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Applied Physics B
DOI: 10.1007/s00340-003-1342-0
a. zybin1,u
y.a. kuritsyn2
v.r. mironenko2
k. niemax1
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
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.
104
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
(1)
R2
1 R2e2()l
(1 R2) 1 + 2()l 1R
2
R2
P0 T 2
1 2()l
,
1 R2
1 R2
Pt =
(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)
ZYBIN et al.
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
2.2
-0,2
2
1
-0,4
5
-0,6
6
0
40
80
time, s
120
160
106
Experiment
FIGURE 2
Experimental arrangement
ZYBIN et al.
12 443.2234 cm1
1.217 1024 cm1 /(molecule
cm2 ) @ 296 K
107
FIGURE 3
FIGURE 4 Scan over the water absorption line at 0.05 mbar water pressure.
Time constant of the lock-in amplifier: 10 s
108
70
60
Appendix
50
40
30
20
0.2
0.4
0.6
0.8
1.0
1.2
1.4
tration
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)
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)
K()E 0 ()ei2t d,
(A.6)
ZYBIN et al.
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.
REFERENCES
1 R. Peeters, G. Berden, G. Meijer: Am. Lab. 33, 60 (2001)
2 R. Engeln, G. Berden, R. Peters, G. Meijer: Rev. Sci. Instrum. 69,
37633769 (1998)
3 K. Busch, M. Busch, Eds.: An Ultratrace-Absorption Measurement
Technique in: Cavity-Ring-down Spectroscopy (American Chemical Society Symposium Series #720, Washington, DC, ACS 1999)
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