Coherent anti‐Stokes Raman spectroscopy

R. F. Begley, A. B. Harvey, and R. L. Byer

Citation: Applied Physics Letters 25, 387 (1974); doi: 10.1063/1.1655519

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 The theoretical curve for the 35-/-lm interaction length
is depicted in Fig. 3, which provides the best fit around
the central portion of the measured profile. From the
fact that the spot size of the fundamental beam on the
film was approximately 45 /-lm and the interaction was
only limited in the region obtainable with a single prism
coupler, the calculated effective interaction length of
35 Mm seems quite feasible, while the coherence length
of the znS single crystal is only about 5 Mm for 1. 064-
/-lm SHG. If two prisms, one for coupling and the other
for decoupling, are set separately to allow the propaga-
tion of proper modes, the longer effective interaction
length could be achieved. Thus the demonstration of the
phase-matched SHG in oriented polycrystalline thin-
film waveguides indicates the potentiality of various
nonlinear thin-film materials for practical use in optical
integrated circuits.
One of the authors (H. Ito) expresses his thanks to
the Sakkokai Foundation for partial support for this
work.
*Present address: Musashino Electrical Communication Lab-
oratory, Nippon Telegraph and Telephone Public Corpora-
tion, Musashino-shi, Tokyo 180, Japan.
lP.K. Tien, R. Ulrich, andR.J. Martin, Appl. Phys. Lett.
17, 447 (1970).
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23, 137 (1973); Y. Suematsu, Y. Sasaki, K. Shibata, and S.
Ibukuro, IEEE J. Quantum Electron. QE-10, 222 (1974).
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Group of Optical and Quantum Electronics (The Institute of
Electronics and Communication Engineers of Japan, Tokyo,
1974), No. OQE 73-75.
5D. B. Anderson, J. T. Boyd, and J. D. McMullen, Proceed-
ings of the Symposium on Submillimeter Waves, MRI
Symposium Proceedings No. 20 (Polytechnic Press, New
York, 1970) p. 191.
6D. B. Anderson and J. T. Boyd, Appl. Phys. Lett. 19, 266
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714 (1955).

Coherent anti-Stokes Raman spectroscopy

R. F. 8egley*, A. B. Harveyt, and R. L. Byer
Microwave Laboratory, Stanford University, Stanford, California 94305
(Received 11 July 1974)

Coherent anti-Stokes Raman spectroscopy offers significant advantages over standard incoherent
Raman spectroscopy. The advantages include 105 improvement in conversion efficiency, spectral and
spatial discrimination against fluorescence, low incident average power, and no requirement for a
monochromator. The potential disadvantages of signal scaling as power cubed and requirement for a
high peak power tunable laser source are largely overcome by presently available tunable laser
sources. The method appears particularly useful for investigating biological compounds where
background fluorescence is a problem for conventional spontaneous Raman studies. We show that for
low concentrations, the density-squared signal dependence becomes linear due to coherent mixing with
an intense solvent Raman mode or the third-order background signal.

Coherent anti-Stokes emission was first observed by
Terhune and Maker 1 over a decade ago. Since that
time, very little has been done toward its application to
Raman spectroscopy due to the requirement for high
peak power tunable laser sources. The development of
nitrogen pumped and double Nd ; YAG laser pumped dye
laser sources now opens this type of spectroscopy to
general use. Recently the method, which we call "co-
herent anti-Stokes Raman spectroscopy" has been used
in the analysis of gases a and for measuring the nonlinear
properties of solids 3- 5 and liquids. 6 In this letter we
evaluate the general use of this technique as a spectro-
scopic tool. Our preliminary results show marked im-
provement over conventional, spontaneous Raman
scattering and illustrate the potential for future exploi-
tation. These improvements are due to orders-of-
magnitude greater Raman efficiencies, the observation
of coherent anti-Stokes emission in a spectral region
largely free of fluorescence, and to an enhancement of
the signal for weak concentrations somewhat analogous
to "intensity borrowing,,7 in classical spectroscopy.
The coherent anti-Stokes Raman process is illustrated
in Fig. 1(a). An incident fixed frequency pump photon at
WI interacts with a tunable photon wa through the third-
order nonlinear susceptibity >:.(3)(_ W3, WI, WI> - Wa) to
generate a polarization component at the anti-Stokes
frequency W3 = 2Wl - wa.
The third-order susceptibility has the form 1
where wa and Wb are electronic transition frequencies,
WR is the Raman vibration frequency, and r R is the
half-width at half-maximum of the Raman mode. >:.(3)
shows resonant behavior as WI - wa approaches w R and
in this way reproduces the Raman spectrum. Note that
X(3) also shows two-photon resonance and shows reso-
nance enhancement as the input frequencies approach
an electronic transition in the same manner as reso-

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 FIRST EXCITED where XR = X; + iX; is the complex Raman susceptibility
- - - - - - - - - - - - - - - - - ELECTRONIC
STATE and XE is the dispersionless background electronic
susceptibility. 4

VIRTUAL STATE At resonance the imaginary component of the Raman

--7..-- ---
susceptibility per molecule is related to the usual differ-
STIMULATED STIMULATED
ential cross section by
Wp STOKES ANTI-STOKES 4
532nm
EMISSION EMISSION " 7TC (dU) (2)
XR = fiWl w~rR \"(m .
/
The total Raman susceptibility is xf: = NX;, where N is
the molecular density.
Simultaneously with the energy conservation condition
__~~_ _V_I_BR_A_T_IO_N_A_L_L_E_V_E_L_~_____ GROUND W3 = 2Wl - W 2 , momentum conservation must also hold.
STATE Figure l(b) shows the wave-vector matching condition.
(aj Due to the positive dispersion of the medium, phase-
matching is possible at a relatively small angle of
8 '" ~ 8' '" 1 0 in solids and liquids. If we define the wave-
vector mismatch by ~k = 2kl - k2 - k3 and let ~klcOb = 7T
define the coherence length, then for solids and liquids
lCOb -1 mm while for vapors lcob - 20-60 cm 0

The conversion efficiency from the tunable input at

(b)
FIG. 1. (a) Level diagram for the four-wave Raman mixing
interaction. The input 532-nm wave mixing with the tunable
dye frequency generates a fluctuation polarization at w2 - wI'
A second 532-nm photon scatters from this induced polariza-
tion giving the anti-Stokes output at w3 = 2w2 - wI' (b) Phase-
matching diagram for the interaction. In positively dispersive
solids and liquids the phasematching angles are e ~ to' ~ r.
The generated spatially coherent anti-Stokes beam is spatially
separated after the intepaction region and is easily selected by
an aperture_
nantly enhanced spontaneous Raman scattering. Intro-
ducing a detuning frequency ~W = Wl - w2 - WR and as-
suming all input frequencies are well away from elec-
tronic levels, XIS) can more generally be written in the
form
(1)
w2 to the generated coherent anti-Stokes output at W3
isS
3
p(W 3 ) _ 2077 x 10- 1 N (3) 12 l2 (P(wJ) 2 (3)
p(w 2 ) - n4A~ X cob A '
where NX(3) is the bulk susceptibility in esu units, lCOb
is the coherence length in cm, A3 is the anti-Stokes
wavelength in cm, and p(wJ/A is the intensity in W/
cm 2 • For example, for NX(3)=L2xI0-12 cm 3/erg, the
value for the 992-cm-1 Raman mode of benzene and
optimum focusing for the I-mm coherence length, the
conversion efficiency at P(w 1 )==1 kW is 2.0xI0- 3. For
comparison, for the same incident power conventional
Raman scattering gives a scattering efficiency of 6
xI0- s which is five orders of magnitude less than the
coherent anti-Stokes signal. In addition, the anti-Stokes
signal is emitted into a 10-4-sr diffraction-limited beam
as compared to a I-sr spontaneous Raman scattered
signal. The coherent anti-Stokes Raman spectroscopy
method offers a nine orders of magnitude discrimination
against background fluorescence signal compared to
conventional spontaneous Raman scattering.
Figure 2 shows a schematic of the apparatus used.
The tunable source is a Rhodamine 6G due laser pumped
by a double Q-switched Nd : YAG laser. The output of
0
the cOllinearly pumped dye laser was adjusted to the 1
phasematching angle by tilting the output cavity mirror.

FIG. 2. Schematic of the

apparatus showing the inter-
nally double, Q-switched
Nd : YAG laser pumped dye
laser. The 532 nm and dye
Doubled output are crossed and fo-
Nd+ :YAG Lose. 532nm DYE
LASER cussed into a sample cell S,
by the lens L. I is the aper-
ture, F is the interference
filter centered at the anti-
Stokes frequency, and D is
the detector.

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 Typical output powers were 2-3 kW at 532 nm and 1 kW
at the due laser frequency at 1-3 mW average power.
Pulse widths were 15 nsec at 532 nm, 30 nsec at the
dye output, and 6 nsec at the anti-Stokes frequency. The
532-nm and dye outputs were focused into a standard
liquid cell. Following the cell, the dye and 532-nm
beams were blocked by an aperture which transmitted
the spatially coherent anti-Stokes beam. Additional
spectral filtering against scattered 532-nm and dye
laser radiation was provided by an inexpensive inter-
ference filter. The output was detected with a silicon
photodiode and displayed on an oscilloscope or pro-
cessed by a boxcar integrator for recording. Spectral
scans were made by slowly tuning the dye laser which
operated with a 2-cm- 1 linewidth.
Initial experiments were carried out with the 992-
cm- 1 mode of benzene. The Raman signal from benzene
is very intense and provides a convenient reference for
experimental investigations of four-wave Raman mixing.
For example, following alignment, the anti-Stokes
emission at 505 nm was easily projected on a card and
visible as a laserlike blue-green beam. A measurement
of the output showed that we generated O. 5-W peak
power at the detector for l-kW peak input powers.
Correcting for the interference filter and lens losses,
the convers ion efficiency is 1.2 xl 0- 3 • This compares
favorably to the previously calculated conversion effi-
ciency of 2.0 X 10-3 using Maker and Terhune'sl value
of NX (3) for benzene, and is within our experimental
uncertainty.
To investigate discrimination against fluorescence
we purposely added Rhodamine 6G dye to the benzene
cell. Although the cell fluoresced brightly, the spatial
discrimination provided by the single aperture and the
spectral discrimination provided by the 100-nm inter-
ference filter were more than adequate to completely
eliminate the fluorescence. A further example of
fluorescence suppression was illustrated during the
study of j3-ionone, 9 a yellow colored liquid, biologically
50%
I
BENZENE
.. IZ.5%
" ~\'
.r
/
• 1
. /
.J'I
J •
. I
/ i Z5°/.
V\
I represent data points
i corrected for a residual
i
i benzene concentration of
\.
970 980 990 1000 1010
(a)
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important material, whose fluorescence makes standard
Raman studies difficult. The 1600-cm-1 Raman mode
was easily recorded by the coherent anti-Stokes Raman
method without fluorescence interference.
To investigate the sensitivity of coherent anti-Stokes
Raman spectroscopy, we investigated a benzene-
toluene mixture over a range of benzene concentrations
from 50% to less than O. 3% .
If we let X~3) and X~3) be the total per molecule
susceptibility of benzene and toluene as defined by Eq.
(1), then the total susceptibility of the mixture is
(4)
The conversion efficiency varies as 1X~I~ 12. Leven-
son4 and Regnier and Taran2 have discussed the inter-
ference between the Raman susceptibility and the back-
ground third-order susceptibility of the same medium.
For this investigation we are interested in the inter-
ference between two neigboring Raman modes. There-
fore, taking the absolute square of Eq. (4) and neglect-
ing the background susceptibility we find
1X~I~ 12 (lI (NBX~)2 + [(NTX~)2 + 2NTX~NBX~](r T/ AWT )2, (5)
where we have assumed tuning to the benzene resonance
AWB = O. Here r T is the toluene half-width and AWT is
the detuning from the toluene Raman resonance. For
our case AWT "" 15 cm- 1 and r T -1.5 cm- 1 so that the
resonance factor [(r T )/AwT ]2-1O-2. Equation (5) shows
clearly that the Raman signal scales as N; over a range
at high concentrations and then, because of the cross
term due to the nearby resonance line, scales linearly
with NB •
Figure 3(a) shows the spectra of benzene at 50, 25,
and 12% concentration in toluene. The peak are
asymmetric as expected from the form of the reso-
nance. However, the measured half-width of 1.8 cm-1
for benzene compares well with the spontaneous Raman
half-width of 1.55 cm- 1 and is probably somewhat
BENZENE - TOLUENE
MIXTURES
FIG. 3. (a) Anti-Stokes
~ Raman spectra of ben-
/ zene-toluene mixtures.
/ (h) A plot of the benzene-
100 /
/ toluene peak signal ratios
/ vs concentration showing
/
// the N2 behavior at higher
. / concentrations going over
/7 the N dependence at lower
10 / I concentrations. At the
very low concentrations
residual benzene in the
solvent caused deviation
from the expected linear
behavior. The triangles
0.17%.
CONC·BjcONC· T
10 100
em-I
(b)
Begley, Harvey, and Byer 389 to IP:
 broadened due to our 2-cm- 1 dye bandwidth. Due to the
proximity of the nearby toluene mode and the residual
532-nm background signal, the expected interference
with the background X~3) susceptibility as observed by
Levenson4 is not seen here.
Figure 3(b) shows a log plot of measured Raman peak
intensity ratios IB/ IT for the range of mixtures studied.
At higher concentrations down to 10% the scaling is
with N2 as expected. However, at smaller benzene
concentrations the cross term in Eq. (5) becomes im-
portant and the signal strength scales linearly with
benzene concentration. A similar cross term and re-
sulting linear scaling behavior holds for the nonreso-
nant electric susceptibility as well. Thus the linear
scaling range is expected to hold down to a level set by
the background electronic susceptibility.
The linear scaling range of the coherent anti-Stokes
Raman spectrum has some interesting aspects. First,
it offers the possibility of measuring much smaller
concentrations than allowed by the N 2 scaling depen-
dence. The ultimate limit is set by the electronic sus-
ceptibility of the sol vent. A case of particular interest,
especially for examination of biological samples, is
water as a solvent. Water has a number of advantages,
among which are broad ill-defined Raman modes and a
very low electronic susceptibility which is only 7.5
x10- 4 that of the benzene Raman susceptibility. 6 The
second aspect of the linear scaling region is its effect
on the spectra produced. Rather than distorted Raman
spectra scaling as [NX~3)J2, the spectra are closely
linear. A good case is that of the {3-ionone spectrum
near the 1600-cm- 1 Raman mode which appeared
remarkably similar to the spontaneous spectrum in
a direct comparison. 9
In conclUSion, we have investigated the use of coherent
anti-Stokes Raman spectroscopy and have demonstrated
a number of potential advantages over conventional
spontaneous Raman scattering. The advantages include
over five orders of magnitude higher conversion effi-
ciency, considerably reduced average required powers
(1-2 mW compared to 1 W) and extremely good rejec-
Carrier mobility profiles for low-dose boron-implanted layers
M. Y. Darwish and H. W. Luginbuhl
Centre Electronique Horloger S.A., Neuchutel, Switzerland
(Received 4 June 1974)
Carrier concentration and mobility profiles of low-dose boron-implanted layers have been measured
for several low-temperature heat treatments. It is found that sufficient activation of impurities can be
obtained, but that significantly lower mobilities have to be expected.
Moderate annealing temperatures are desirable for
certain applications. It is known that for low-dose
boron implants (Q < 5 X 1012 cm- 2) sufficient activation
can be obtained with anneal temperatures of about
500°C. 1 However, it is also important that the carrier
mobility in these layers attains a reasonable value.
This article
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article.
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tion against background fluorescence of nearly nine
orders of magnitude. In addition, the use of available
pulsed high peak power tunable lasers allows this form
of Raman spectroscopy to be readily carried out without
the use of a monochromator or expensive sensitive
detectors. The potential disadvantage of square-law
scaling does not appear to be a serious problem espe-
cially at concentrations where linear scaling holds.
Because of these advantages, coherent anti-Stokes
Raman spectroscopy should find increaSingly wider
applications.
We want to acknowledge the initial assistance of
Chromatix Inc., and the use of a Chromatix dye laser
for these measurements. We also want to acknowledge
useful discussions with Professor S. E. Harris and the
support of the Sloan Foundation.
*Present address: Allied Chemical Corporation, Materials
Research Center, Morristown, N. J. 07960.
tVisiting Research Associate, permanent address: Naval
Research Laboratory, Washington, D. C. 20375.
fsloan Fellow, 1974-1976.
iR. W. Terhune, Bull. Am. Phys. Soc. 8, 359 (I963); see also
P. D. Maker and R. W. Terhune, Phys. Rev. 137, A801
(1965).
2P.R. Regnier andJ.P.E. Taran, Appl. Phys. Lett. 23,
240 (1973).
3J. J. Wynne, Phys. Rev. Lett. 29, 650 (1972).
4M.D. Levenson, C. Flytzanis, andN. Bloembergen, Phys.
Rev. B 6, 3962 (1972).
5E. Yablonovitch, C. Flytzanis, and N. Bloembergen, Phys.
Rev. Lett. 29, 865 (1972).
6M. D. Levenson, IEEE J. Quantum Electron. QE-10, 110
(1974).
7G. Herzberg, Molecular Spectra and Mol ecular Structure
II-Infrared and Raman Spectra of Polyatomic Molecules
(Van Nostrand, Princeton, N.J., 1945), p.265-266.
8S. E. Harris, Application Note No.6, Chromatix Inc. , .1974
(unpublished) .
9R. F. Begley, A. B. Harvey, R. L. Byer, and B. S. Hudson
(unpublished) .
Carrier concentration and mobility profiles have been
measured for several low-temperature heat-treatments.
Using a new test structure, 2 we have been able to mea-
sure implanted profiles close to the surface even at low
carrier concentrations. The fabrication of the simple
test device is entirely compatible with standard tech-
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