1070 J. Opt. Soc. Am. B/Vol. 3, No. 8/August 1986
Two-tone frequency-modulation spectroscopy
G. R. Janik, C. B. Carlisle, and T. F. Gallagher
Department of Physics, University of Virginia, Charlottesville, Virginia 22901
Received January 21, 1986; accepted April 28, 1986
A new method for performing high-frequency, visibleFM spectroscopy by using low-frequency detection is demon-
strated. By using this technique, a detection limit of 323 uTorr m (path length) has been established for
atmospheric-pressure-broadened NO2 . This corresponds to a differential absorption of 1.0 X 10-6.
INTRODUCTION
Optical frequency-modulation (FM) spectroscopy has prov-
en to be a significant addition to the field of high-sensitivity
absorption spectroscopy since it was first proposed and dem-
onstrated by Bjorklund.1 Originally developed by using a
single-mode cw dye laser whose frequency was modulated at
hundreds of megahertz, FM-spectroscopic techniques were
subsequently employed with pulsed dye2 3 and multimode
CW4 lasers with modulation frequencies extending to as many
as several gigahertz. Such efforts illustrate the desire to
construct an FM detection system more suitable for remote-
sensing applications outside the laboratory.
The use of tunable dye lasers that are simpler to align and
operate than the extremely delicate single-mode versions
consequently introduces more laser noise into the FM signal
from the increased laser linewidth. Thus there is a concomi-
tant requirement for higher modulation frequencies in such
systems in order to maintain the same signal-to-noise ratio
(SNR). Additionally, FM detection of atmospheric-pres-
sure-broadened spectral lines (whichmay have widths of the
order of 10 GHz) requires modulation frequencies of at least
the same order. Since the signal in FM systems is phase
detected at the modulation frequency, a photodetector with
a response bandwidth of many (as much as 20) gigahertz is
required. Such detectors have the dual disadvantage of (1)
not being available commercially and (2) having minute and
highly damage-sensitive active areas. However, experimen-
tal versions of GaAs photodiodes with bandwidths of 20 GHz
(Ref. 5) have, in fact, been used in some pulsed FM-spectros-
copy experiments. The difficulties inherent in their use
have provided ample motivation to develop some means of
reducing the bandwidth demands on the photodetectors. A
double-modulation FM system was demonstrated by using a
He-Ne laser with this as its aim.6 Unfortunately, the com-
plications of this approach, which required two separate
high-frequency microwave modulators, all but negated the
simplification achieved in detection electro-optics.
We have devised a new FM detection system that retains
the desirable characteristic of a high modulation frequency
(ours was 16 GHz) and the relative operational simplicity of
an unstabilized multimode cw dye laser while eliminating
the need for high-frequency detection or two separate modu-
lators. We call this technique two-tone FM spectroscopy,
borrowing from standard rf terminology. We believe that
this technique constitutes a notable advance toward a more
0740-3224/86/081070-05$02.00
Janik et al.
versatile FM system operating in the visible spectrum, one
that is suitable for laboratory as well as field-atmospheric
measurements. It should be duly noted that the essential
novelty contained in the two-tone approach, which is the
idea of simultaneously modulating the laser with two differ-
ent frequencies, has been previously demonstrated in micro-
wave7 and infrared8 spectroscopy under the name of tone-
burst modulation. Two-tone techniques have also been
used for wavelength-modulation spectroscopy with tunable
diode lasers at kilohertz modulation frequencies.9 Howev-
er, it has not, to our knowledge, been utilized in visible FM
spectroscopy, with a tunable laser, or at microwave modula-
tion frequencies.
FM THEORY
It is worthwhile to review the basic principles of FM spec-
troscopy. A laser beam of optical angular frequency wo is
directed through an electro-optic phase modulator that is
driven at a microwave angular frequency co,. After the beam
leaves the modulator, its electric field amplitude is given by
the real part of
E 2 (t) = E0 exp(ico0 t) 3 JjQ3)exp(inccjt), (1)
n=--
where Al is commonly referred to as the modulation index
and is a function of the modulation power. The effect of the
phase modulator on the laser beam is to produce an infinite
set of sidebands spaced at integral multiples of the modula-
tion angular frequency wl from the carrier frequency c.
Each sideband has an amplitude that is proportional to
Jn(Q1). For practical purposes Alis usually less than one and
only the carrier and first pair of sidebands have significant
amplitudes. Suppose that we modulate this beam again at
an angular frequency W2. The field amplitude of the laser
after modulation is then
E2 (t) = E0 exp(icwot) 3 JG(l)exp(inc 1 t)
n=-x
X EJ.(02)exp(iMW20)
m=-X
= Eo exp(ic 0t) 3
n,m
Jn(G1)Jm( 2 )exp(nwc + mCc2 )t. (2)
1986 Optical Society of America
Janik et al. Vol. 3, No. 8/August 1986/J. Opt. Soc. Am. B 1071

--W
From this expression it is apparent that performing succes-
sive modulations at angular frequencies tol and 2 is equiva- E3(t) = Eo(To exp(icot)-+ exp[i(c + )t]
lent to simultaneous modulation at the two frequencies.

- )ir
To obtain a tractable expression at this point, we must
make some simplifying approximations. First, we set fl1 = - exp[i(cc
0 -Q)t] + T+1 exp izcO+ + 2)t]
ItI
12 = , which is tantamount to taking the modulation power

-
associated with cc and cc2 to be equal. We also take 13< 1
and consider only the zeroth- and first-order sidebands asso- + exp[i(c 0 + W. )
ciated with each frequency to be significant. Then Jo(B)
2 LX
1, hu(,) - +1/2, and
+ T. - exp i cO

~~2
'0

E 2 (t) _ E exp(icc0 t) +
12 exp(it) - - exp(ict)1
-- explilC 0 Cor+ itI? (6)
2 LX( 2 /jjl
X[1+-2 exp(i 2 t) --
2Iexp(-io20 (3)
This field is incident on the photodetector that detects in-
tensity, 13 (t) = c(E*3E3)/8-7r. Because we extract the signal
We can express the two modulation frequencies as through narrow-band heterodyne detection at frequency Q,
we are interested only in the photocurrent output at Qfrom
the photodiode, although there will certainly be output at
cc1 = m+ 2
other frequencies. After some algebra we obtain
cE 0 2=+2
Q ~[exp(-26 1 ) + exp(-2&- 1 )
2 -< o-3, (4)
13 (at 2) =
16r
ccm
- 2 exp(-23 0 )] cos($t), (7)
and obtain the spectral distribution of the laser field
which for small absorptions simplifies to
E3 (t) = E exp(iwot) - exp[i(wo+ Q)tJ cE0 2 2
13(at ) = 8 (26 o - 61 - &9cos(Wt). (8)
To illustrate these ideas, consider the effect of tuning the
- exp[i(coo - 2)t] + -2 expL(co + Ccm+ )tJ laser across an absorption line from below in frequency.
First, the upper sideband pair will be absorbed. Thus b in
Eq. (8) becomes nonzero, and a net negative signal results.
+ exp[i(co + m- ) t] Further scanning of the laser brings the absorption line onto
the central group of sidebands and 26o becomes nonzero, and
2 P((o m2)] a net positive signal results. Finally, absorption of the lower
-~exp
iWcc - WcM- *)t]
sideband pair creates a nonzero b&1,and again a negative
signal results. The recorded absorption spectrum will thus
have a central positive peak and two symmetrically placed
- exP[i(co
- cm+ )t]} (5) negative peaks with one half the height of the central peak.
As shown in Fig. 2(a), a recorded scan over the sodium D
This spectrum is shown pictorially in Fig. 1, which is not lines verifies this line shape produced from two-tone FM
drawn to scale, as the size of Qis greatly exaggerated in order detection.
that the separate sidebands be discernible. In our experi- The observed broadening of the D line spectra is due to the
ment, cm = 27rX 16 GHz, while Q 2r X 12 MHz. Thus the dye laser linewidth, which is -8-10 GHz. Figure 2(b) shows
pair of sidebands cc and 2 will experience virtually equal
absorptions when they are within an atomic or molecular
linewidth, which is typically broad with respect to our detec-
SINGLE TONE
tion frequency = c1 - 2-
With this in mind, let us define the quantity Tj = exp(-bj LOWER
SIDEBAND
- ij), j = 0, 1, to describe the effect of the sample's t
interaction with the modulated laser beam. In this expres- CARRIER UPPER
SIDEBAND
sion, bjis the amplitude attenuation and Xk is the phase shift
that is experienced by the sidebands within the jth envelope,
which is jm removed from the carrier angular frequency.
TWO- TONE
From Fig. 1 we see, for example, that for j = 1 there are two
spectral components whose interactions with the sample are
both described by T1, while for j = 0 there are three compo- * 4
ti
nents affected by To.
Thus we have the expression for the modulated laser field Fig. 1. Spectral components of the laser after two-tone modula-
after interaction with the sample: tion.
1072 J. Opt. Soc. Am. B/Vol. 3, No. 8/August 1986
2 detection frequency to any value from a few megahertz up
(a)
H
LL
0
H EXPERIMENTAL APPARATUS
-1
I crystal oscillator is mixed with the output of an HP 8690B
16973 16970 16965 16960 16956
E K (car 1)
H NO2 gas in 1 atm of N2 buffer gas, simulating an atmospheric
z 0.5
LL
Z Hamamatsu S1223-01 photodiode whose window has been
16973 16970 16965 16960 16956
EK (CM'1)
Fig. 2. Comparison of direct and two-tone FM absorption signals
of the Na D lines, with 2%absorption in the D2 line. (a) FM signal
with P = 0.25 at 17 GHz. (b) Direct absorption signal. The D2 line
is barely visible and the D1 line cannot be seen.
the light intensity as the laser is scanned over the D lines; the
contrast between the SNR in Fig. 2(a) and in Fig. 2(b) em-
phasizes the greatly enhanced sensitivity of FM detection
versus ordinary absorption spectroscopy. We have not yet
determined the cause of the slight asymmetry of the FM line
shape.
We note from Eq. (8) that there is no dispersion signal in
quadrature, as there is in conventional FM spectroscopy.
Also, the signal is proportional to 132instead of 13and thus
requires a commensurate increase in modulator efficiency.
Our resonant-cavity design modulator is uniquely suited to
meet this requirement.' 0
We further note that if 6 = 6-1 = 31,i.e., if there is no
differential absorption, there is perfect cancellation and no
signal. Thus the most attractive feature of conventional
FM detection-a signal arises from zero background-is
preserved in two-tone FM detection.
Two notes of caution should be added. Because there is
no quadrature dispersion signal, wandering of the local-os-
cillator phase that is used for heterodyne detection will re-
sult only in a decrease in signal strength and not in a distort-
ed line shape. Thus it is important to ensure that the local
oscillator phase shifter is adjusted for maximum signal.
Also, we are detecting at a low frequency (12 MHz in our
case) that is well within the envelope of our dye laser, which
has a linewidth of -8 GHz. However, we found that as long
as the detection frequency is not coincident with the laser
mode spacing (or integral multiples of it) and is outside the
width of a single mode, s5 MHz, there is no problem with
laser noise in our signal. We are at liberty to adjust our
Janik et al.
to the limit imposed by the Q of our resonant-cavity modula-
tor's resonance. This upper limit is about 80-100 MHz.
Our experimental setup is depicted in Fig. 3. A 6-MHz
sweep oscillator at 16 GHz to produce sum and difference
frequencies at 16.006 and 15.994 GHz, which constitute the
two tones. These tones are amplified by a traveling-wave
tube amplifier whose output drives the phase modulator
that employs electro-optic LiTaO3 crystals to perform the
modulation. The modulator design is discussed in detail in
Ref. 10. A laser beam from a tunable cw dye laser is focused
through the modulator and is recollimated before passing
through the absorption cell containing small amounts of
environment for a pollutant. The beam is detected by a
removed. The photocurrent at 12 MHz is amplified, fil-
tered, mixed down to dc, and filtered again. The final dc
amplifier has a time constant of I sec. The signal is dis-
played on an x-y recorder as the laser is scanned.
The dye laser is a modified Spectra-Physics Model 375. A
fourth 10.3-mm-thick quartz plate has been added to the
standard birefringent filter. The laser cavity has been ex-
tended to accommodate the larger filter. When running
with Rhodamine 6G and about 2 W of argon-laser pump
power, an output of about 50 mW with a bandwidth of less
than 10 GHz can be achieved. Because the fourth plate
thickness is not an integral multiple of the other three plates,
the continuous tuning range is limited to about one third of
the total range without the fourth plate. This is still more
than adequate for our purposes and far exceeds that obtain-
able by using 6talons.
RESULTS
The absorption cell used for the NO2 measurements is a 38-
cm-long Pyrex tube with Brewster-angle windows. The la-
ser power at the photodiode is about 2 mW. Trace (a) of Fig.
4 shows an FM absorption signal from I Torr of NO2 gas in a
region near 590 nm with a scan range of about 25 cm-'.
Trace (b) shows the same scan with 1 atm of N2 added to the
cell. The spectral features are now pressure broadened to
more than 10 GHz. The cell was then partially pumped out
and refilled with N2 to maintain 1-atm total pressure. This
dilution was repeated until the background became signifi-
cant. By scaling the signal strength from the 1-Torr value,
this signal represents 1.7 mTorr of NO2 and is shown in trace
(c) of Fig. 4. The oscillatory background has a period of
about 5 GHz and results from 6taloning and other effects in
our 16-mm-longmodulator crystal. Trace (d) is a scan over
the region after the NO2 is pumped out. The marks on
traces (b)-(d) of Fig. 4 indicate the peaks used in the scaling
calculations to determine the smallest partial pressure of
NO2 detected [trace (c)] and the equivalent partial pressure
of our noise background [trace (d)]. The relative gain fac-
tors between the scans are listed beside each of them.
Janik et al. Vol. 3, No. 8/August 1986/J. Opt. Soc. Am. B 1073

TWO-TONE FREQUENCY MODULATION

Fig. 3. Schematic of the experimental setup.

Careful inspection of the scans reveals that there are some

frequency offsets between them and also that the frequency
scale is not constant for all the figures. These discrepancies
result from the manner in which the data were recorded,
with the frequency scale fitted to a somewhat coarse time
sweep. Still, major peaks (or, more properly, groups of Rf Attenuation
peaks) are discernible and can be used to verify the presence
of NO2 . A separate calibration of our dilution procedure 50 dB
was not possible, since the NO2 was somewhat reactive and (a)
tended to adsorb irregularly on the vacuum hoses, fittings,
and our cell walls."l
The background residual-amplitude modulation, or
RAM, 2 in fact determines our current detection limit. The (b)
strength of this RAM signal is equivalent to a partial pres-
sure of about 850 gTorr. We can therefore claim, as a figure
of merit, a detection limit (DL)
DL 323 Torr m, (9)
'O dB
using a modulation index = 0.35. We note that Gehrtz et 0.8
3
al.1 achieved a DL - 0.7 Torr m for NO 2 detection. How-
ever, this limit was reached for 102at low-pressure condi-
tions, i.e., in the absence of atmospheric-pressure broaden-
ing. Since NO2 features are pressure broadened to 10 GHz
or more at atmospheric pressures, the detection sensitivity
of the dual-beam, low-frequency (fin'- 250MHz) FM system (d)
used by Gehrtz et al. would be decreased. The extent to
which pressure broadening degrades SNR in conventional 0 200 400 600 800
FM detection can be established roughly as follows. Con- GHz
sider the pressure-broadened absorption line to be a Lo- Fig. 4. Two-tone FM scans with modulator frequency = 16 GHz,
rentzian with FWHM = 10 GHz. The in-phase signal in = 0.35. Note that the attenuation refers to electronic attenuation
conventional FM is proportional to the difference of the (in power), i.e., 40 dB = X 100 in voltage (also decibels). (a) FM
signal from 1 Torr of NO 2 gas near 590 nm with a scan range of about
absorption coefficients of the first-order sidebands, 61 - 6 -1. 25cm 1 . (b) Same scan as in (a) but with 1-atm N 2 added to the cell.
We assume that the absorption line is centered at the upper (c) FM signal from 1.7 mTorr of NO2 with 1-atm N2 added to the
sideband (i.e., at frequency f, + [n). Then cell. (d) FM signal from empty absorption cell.
1074

6_ = 6
6
1
J. Opt. Soc. Am. B/Vol. 3, No. 8/August 1986

1
+ [2(wi -W)j2

[
+
1

12Qo..i-
=6,

=6 I)]=
+~~~~
16fm2z
CONCLUSION
In conclusion, two-tone FM spectroscopy has been demon-

copy at high modulation frequencies with low-frequency

detection. Since an unstabilized multimode cw dye laser
and a modest bandwidth photodetector are employed, this
Janik et al.

strated as a technique for performing sensitive FM spectros-

method constitutes a noteworthy simplification in high-fre-

and
1 + 16 Q?)1
Taking f,, = 250 MHz,
6 - 6, 6 [i- 1 +10.011
=_ 6 Power Research Institute.
101
Thus pressure broadening would reduce the signal strength
of Gehrtz et al. by roughly 2 orders of magnitude.
The minimum differential absorption bmi,that can be
detected by sing FM techniques is set by the quantum
nature of the laser light. Bjorklund et al.14 established
through a complete SNR analysis that for quantum, or shot-
noise, limited conditions
A6 2 Afhwo 1/2
Gaminwr7
= [ c1 0
where e is the photodetector quantum efficiency and Af is
the bandwidth of the detection electronics. This expression
also holds for two-tone FM detection but with 13replaced by
12 and A6 min signifying 6o - 6 instead of 61 - 6-,. For our
system, 2 = 0.1, A = 1 Hz, Io = 2 mW, and taking e = 1 we
find
A6min= 2.6 X 107.
At present the smallest differential absorption that we can
detect is 1 X 10-5, a factor of 38 above the quantum limit for
our apparatus.' 5 As we approach this sensitivity limit, laser
noise may pose a substantial barrier to optimum sensitivity.
RAM due to talon effects from our optical instruments
(most prominently from our modulator crystal) currently
determines the practical limitation on our sensitivity. We
have succeeded in eliminating much of this RAM by employ-
ing only reflective optics after the modulator. We are cur-
rently pursuing a method of actively suppressing the RAM
by using feedback.
Our detection method does not provide us with informa-
tion on the absorption line shape due to the width of our
laser and the overlapping of the pressure-broadened lines.
That pressure broadening tends to wash out the structure of
the individual line shapes is evident in the contrast between
traces (a) and (b) of Fig. 4; there are some visible, narrow
lines in trace (a) that vanish in trace (b), which is a pressure-
broadened scan.
quency FM detection. In support of this claim, detection of
less than 650 MATorr m (path length) of pressure-broadened
NO2 is adduced and a detection limit of 323 aTorr m (path
length) is established for our system.
ACKNOWLEDGMENTS
The authors would like to express their appreciation to B. S.
Deaver for the generous loan of rf equipment. They would
also like to thank L. S. Andrews for helpful advice on NO 2
and its handling. This work is supported by the Electric
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