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OPTICS LETTERS / Vol. 20, No. 10 / May 15, 1995

Measurements of the tensor properties of third-order

nonlinearities in wide-gap semiconductors
Todd D. Krauss, Jinendra K. Ranka, Frank W. Wise, and Alexander L. Gaeta
School of Applied and Engineering Physics, Cornell University, Ithaca, New York 14853

Received January 12, 1995

We extend the z-scan technique to provide for measurements of the sign and the magnitude of all the independent
components of x s3d for isotropic and cubic-symmetry materials. This technique is used to measure the dispersion
of the tensor components of the real and the imaginary parts of x s3d for various wide-gap semiconductor materials
by use of femtosecond laser pulses. Our measurements of the polarization dichroism of the nonlinear-index and
two-photon absorption coefficients are in fair agreement with recent theoretical calculations; however, substantial
discrepancies exist between the measured and predicted values for the corresponding anisotropy parameters.

The tensor nature of the third-order susceptibility x s3d of optical materials plays an important role
in nonlinear-optical devices that rely on intensitydependent changes of the polarization of the light.
For example, laser mode locking by nonlinear ellipse
rotation1 and nonliner-optical polarization switching2
are based on the tensor properties of x s3d . Various
nonlinear-optical techniques such as third-harmonic
generation, nonlinear ellipse rotation,3 and degenerate four-wave mixing4 have been developed to measure the various components of x s3d . Sheik-Bahae
et al.5 recently developed a technique called the z
scan that relies on the transmittance of a single selffocused or -defocused laser beam through an aperture
as the sample is scanned through the focus of the laser
beam. This technique has been employed to measure
the nonlinear refractive-index coefficient and the twophoton absorption (TPA) coefficient for linearly polarized light for various solid-state optical materials.6 8
More recently it was demonstrated9 that the z-scan
technique can be extended to measure the anisotropic
nature of x s3d for various crystalline materials. Similar measurements10 of the TPA coefficients for various
zinc-blende semiconductors by use of a two-wave mixing technique have also been recently reported. By
measuring the amount of circularly polarized light
generated in the two-wave mixing scheme Schroeder
et al.11 were able to measure the sign and the magnitude of the various components of the third-order
susceptibility for various semiconductor materials.
Extensive theoretical study was recently performed
that addresses the polarization dependence of TPA
(Refs. 12 and 13) and nonlinear refraction.14
In this Letter we demonstrate that, by making appropriate measurements of the nonlinear-index change
for linearly and circularly polarized light, it is possible
to determine the sign and the magnitude of the independent tensor elements of the third-order susceptibility for isotropic and cubic-symmetry materials. We
use this approach to measure the dispersion of the tensor properties of the real and the imaginary parts of
x s3d in various semiconductor materials. The experimental results are compared with recent theoretical
predictions.12 14,15
0146-9592/95/101110-03$6.00/0

The equations describing an optical field that propagates along one of the crystal axes of a cubic-symmetry
crystal are given by16
dEx, y
isx1 jEx, y j2 1 2x2 jEy, x j2 dEx, y 1 ix3 Ey, x 2 Ex,p y ,
dz
(1)
where Ex and Ey are the complex field amplitudes for
the field along the two other crystal axes and the nons3d
,
linear coefficients are given by x1 s6pvyn0 cdxxxxx
s3d
s3d
x2 s6pvyn0 cdxxyxy
, x3 s6pvyn0 cdxxyyx
, where n0
is the linear index of refraction. For an isotropic
medium, x1 2x2 1 x3 , and the number of independent elements of x s3d reduces to two.17 It is useful to
r, i
r, i
define the anisotropy parameters sr, i sx1 2 2x2 2
r, i
r, i
i
x3 dyx1 , where xjr and xj are the real and the imaginary parts of the j th nonlinear coefficient; these parameters are a measure of the anisotropy in the real
and the imaginary parts of x s3d of a cubic crystal with
respect to an isotropic medium. Yumoto and Otsuka16
showed that there exist three nonlinear eigenpolarizations (i.e., the polarization state of the beam does
not change as it propagates through the nonlinear
medium). These nonlinear eigenpolarizations are circular polarization and linear polarization along a crystal axis or along a direction 45 to one of the crystal
axes. Thus the nonlinear-index and TPA coefficients
for each of the nonlinear eigenpolarizations can be related to the nonlinear coefficients xj as follows:
s0d

n2 1 i

s45d

n2

circ
2

1i

c s0d
2p
b
x1 ,
2v
n0 v

c
2p
b s45d
2v
n0 v

12

(2a)

si i
sr r
x1 1 i 1 2
x1 ,
2
2
(2b)

sr r
x1
2

si i
,
x
1 i 2x2i 1
2 1

c
2p
b circ
1i
2v
n0 v

2x2r 1

1995 Optical Society of America

(2c)

May 15, 1995 / Vol. 20, No. 10 / OPTICS LETTERS

s0d

s45d

where n2 fb s0d g, n2 fb s45d g, and ncirc

sb circ d are the
2
nonlinear-index (TPA) coefficients for light linearly polarized at 0 and 45 to a crystal axis and for circularly
polarized light, respectively. These results demonstrate that the z-scan technique can be used in a simple
and straightforward manner to determine the sign and
the magnitude of the tensor components of x s3d . For
s45d
s0d
the case of an isotropic medium [i.e., n2 n2 n2lin ]
the measured nonlinear-index changes for linearly polarized light and for circularly polarized light yield
sufficient information to specify the two independent
nonlinear coefficients. For the case of a cubic crystal,
measurements of the nonlinear-index change for light
linearly polarized along one of the crystal axes (e.g.,
x or y) and at 45 to one of the crystal axes must be
made in addition to a measurement of the index change
for circularly polarized light. In this manner the real
and the imaginary parts of all three independent components can be determined.
We use the analysis above to characterize the dispersion in the tensor properties of the real and the imaginary parts of the third-order susceptibility for various
semiconductor materials. We measured the nonlinear coefficients using the standard z-scan technique5
with two different sources of femtosecond-duration
pulses. The first system was a Ti:sapphire laser that
operated at wavelengths between 770 and 870 nm
with 75-fs pulses or at 990 nm with 85-fs pulses. The
second system was a recently developed Cr:forsterite
laser18 that generated 80-fs pulses at 1260 nm. The
semiconductor samples consisted of GaAs and ZnTe
single crystals and polycrystalline ZnS and ZnSe.
The cubic symmetry and orientation of the single crystals were verified with x-ray diffraction measurements.
The ratios of sample thickness to diffraction lengths
inside the sample were approximately 0.3 for ZnTe,
0.1 for GaAs, 0.9 for ZnSe, and 1.5 for ZnS. Further
details concerning the experimental setup and procedure are given in Ref. 8. For the measurements
with circular polarization a zeroth-order quarter-wave
plate was inserted after the reference-arm beam splitter. The major and minor axes of the polarization did
not differ by more than 5% over the wavelength range
that was studied. Measurements were made at different intensities to ensure that contributions to the
differential transmission from excited-state absorption, free-carrier refraction, and thermal effects were
negligible.7,8 The peak intensities within the singlecrystal and polycrystalline samples were 0.9 2.0 and
3.75.2 GWycm2 , respectively. Changes in the peak
intensity as a result of the group-velocity dispersion in
the samples were accounted for in the data analysis.
The data for ZnS were analyzed by use of a calculation based on ray-matrix techniques that is appropriate for thick samples,19 and data from the other
samples were analyzed based on a Fresnel wave-optics
approach that assumes that the sample is thin compared with the confocal parameter.5,7 The relative uncertainty in the measured values of the ratio of tensor
components of x s3d ranged from 15% to 30%. In measurements in which TPA is the dominant contribution
to the z-scan signal, the closed-aperture fit is relatively
insensitive to variations in the nonlinear index of re-

1111

fraction, which results in uncertainties of 2530% in

the value of the nonlinear-index coefficient.
We characterize the dispersion in the polarization
dichroism of the nonlinear-index and TPA coefficients
for various wide-gap semiconductor materials by plots0d
ting in Figs. 1(a) and 1(b) the parameters dr fn2 2
s0d
n2circ gyn2 and di fb s0d 2 b circ gyb s0d , respectively, as
functions of the frequency v of the applied field normalized to the band-gap energy Eg . The samples of
polycrystalline ZnS and ZnSe are isotropic, and we find
[Fig. 1(a)] that, for the case in which the frequency of
the applied field is below the TPA edge shvyE

g , 0.5d,
dr 1y3, as would be expected from a nonresonant
electronic nonlinearity. Above the TPA edge the data
for dr for ZnSe, ZnTe, and GaAs are consistent with
theoretical predictions,14,15 except for the ZnTe point
at hvyE

The measured values of the various

g 0.7.
nonlinear-index changes in GaAs at 1260 nm were too
small to yield reliable values of the dichroism parameter. The measured values for the TPA dichroism parameter di of GaAs are also consistent with previously

measured9,10 values (at hvyE

g 0.89) and with the
anisotropic band-structure model.13 The dispersion in
the measured values of di for ZnTe is much larger than
predicted by the isotropic four-band model.13
In Figs. 2(a) and 2(b) we plot the measured values of the anisotropy parameters sr and si , respecLarge negative values
tively, as functions of hvyE

g.
of sr are obtained, which suggest that ZnTe could
possibly be used as a polarization rotation switch.2,11

Fig. 1. Measured values of the polarization dichroism parameters (a) dr and ( b) di associated with the real and
imaginary parts of x s3d plotted as a function of the ratio
of the photon energy hv
to the energy gap Eg for various
semiconductor samples. The solid curves are theoretical
calculations of (a) dr and ( b) di for GaAs from Refs. 15 and
13, respectively. The dashed curve is the theoretical prediction of an isotropic model (Ref. 15), which is appropriate
for the polycrystalline samples.

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OPTICS LETTERS / Vol. 20, No. 10 / May 15, 1995

the anisotropy parameters sr and si disagree with existing theories of zinc-blende semiconductors.
The authors thank Chris Xu for his assistance with
some measurements and D. C. Hutchings and B. S.
Wherrett for providing theoretical data before publication. Portions of this study were supported by the
National Science Foundation under award DMR8957988.

References

Fig. 2. Measured values for ZnTe and GaAs of the

anisotropy parameters (a) sr and (b) si associated with
the real and imaginary parts of x s3d plotted as a function
of the ratio of the photon energy hv
to the energy gap Eg .
The solid curves are theoretical calculations of (a) sr and
(b) si for GaAs from Refs. 15 and 13, respectively.

The results for sr for ZnTe cannot be compared directly with theoretical predictions because of a lack
of detailed band-structure data. The measured values of the anisotropy parameter si for TPA [Fig. 2(b)]
for both GaAs and ZnTe exhibit a dispersive nature
that contradicts the theoretically predicted trend12,13
for zinc-blende semiconductors. For example, si of
GaAs is found to be more negative at hvyE

g 0.7 than

0.89;
theoretical
analysis
in
this
regime of
at hvyE

g
photon energies predicts that the value should become
less negative at smaller values of hvyE

Note that
g.

our measured value of si 20.7 at hvyE

g 0.89 is
consistent with previously measured values.9,10
In conclusion, we have extended the z-scan technique to provide for straightforward measurements of
the sign and the magnitude of the independent components of the x s3d susceptibility for materials that are
isotropic or have cubic symmetry. We use this technique to measure the dispersion in the anisotropy and
polarization dichroism parameters associated with the
real and the imaginary parts of x s3d for various zincblende semiconductors. Most of our measurements of
the dichroism parameters dr and di agree with theoretical predictions; however, most of our measurements of

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