UMEA UNIVERSITY Lab PM

Department of Physics April/May 2013

Cavity Ring-Down Spectroscopy

Detection of CO2 in air

Aim: To characterize a high finesse optical cavity and use cavity

ringdown spectroscopy for detection of CO2 in air.

Prerequisites: Intensive study of these lab instructions. All questions

marked with Question must be answered before coming
to the lab.

Lab instructions for the course: Laser-based spectroscopic techniques

aleksandra.foltynowicz@physics.umu.se
jonas.westberg@physics.umu.se
Department of Physics
Umea University
SE-901 87 Umea, Sweden
1 Introduction
In 1988, OKeefe and Deacon [1] introduced a new spectroscopic technique, cavity ringdown
spectroscopy (CRDS), which has significantly higher detection sensitivity than conventional
direct absorption techniques. CRDS is based on the measurement of the decay rate of the
light intensity leaking out of a high finesse cavity rather than the change of intensity due to
absorption. The high sensitivity stems mainly from the intrinsic insensitivity of CRDS to laser
power fluctuations and the extremely long effective interaction pathlengths (many kilometers)
that can be achieved using the optical cavity.
The basic principle of CRDS is that pulses of laser light that are coupled into the cavity,
which consists of two high reflectivity mirrors with non-zero transmission, are stored in the
cavity for a given amount of time and leak out on each reflection. The decay of the transmitted
power is exponential, and the decay time is inversely proportional to the losses in the cavity.
For an empty cavity the losses are given by 1 R, where R is the reflectivity of the cavity
mirrors, and the decay time is longer for higher reflectivity mirrors. Introducing an absorbing
medium into the cavity causes additional losses from the interaction of light with the absorbing
molecules, which thus shortens the decay time. The absorption coefficient can be determined
from a comparison of the decay times for a cavity with and without absorbers.
Although the CRDS technique was initially developed for pulsed laser sources it is also possible
to do it with continuous-wave (cw) lasers by sweeping the frequency of the laser quickly across
the cavity modes. In this lab you will get acquainted with the CRDS technique based on a cw
laser and use it to detect CO2 in air. You will also have the opportunity to familiarize yourself
with an optical cavity and to characterize some of its properties.

2 Theory
2.1 Cavity properties

R+T+A = 1 R+T+A=1

L
Figure 1: Schematic illustration of an optical cavity with length L. The mirrors have reflectivity
R, transmission T and losses A. In order to sustain a stable Gaussian mode inside the
cavity the curvature of the cavity mirrors has to match the curvature of the Gaussian
beam. Therefore at least one of the mirrors has to be curved.

A Fabry-Perot cavity consists basically of two mirrors with high reflectivity and non-zero
transmission, as shown in Figure 1. Only the light that is resonant with the cavity, i.e. satisfies
the standing wave condition, can be coupled into the cavity and transmitted through it. The
transmission spectrum of the cavity, shown schematicaly in Figure 2, consists therefore of a
series of modes with frequencies

qc
q = , (1)
2L

3
where q is the cavity mode number, c is the speed of light, and L is the cavity length. The
distance between two consecutive cavity modes is the so-called cavity free-spectral range (FSR),
which is visualized in Figure 2 and determined solely by the length of the cavity

c
. FSR = (2)
2L
The width of the cavity modes, c , is given by the ratio of the spacing of the cavity modes and
the cavity finesse, F , which in turn is determined by the reflectivity, R, of the cavity mirrors

R FSR
F = = . (3)
1R 2c

FSR

2c

Figure 2: Spectrum of the cavity transmission.

Question A laser with a wavelength of 1572 nm is resonant with a mode of a 60 cm long cavity.
What is the order of magnitude of the cavity mode number, q?

q .............................................................................

Question What is the FSR of a 60 cm long cavity?

FSR = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Question What is the finesse of a cavity with mirror reflectivity 0.99, 0.999, 0.9999?

R = 0.99 F = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

R = 0.999 F = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

R = 0.9999 F = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4
Question What is the cavity mode width for these three cases (cavity length of 60 cm)?

R = 0.99 c = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

R = 0.999 c = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

R = 0.9999 c = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.2 Cavity Ring-Down Spectroscopy (CRDS)

For simplicity the following description is based on a pulsed laser source, however, the same
principles and equations apply also to the case of a cw laser, which is used in this lab. First,
consider a laser pulse with power P0 that is coupled into the cavity, which comprises two high
reflectivity mirrors with equal reflectivities R. The pulse travels back and forth in the cavity
multiple times, and a fraction of it leaks out through the cavity mirrors on each reflection. The
transmission of a cavity mirror, T , is given by

T = 1 R A, (4)

where A includes the losses from scattering, absorption and diffraction in the cavity mirror coat-
ings. When the cavity is filled with an analyte with absorption coefficient (), the transmitted
power after n round-trips in the cavity is

2n
Pn () = Re()L P1 () = P1 ()e2n[ln R()L] ,

(5)

where P1 () is the transmitted power after the first round-trip, given by

P1 () = T 2 e()L P0 . (6)

Assuming high reflectivities of the mirrors, i.e. R ' 1, implies that ln R R 1 = (T + A),
which leads to the following expression for the transmitted power

Pn () = P1 ()e2n[T +A+()L] . (7)

The time for one round-trip of a pulse in the cavity is t1 = 2L/c, which implies that the pulse
leaking out of the cavity after n reflections will be detected at the time tn = 2nL/c. A detector
with a time constant that is larger than t1 will average over subsequent pulses and record a
ring-down event, i.e. an exponential decay of the transmitted power according to

P (, t) = P1 ()et/1 () , (8)

where 1 () is the decay time in the presence of absorber, given by

L/c
1 () = . (9)
T + A + ()L

5
The decay time in the absence of absorber [() = 0] reduces to

L/c L/c
2 = = . (10)
T +A 1R
This implies that the absorption coefficient, (), can be determined from the difference of the
reciprocal decay times multiplied by c according to

1 1
() = . (11)
c1 () c2

In conclusion, it is possible to determine the absorption coefficient, , by measuring the decay

times of the transmitted power of the light with and without absorber, respectively. Alterna-
tivley, 2 can be measured at a frequency far detuned from the molecular transition.
When a cw laser is used instead of a pulsed laser, a cavity ring-down signal can be observed
if the laser frequency is scanned around the cavity resonance at a high enough rate. In general,
the scanning rate should be so high that the laser interacts with the cavity mode over a time
much shorter than the ring-down (decay) time. In this way, not all laser power is coupled
into the cavity, but the laser frequency is moved away from resonance quickly enough so that
only light leaking out of the cavity is detected in cavity transmission. Figure 3 illustrates the
general behaviour of the CRDS signals as the laser frequency is scanned across cavity modes.
By fitting an exponential function to the decay of each cavity mode with and without absorbers
it is possible to determine the ring-down times 1 and 2 , which can be related to the molecular
absorption at the cavity mode frequency through equation (11).

Figure 3: Typical CRDS signals.

Question What is the ring-down time for an empty cavity with length of 60 cm and mirror
reflectivity 0.99, 0.999 and 0.9999?

2 = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6
Question Derive an expression for the empty cavity ring-down time in terms of the cavity
finesse and FSR (or cavity mode linewidth).

2 = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3 Experimental setup

fiber
ramp
laser laser function MatLab
controller generator

lens R+T+A = 1 R+T+A = 1 lens

collimator detector

L
Figure 4: Schematic illustration of the experimental setup.

The experimental setup is shown schematically in Figure 4. The source of light is a distributed
feedback (DFB) laser with a fiber coupled output working at 1572 nm. The laser wavelength is
controlled with a combined temperature and current driver. The driver has an external voltage
input that allows modulating the laser wavelength. A function generator is provided for that
purpose. The cavity is made of two mirrors with highly reflective dielectric coatings designed
for 1550 nm. The input mirror is flat whereas the output mirror is concave with a 1 m radius of
curvature. The mirrors are glued to a 60 cm long stainless steel tube that provides mechanical
stability and is open to air via two tubes. The fiber-coupled output of the laser is connected
to an output collimator, which provides a Gaussian beam profile. An optical isolator is used
to prevent optical feedback into the laser, i.e. it prevents the light reflected from the cavity to
go back into the laser, which would disturb its single mode operation. The Gaussian beam is
mode-matched to the cavity by a mode-matching lens (focal length of 1 m) placed at a correct
position prior to cavity. The light that is transmitted through the cavity is focused on an
InGaAs detector with a bandwidth of 5 MHz and a gain of 175 kV/W. The detector signal can
be observed on an oscilloscope or alternatively recorded with a fast acquisition card (10 MHz)
and stored on a computer for analysis.

4 Tasks
4.1 Characterize the cavity
1. Tune the laser to center current of 145 mA, which corresponds to a laser frequency far
detuned from any molecular resonances. Use the signal from the function generator to
sweep the laser frequency. Set the scan frequency to 10 Hz and adjust the amplitude so
that you can see many cavity modes. Are the cavity modes wide or narrow compared to
the cavity FSR? Is the signal stable and repeatable? If not, why?

7
 .......................................................................................

Now zoom into one cavity mode by decreasing the scan amplitude. Do you see the ring-
down signal? If not, you need to scan the laser frequency faster - increase the scan
frequency until you can observe clear ring-down signal.

2. Record the averaged ring-down signal with the provided program. Determine the decay
time from an exponential fit to the measured data.

2 = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3. From the measured ring-down time determine the mirror reflectivity, cavity finesse and
the linewidth of the cavity mode.

R = ............................................................................

F = ............................................................................

c = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.2 Measure CO2

1. Tune the laser current to 140 mA, which corresponds to a laser frequency close to the
resonance of a CO2 transition. Measure the ring-down signal and calculate the decay
time. How much did it decrease? What is the intracavity absorption due to the CO2
transition at this wavelength?

1 = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

()L = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2. Would direct absorption spectroscopy, which usually has a limit (0 L)min = of 103 , be
able to detect this signal?

8
 .......................................................................................

3. Decrease the frequency of the sweep to 10 Hz while increasing the amplitude to 600 mV
so that you see many modes again. Record the ring-down signals using the provided
program.
4. What is the on-resonance absorption of CO2 ?

0 L = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

5. This particular CO2 transition has a gas linestrength, S 0 , of 4.96 104 cm2 /atm. Cal-
culate the concentration, crel , of CO2 in air, using the relation

0 = S 0 crel p0 . (12)
where p is pressure in atm and 0 is the peak value of a Lorentzian lineshape function,
given by

2c
0 = , (13)
L
where c is the speed of light (cm/s) and L is the FWHM pressure broadened linewidth
(Hz) equal to 4.4 GHz/atm.

crel = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6. How does your result compare to the tabulated data of CO2 concentration in air?

.......................................................................................

7. What is the detection limit, in terms of concentration, for CO2 using this CRDS setup?

.......................................................................................

9
8. What is it in terms of absorption?

.......................................................................................

10
References
[1] A. OKeefe and D. A. G. Deacon. Cavity ring-down optical spectrometer for absorption
measurements using pulsed laser sources. Review of Scientific Instruments, 59:25442551,
December 1988. doi: 10.1063/1.1139895.

[2] Aleksandra Foltynowicz. Fiber-laser-based noise-immune cavity-enhanced optical heterodyne

molecular spectrometry. PhD thesis, Umea University, Department of Physics, 2009.

[3] W. Demtroder. Laser spectroscopy. Laser Spectroscopy. Springer-Verlag, 2008. ISBN

9783540749547. URL http://books.google.se/books?id=Wv2OIC SaDUC.

[4] L. S. Rothman, I. E. Gordon, A. Barbe, Benner, P. F. Bernath, M. Birk, V. Boudon, L. R.

Brown, A. Campargue, J. P. Champion, K. Chance, L. H. Coudert, V. Dana, V. M. Devi,
S. Fally, J. M. Flaud, R. R. Gamache, A. Goldman, D. Jacquemart, I. Kleiner, N. Lacome,
W. J. Lafferty, J. Y. Mandin, S. T. Massie, S. N. Mikhailenko, C. E. Miller, N. Moazzen-
Ahmadi, O. V. Naumenko, A. V. Nikitin, J. Orphal, V. I. Perevalov, A. Perrin, A. Predoi-
Cross, C. P. Rinsland, M. Rotger, M. Simeckova, M. A. H. Smith, K. Sung, S. A. Tashkun,
J. Tennyson, R. A. Toth, A. C. Vandaele, and J. Vander Auwera. The HITRAN 2008 molec-
ular spectroscopic database. Journal of Quantitative Spectroscopy and Radiative Transfer,
110(9-10):533572, June 2009. ISSN 00224073. doi: 10.1016/j.jqsrt.2009.02.013. URL
http://dx.doi.org/10.1016/j.jqsrt.2009.02.013.

[5] P.W. Milonni and J.H. Eberly. Lasers. Wiley Series in Pure and Applied Optics. Wiley,
1988. ISBN 9780471627319. URL http://books.google.se/books?id=nxlRAAAAMAAJ.

[6] P. Zalicki and R. N. Zare. Cavity ring-down spectroscopy for quantitative absorp-
tion measurements. Journal of Chemical Physics, 102:27082717, February 1995. doi:
10.1063/1.468647.

[7] G. Berden, R. Peeters, and G. Meijer. Cavity ring-down spectroscopy. International Reviews
in Physical Chemistry, 19:565607, 2000. doi: 10.1080/014423500750040627.

11
NEL Laser Diodes
March2005

NLK1L5EAAA
1565-1625 nm DFB laser diode in a butterfly-type 14 pin package with thermo-electric cooler.
Pigtail fiber is connectorized with an FC/PC connector.

FEATURES
* Wavelength Range 1565 - 1625 nm, ITU-T grid wavelength
* Fiber Output Power 10mW

ABSOLUTE MAXIMUM RATINGS(Tsub=25deg.C)

Parameter Symbol Ratings Units
Laser diode reverse voltage VR 2.0 V
Laser diode forward current IF 225 mA
Operating case temperature Tcase -5 to 70 deg.
Storage temperature Tstg -40 to 85 deg.
Photodiode reverse voltage VDR 10 V
Photodiode forward current IDF 10 mA
Peltier current IP 1.4 A

ELECTRICAL/OPTICAL CHARACTERISTICS(Tsub=25deg.C)
Parameter Symbol Condition Min. Typ. Max. Units
Forward voltage V F IF=30mA 1.2 1.6 V
Threshold current I(TH) CW 10 20 mA
Fiber output power e CW,IF=80mA 10 mW
Peak wavelength p CW, e =10mW -1 ITU-T +1 nm
Spectral linewidth *
CW,e=10mW 2 MHz
Side mode suppression ratio SMS CW,e=10mW 35 dB
Monitoring Current(PD) IR(E) CW,e=10mW 0.1 mA
Dark current(PD) Ir(0) CW,VDR=5V 100 nA
Tracking error ER IR(E)=constant -0.5 +0.5 dB
Cooling capacity *
TPE e=10mW,Tcase=70deg. 45 deg.
Peltier current IPE Tcase=-5 to 70deg. 1 A
Peltier voltage VPE Tcase=-5 to 70deg. 2 V
Thermister resistance* R Tsub=25deg. 10 k
*
Isolation Is Tsub=25deg. 30 dB
T=| Tcase-Tsub |
*
Data is not attached.

! WARNING

If you plan to use these products in equipment which could endanger lives in the event of a product failure,
please consult an NEL engineer before usage. Improper application of these products may endanger life. To
avoid possible injury, make certain these products are used in a redundant configuration.

1 These products are subject to export regulations and restrictions set force by the Japanese Government.
2 NTT Electronics Corporation reserves the right to make changes in design,specification or related
information at any time without prior notice.
3 The characteristics which are not specified in the data sheet are not guaranteed.
4 The characteristics under the different operation conditions from the ones specified in the data sheet are not guaranteed.