fn . Following [8],
the relative dispersion of a single peak value depends on the
modulation velocity and ranges within 0.15 0.5 depending on the modulation rate. As a result of this fluctuation the
relative dispersion of the current integrated over time T is approximately


I
= 1/NT = 1/(2 fnT)
=
(7)
I
The noise considered can be reduced by diminishing the
bandwidth of the registration, in other words, by increasing
the detection time.
For T = 1 s, f = 7 103 Hz, and n = 5(mod 2Doppl.
= 1.5 GHz) according to [8] 0.15 and (7) gives =
6 104 s1/2 .
As one can see from (7), an increase in frequency and the
number of modes n can improve the sensitivity. The value n
can be increased by a slight misalignment of the laser beam
with the cavity. The S/N improvement of about a factor 23
was achieved in our measurements by slight misalignment of
the laser beam.
Another way to decrease the number of modes is a socalled off-axis coupling. Thereby, the FSR decreases dramatically and in limiting case the cavity modes amalgamate so that
the effect disappears which was discussed in Sect. 2.3. This
approach was investigated in details in [16, 17]. It provides excellent sensitivity. Unfortunately, it requires a relatively big
diameter of the absorption cell and could not be used in our
measurements applying a plasma in a thin capillary.
The procedure to estimate the noise of WM-ICOS as
suggested in present paper can also be applied for ICOS
if the scanning rate is used instead of the modulation frequency f in (7). It is interesting to see that measured noise
data from different ICOS publications are in good agreement
with the theoretical noise obtained by formula (7). For instance, the noise level found in [18] was I/I0 of 3 106.

106

Applied Physics B Lasers and Optics

This corresponds to an enhanced (multi-pass) absorption of

2.3 103 s1/2 taking into account an enhancement factor of
1300 derived from the ring-down time. The calculated value
according to (7) gives 2.4 103 s1/2 (n = 130, f = 15 Hz).
In another publication [5] the measured minimum absorption was 4 103 s1/2 . Theory gives 2 103 s1/2 . The wavelength scans in [18] and [5] were of the same order of magnitude ( 0.15).
3

Experiment

Figure 2 shows schematically the experimental

arrangement for ICOS with wavelength modulation. A freerunning laser diode (Spectra Diode Labs 5311-G1: =
806 nm; P = 100 mW) was used for the measurements of
water absorption. For the measurements of carbon, a diode
laser from Hitachi (HL 8325G: = 830 nm, P = 40 mW)
was used. For water the absorption transition at 803.43 nm
was selected from the HITRAN 2000 database while carbon
was measured at the 833.515 nm line (transition: 2 p3s 1P10
2 p3 p 1S0 ).
A Faraday isolator was placed in the beam directly in front
of the laser source in order to minimize optical feedback from
the cavity. The laser radiation was coupled into a high finesse
optical cavity formed by two identical concave mirrors with
a diameter of 8 mm. The radius of curvature of the mirrors
was r = 50 cm and the reflectivity R > 0.999 (Lyertec GmbH,
Mellingen, Germany). The mirrors were mounted 55 cm apart
and could be aligned individually. A quartz capillary with the
inner diameter of 0.4 cm was placed between the mirrors to
provide a sealed volume inside the cavity. The capillary was
placed in a Beenaker-type resonator for the microwaves for
the measurement of excited carbon atoms in plasma. A microwave power (up to 300 W) was produced by a 2.45 GHz
generator (Feuerbacher GMW 24-303 DR).
The injection of the laser radiation into the cavity was
optimized observing the integrated cavity transmission. No
optics was used to correct ellipticity and astigmatism of the
laser beam and to suppress transversal modes. The cavity was

not stabilized and was mounted on a normal, unstabilized

laboratory table. It should be stressed that a perfect optical
alignment is not necessary in ICOS which makes the application very easy. Moreover, the improvement of S/N ratio
by a factor of 23 was obtained by a slight misalignment of
the coupling of laser radiation and spatial cavity mode. This
misalignment which reduced the integrated cavity transmission by about 30%, caused an increase of the number of laser
modes due to the appearing of transversal cavity modes and,
therefore, a reduction of the noise according to Sect. 2.3. It
was checked that the misalignment did not caused a measurable reduction of the enhancement factor even when the
integrated transmission was reduced by the misalignment by
a factor of 4.
The diode laser was powered by a commercial temperature and current supply driver (Profile PRO 800). The laser
wavelength was modulated around a center wavelength with
a frequency of f 1 = 6 kHz using a function generator by
Wavetek (model FG-5000). The peak to peak amplitude corresponded to a wavelength tuning of about 6.5 pm. Additionally
the center wavelength of the laser diode was scanned at lower
frequency (0.01 10 Hz) using a function generator (Hameg
HM 8130). In order to increase the detection power, in particular for one-pass absorption measurements, the plasma was
also modulated (turning the plasma on and off with a frequency in the kHz range). The technique of double modulation is described in detail in [13]. The plasma modulation
frequency was f2 = 5.5 kHz applying a square wave generator
(Wavetek, model FG-5000). The signal was phase-sensitively
detected at the sum frequency f = 2 f 1 + f2 as described
in [13].
The transmitted radiation of the cavity was directed on
a diffraction grating (1180 grooves/mm) and the first order
reflection (15% reflectivity) was detected by a photomultiplier (Hamamatsu R928) loaded with a 50 resistor. The
photomultiplier signal was processed with a lock-in amplifier
(Stanford Research 830). The laser wavelengths were measured using a 4 step Fizeau wavemeter (ATOS: LM007).
The quality of the cavity mirrors was tested by measuring the cavity ring-down decay time . The -value found
(2.9 106 s) corresponds to mirror reflectivities of 0.99937.
The transmission of one mirror was of T = 1.4 104, hence
the loss L = 4.9 104. Taking into account these data one
should expect an enhancement in ICOS due to multiple passing of about G = 1600, so that the effective absorption path
leff = c would be 8.8 104 cm. It should be noted that during about four weeks work with the plasma no measurable
reduction of the ring-down time was observed, although no
particular protection of the mirrors, e.g., by gas fluxes, were
applied.
4

FIGURE 2

Experimental arrangement

Results and discussion

The applications of diode laser atomic absorption

spectroscopy for the detection of molecular species in lowpressure plasma is discussed, e.g., in [13, 14]. The molecules
introduced with the plasma gas into the plasma dissociate and
excited atoms are created which are measured by laser absorption. A 3 -detection limit of 2 107 relative absorption
was obtained in microwave-induced plasma (MIP) applying

ZYBIN et al.

Cavity enhanced wavelength modulation spectrometry for application in chemical analysis

the double modulation technique (diode laser wavelength and

plasma) [13]. This is near to the shot noise limit for the applied intensity of about 2 mW. Detection limits in the sub-ppb
range were obtained for elements which have absorption lines
from metastable levels in the wavelength range of commercial laser diodes. These long-lived levels are relatively well
populated in low-pressure plasmas. Unfortunately, many important elements, such as C or P, do not have such favorable
levels. For these elements absorption lines from short-lived
levels have to be used. These levels are a factor of 101000
less populated in low-pressure plasmas than metastable levels. Therefore, a further improvement of the detection limit by
means of cavity enhanced absorption is especially important
for the analysis of these elements. The lifetime of the initial level of C which was probed by absorption in the MIP
is relatively short ( = 30 ns [19]). The absorption signal of
the C 833.515 nm line was about two orders of magnitude
smaller than that of the 837.594 nm Cl line which starts from
a metastable state.
The technique was tested and optimized without the
plasma choosing the weak water line at 803.43 nm. The
HITRAN 2000 database gives the following parameters for
this line:
Frequency
Intensity
Weighted transition
moment-squared
air-broadened HWHM

12 443.2234 cm1
1.217 1024 cm1 /(molecule

cm2 ) @ 296 K

4.188 109 Debye2

0.0969 cm1 /atm @ 296 K

the cavity were used to check the absence of optical saturation

of the absorption line in the cavity.
It is interesting to observe a slight decrease of the 2 f signal
beyond 300 mbar (see Fig. 3). 300 mbar is about the pressure where the line shape transforms more and more from
a Doppler profile (constant line width) to a Lorentzian profile
whose width depends linearly on pressure. According to [20]
the peak height of the 2 f signal for Lorentzian profile is at the
factor of 1.37 smaller than that for the Gauss one. Therefore,
an influence on the 2 f signal appears at the transition from
Doppler to Lozentzian broadening.
The noise at the detection frequency was about 3.2
104 s1/2 what is slightly better than the estimate in Sect. 2.3
thanks to the misalignment of the laser beam as discussed in
Sect. 2.3. This signal corresponds to the enhanced absorption
of about 103 s1/2 (one pass absorption 7 107 s1/2 ).
Figure 4 shows a scan over the water absorption line at
9 mbar air pressure which corresponds to about 0.05 mbar water pressure. It can be estimated that the S/N ratio for 3 103
absorption is about 10 at a lock-in time constant of 10 s.
4.1

Measurement of excited carbon atoms in

a microwave induced plasma

The microwave-induced plasma was operated in

a mixture of helium and freon-22 (CHClF2 ) flowing through
a quartz capillary. The mixture was prepared in a 10 gas
bottle at a pressure of about 6 bar. The freon molecules dissociated in the plasma and the absorption of exited carbon
atoms at = 833.515 nm was observed. The absorption signal was measured first in the one-pass mode (with Brewster
windows) and then in the cavity enhanced mode at the same
plasma parameters. The plasma pressure was 30 mbar and
the microwave power 120 W. The flow rate of the gas was
about 1 m /min. The absorption measured in one-pass mode
was about I/I = 2.1 104 at a carbon concentration of
1.4 ppm. By cavity enhanced measurements an absorption of
about 0.3 was measured at the same concentration. This corresponds to an enhancement factor G of about 1400. The
G -value found experimentally is slightly smaller than expected one from the ring-down time, obviously due to a nonlinearity of the absorptionconcentration dependence accord-

2f signal, arb. units

The theoretical absorption in the line center corresponds to

A = I/I0 = 6 105 for 1 m absorption length at 0.6% H2 O
in air at normal conditions (relative humidity 40%).
Figure 3 shows the cavity enhanced absorption signal in
dependence on air pressure in the cavity. The modulation amplitude was adapted to the broadened line width at each pressure above 30 mbar. The air was flowing through the capillary
during the measurement to eliminate the influence of water
vapor coming from the walls of the capillary. The signal due to
water coming from the walls could be seen when the flow was
stopped, in particular at low pressure. Optical filters in front of

107

FIGURE 3

Dependence of the water absorption signal on air pressure

FIGURE 4 Scan over the water absorption line at 0.05 mbar water pressure.
Time constant of the lock-in amplifier: 10 s

108

Applied Physics B Lasers and Optics

The cavity enhanced wavelength modulation method was

demonstrated by absorption measurements of excited carbon
atoms in a microwave-induced plasma.

absorption signal, arb. units

70
60

Appendix
50
40

30
20
0.2

0.4

0.6

0.8

1.0

1.2

1.4

carbon concentration (as CHFCl 2) in He, ppm

FIGURE 5

Dependence of the carbon absorption signal on carbon concen-

tration

ing to LambertBeers law. It was carefully checked that the

relative absorption signal did not depend on the laser intensity
which means that no optical transition saturation took place.
Outside the carbon line the transmittance of the cavity was not
affected by the plasma which shows that the one-pass loss due
to non-specific absorption of the plasma was less than (1 R).
Figure 5 shows the absorption signal dependence on the
carbon concentration in the gas mixture. Unfortunately, the
He used was not pure enough to make measurements near
to the detection limit of the method. The enhanced noise
equivalent absorption was about 103 s1/2 which corresponds
to a one-pass absorption of 7 107. The intensity of
plasma emission on the photo-detector was comparable with
the integrated laser intensity but this did not contribute to the
noise because the laser phase noise exceeded the shot noise
significantly.
It should also be mentioned that this result is worse than
the absorption limit of 2 107 obtained by the double beamdouble modulation technique found in the earlier work of our
group [13]. However, the detection power of the proposed
ICOS-WM method can apparently be improved if mirrors
with higher reflectivity are applied.
5

Conclusions

In this work we have demonstrated that the sensitivity of the integrated cavity enhanced absorption method
can be substantially improved using wavelength modulation
technique. By choosing appropriate values of laser source
wavelength modulation parameters, it is possible to obtain
rather flat cavity transmission and determine second harmonic output signal in a fashion similar to that employed
in conventional WM-DLAS measurements. The detection
limit in one pass-absorption was found to be I/I0
7 107 s1/2 or 1.3 108 cm1 s1/2 with an enhancement
factor G = 1600.
The laser phase noise was shown to be the main limiting
factor by integrated cavity absorption measurements. Based
on the model developed in [8] the estimated noise is in a good
agreement with the experimental data.

Although the description in terms of photon fluxes gives correct values it is desirable for completeness to consider how the
light interferences are averaged under the action of modulation. If to consider an interference of fields, it is necessary to
summarize amplitudes as usually done in calculation of the
FabryPerot interferometer transmission. Let a radiation field
falling on a high-finesse cavity E = E 0 ei0 t , where 0 is the
angular frequency and E 0 the complex amplitude. The summation of the beam amplitudes leaving the resonator gives for
the transmitted light amplitude E tr



E tr = E 0 ei/2 T 1 + Rei + R2 ei2 + . . .
E 0 T ei/2
=
= K()E 0 ,
(A.1)
1 Rei
where
= 2kl =

4nl

(A.2)

and
Ptr |E tr |2 =

P0 T 2
.
1 + R2 2R cos()

(A.3)

Averaging over leads to

1
Ptr () =
2

2
Ptr () d =
0

P0 T 2
,
1 R2

(A.4)

i.e., exactly the same result as obtained earlier using the description of ICOS in terms of fluxes.
The role of averaging becomes clearer if it is made before
summation:
Ptr E tr E tr 


= P0 T 2 < 1 + Rei + Rei2 + . . .



1 + Rei + Rei2 + . . .

= P0 T 2
Rm+n ei(nm) 
m,n=0


P0 T 2
= P0 T 2 1 + R2 + R4 + . . . =
1 R2

(A.5)

Thus, interference components with m = n becoming zeroed

by the averaging over .
To be
more formal, let us consider the tunable radiation

E 0 (t) = E 0 ()ei2t d falling on a high-finesse cavity.

The radiation leaking out of the cavity is of the form

E tr (t) =

K()E 0 ()ei2t d,

(A.6)

ZYBIN et al.

Cavity enhanced wavelength modulation spectrometry for application in chemical analysis

with the spectral component |E tr ()|2 = |K()|2 |E 0 ()|2 .

After an averaging procedure over the mode interval one again
get the former result if () is a smooth function between the
modes:


P0 T 2
R2
Ptr
(A.7)
1

2()l
.
1 R2
1 R2
At fast wavelength modulation the cavity transmission
peaks will broaden. This follows from (A.6) or from the
 und
2
certainty principle t 1, d
t

1
and
t

1/
.
dt
dt
At sufficiently fast modulation the baseline will be flat.
ACKNOWLEDGEMENTS Financial support by the Deutsche
Forschungsgemeinschaft (project no. 436 RUS 17/93/01) is gratefully acknowledged.

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3 K. Busch, M. Busch, Eds.: An Ultratrace-Absorption Measurement
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