Linear and nonlinear optical properties of ZnGeP2

crystal for infrared laser device applications: revisited

Subhasis Das, Gopal C. Bhar, Sudipto Gangopadhyay, and Chittaranjan Ghosh

Measurement of refractive indices in the spectral bands 9 –11 ␮m and 1.32 ␮m from a cw CO2 laser and
a Q-switched Nd:YAG laser, respectively, is reported in a ZnGeP2 crystal. A new set of Sellmeier
dispersion relations has been derived from the measured refractive indices data in this crystal. Second-
harmonic generation 共SHG兲 of CO2 laser radiation in this crystal is also reported. It is also seen that the
previously reported phase-matching data for others experiments in SHG and optical parametric devices
is explained satisfactorily with this new set of Sellmeier dispersion relation. © 2003 Optical Society of
America
OCIS codes: 190.2620, 190.4360, 190.4410, 160.4330, 140.3070.

1. Introduction Sellmeier dispersion.4,27–30 For this reason, we have

ZnGeP2 共ZGP兲 is considered to be one of the most
promising crystals for infrared laser device applica-
tion, particularly in the mid-infrared 共2–12 ␮m兲 re-
gion, owing to its high nonlinearity 共75 pm兾V兲, good
infrared transmission 共12 ␮m兲 coupled with visible
edge transmission 共0.75 ␮m兲, high cw 共200 kW兾cm2兲
and pulsed laser damage threshold 共60 MW兾cm2兲,
and good mechanical properties.1–3 ZGP is superior
to AgGaSe2 for high average power application, be-
cause its thermal conductivity is more than 10 times
higher than that of AgGaSe2. Since the invention of
ZGP, its application as a nonlinear laser device did
not get much attention, owing to the unavailability of
a good optical quality crystal. With the develop-
ment in growth technology, very good optical quality
ZGP crystal is now available, and various nonlinear
laser device applications like efficient second- and
fourth-harmonic generators for tunable CO2 laser ra-
diation, and optical parametric oscillators 共OPOs兲
and optical parametric generators have been
reported.2,3,4 –27 But it is found that the experimen-
tally observed phase-matching angles for various
nonlinear devices are differing significantly from the
theoretically predicted values using the available
The authors are with the Department of Physics, Laser Labora-
tory, Burdwan University, Burdwan 713 104, India. G. C. Bhar’s
e-mail address is dgp_buphygcb@sancharnet.in.
Received 23 August 2002; revised manuscript received 6 April
2003.
0003-6935兾03兾214335-06$15.00兾0
© 2003 Optical Society of America
again under took the task to characterize this crystal
by measuring its refractive indices and phase-
matching angle since almost all the Sellmeier disper-
sions available now were derived from the measured
refractive indices data of Boyd et al.1 In this paper
we discuss the measurement of refractive indices in
this 共ZGP兲 crystal at the tunable CO2 laser wave-
lengths, and from this measured refractive indices we
derive new Sellmeier equations. We also measure
the phase-matching angle for the second-harmonic
generation 共SHG兲 of tunable CO2 laser radiation, and
it is found that the measured phase-matching angles
agree well with the theoretically predicted value with
use of our new Sellmeier equations. It is also seen
that the previously reported2–27 phase-matching an-
gles for different laser device applications agree well
with the predicted values obtained by use of our new
derived Sellmeier equations.
For measurement of refractive indices, a crystal
prism of ZGP having apex angle 29⬘30⬙ with an optic
axis parallel to the base of the prism was made avail-
able from Inrad Inc. of Northvale, N.J. We measure
the refractive indices for both the polarizations, i.e.
ordinary and extraordinary, in this crystal at the
9 –11 ␮m spectral range available from a tunable cw
CO2 laser source. A minimum deviation technique
is used to measure the refractive indices. The crys-
tal prism is placed on a prism table of a spectrometer
having a least count of 20⬙. By rotating the prism
clockwise and counterclockwise on a horizontal plane
the minimum deviation position is ascertained. The
CO2 laser radiation viewing plates with different sen-
sitivity monitor this minimum deviation position.

20 July 2003 兾 Vol. 42, No. 21 兾 APPLIED OPTICS 4335


Fig. 1. Measured refractive indices in ZGP crystal. The dotted
curve represents the interpolation of our measured refractive in-
dices as per our fitted Sellmeier dispersion relations. Dots 共F兲
represent our measured value. The solid curve represents the
interpolation of the Boyd et al.1 measured refractive indices.
The polarization of the CO2 laser beam as such gives
us the ordinary refractive index in this crystal. To
measure the extraordinary refractive index we rotate
the polarization of the laser beam through a rotation
of the entire laser system by 90°. Noting the mini-
mum deviation and using the conventional formula,
we calculate the refractive indices in this crystal.
The measured refractive indices are shown in Fig. 1.
The dots 共F兲 represent the experimentally measured
value at some spot wavelengths from a cw tunable
CO2 laser. To get the refractive indices at different
wavelengths in this spectral range, we interpolate
the measured value obtained from our fitted
Sellmeier coefficients, which are represented by the
dotted curves. We find that our measured refractive
indices both at ordinary and extraordinary polariza-
tion are about 0.007 and 0.005 higher, respectively,
than that of the measured value of Boyd et al.,1 which
are in sharp contrast of the measured value of Zelmon
et al.29 The accuracy of our measurement of refrac-
tive indices is 5 ⫻ 10⫺4. We also measure refractive
indices both at ordinary and extraordinary polariza-
tion from a Q-switched Nd:YAG laser and find the
measured refractive indices are about 0.01 higher
than that of the measured value of Boyd et al.1 How-
ever, our measured birefringence is found to be ap-
proximately 0.002– 0.003 lower than that of the
measured value of Boyd et al.1 共Fig. 2兲. Based on our
measured refractive indices at 1.32, 9 –11, and also at
5 ␮m spectral bands obtained by frequency doubling
of CO2 laser wavelengths in another ZGP crystal, we
then derive the different Sellmeier coefficients in the
form of A ⫹ B兾共1 ⫺ C兾␭2兲 ⫹ D兾共1 ⫺ E兾␭2兲, which are
presented in Table 1, to get the refractive indices at
any desired wavelengths.
We also carry out the SHG of CO2 laser radiation in
a ZGP crystal. For this purpose a 3-mm-thick 81°
type-I cut crystal was obtained from Inrad, Inc. Be-
fore implementing SHG we measure the absorption
4336 APPLIED OPTICS 兾 Vol. 42, No. 21 兾 20 July 2003
Fig. 2. Illustration of birefringence of ZGP crystal from different
Sellmeier dispersion relations. The smooth curves 共1兲, 共2兲, 共3兲,
and 共4兲 are obtained from the Sellmeier dispersions of Kato,4 this
paper, Zelmon et al.,29 and Madrasz et al.,28 respectively. We do
not represent here the theoretical curves from Sellmeier disper-
sions of Bhar30 and Barnes et al.,27 which follow very closely with
the value of Madrasz et al.,28 to avoid clumsiness. From this
figure it can be seen that the birefringence values obtained from
the dispersion of Kato4 decreases with decrease of wavelength
instead of increase near and below 2 ␮m. This is not at all ac-
ceptable, as there is no reported isotropic point 共crossing of refrac-
tive indices, as in the case of AgGaS2 and AgGaSe2兲 in this crystal.
at some spot wavelengths with the tunable CO2 laser
radiation. It is found that the absorption coefficient
共␣兲 of this crystal is within 0.5– 0.6 cm⫺1 at the spec-
tral region 9.2–10.6 ␮m, except a small peak at 9 ␮m,
as shown in the inset of Fig. 3. We also check our
measured ␣ with that obtained from the spectropho-
tometer measurement.
For the SHG of the CO2 laser radiation, the crystal
is placed on a precision circular table having least
count of 0.1° capable of rotating in a vertical plane,
because the polarization of the laser radiation is ver-
tical, to satisfy the type-I phase-matched interaction.
The CO2 laser beam is focused onto the crystal by a
12-cm-focal-length ZnSe lens. The crystal is placed
at a distance of 13 cm from the lens to avoid any
surface damage. One 3-mm-thick sapphire plate is
sufficient to block the residual unconverted CO2 laser
radiation, and a liquid-nitrogen-cooled mercury cad-
mium telluride detector senses the generated radia-
tion. The output signal from the detector is
displayed on a 100-MHz storage oscilloscope. An in-
tracavity chopper chopped the cw CO2 laser at 300 Hz
internally to increase the peak power. The mea-
sured external phase-matched angle is appropriately
converted to the crystal internal angle. The angular
Table 1. Sellmeier Coefficients for ZnGeP2 Crystal 共␭ Is in Microns兲
n2 ⫽ A ⫹ B兾共1 ⫺ C兾␭2兲 ⫹ D兾共1 ⫺ E兾␭2兲
Polarization A B C D E
Ordinary 5.67491 4.077926 0.159328 1.896005 900
Extraordinary 3.65014 6.310153 0.125099 1.731381 900
Fig. 3. Phase-matched angular tuning characteristics for SHG
共type-I兲 in ZGP crystal throughout its transmission range from
different Sellmeier dispersions. The smooth curves 共1兲, 共2兲, 共3兲,
and 共4兲 are from the Sellmeier dispersions as in the Fig. 2 caption.
Dots 共F兲 represent the experimental points of this investigation,
while 共■兲 and 共Œ兲 represent the previously reported experimental
values by Kato4 and Andreev et al.,3 respectively. They are ex-
panded in Figs. 4共a兲 and 4共b兲. We do not represent here the
theoretical curves from Sellmeier dispersions of Bhar30 and Barnes
et al.27 to avoid clumsiness. Inset shows the measured absorption
coefficients in this crystal. Dots 共F兲 represent the measured value
at some spot wavelengths from a tunable CO2 laser, whereas the
smooth curve is from a spectrophotometer measurement. There
is an increase of absorption near 9 ␮m due to the three-phonon
absorption. The transmission cutoff at 12 ␮m is due to usual
two-photon absorption.
tuning characteristics for SHG throughout its trans-
mission range in this crystal is shown in Fig. 3.
The different dots in Fig. 3 represent the experi-
mental phase-matched angles as reported by differ-
ent investigators,3–5,7 including this measurement,
while the different smooth curves represent theoret-
ical predictions obtained from the Sellmeier disper-
sions of Kato,4 Zelmon et al.,29 Madarasz et al.,28 and
also the Sellmeier coefficients presented in Table 1 of
this paper. It is seen that our measured phase-
matched angles agree well with that of the theoretical
predictions obtained from the Sellmeier coefficients
as presented in Table 1 and in Kato.4 This is also
represented in an expanded curve in Fig. 4共a兲. It
can also be seen from Figs. 3 and 4共a兲 that our mea-
sured phase-matched angles for SHG in the 10.2–
10.63-␮m spectral range differs significantly from
that obtained from the Zelmon et al.29 and Madarasz
et al.28 Sellmeier coefficients. We also examine the
agreement between the predicted phase-matched an-
gles for SHG from CO2 laser radiation obtained from
the Sellmeier coefficients presented in Table 1 of
Fig. 4. Phase-matched angular tuning characteristics for SHG
共type-I兲 in ZGP crystal in the 共a兲 9 –11- and 共b兲 5.5-␮m band ob-
tained from different Sellmeier dispersions. The smooth curves
共1兲, 共2兲, 共3兲, and 共4兲 are as in the Fig. 2 caption. In 共a兲, dots 共F兲
represent the experimental points of this investigation, while 共Œ兲,
共■兲, 共⫻兲 represent the previously reported experimental values by
Kato,4 Andreev,3 and Bhar et al.,5 respectively. In 共b兲, dots 共F兲
represent the experimentally measured values of Kato,4 while 共■兲
represents experimentally measured values of Andreev and co-
workers.8,9,16 We do not represent here the theoretical curves
from Sellmeier dispersions of Bhar30 and Barnes et al.27 to avoid
clumsiness.
this paper and the measured values reported
previously.3–5,7 These are also represented in Figs.
3 and 4共a兲. It is found that the previously reported
phase-matched angles agree well with the prediction
from the Sellmeier coefficients given in Table 1 of this
paper. It is also seen that our previously reported5
phase-matched angles differs significantly from the
present investigation. This may be due to the error
in crystal cut and at the same time may be due to
birefringence variation arising from crystal stoichi-
ometry, because our former crystal was from the
former Soviet Union. Kato4 also noted this differ-
ence.
In our experiment we could measure SHG from
10.2-␮m radiation up to the wavelength of 10.63 ␮m,
which is nearly noncritical. With the present crys-
tal cut we could not get the phase-matched SHG in a
20 July 2003 兾 Vol. 42, No. 21 兾 APPLIED OPTICS 4337
9-␮m spectral band, because a large rotation of the
crystal is needed, which can not be accommodated
with this crystal cut. Again we could not detect
SHG phase matching above 10.63 ␮m owing to a
decrease in effective nonlinearity with an increase in
phase-matching angle and hence a decrease in con-
version as well as output signal 共deff value in a posi-
tive crystal vanishes at noncritical angle兲. It is seen
that the phase-matched full angular acceptance an-
gle increases from 4° at 10.2 ␮m to 6.2° at 10.63 ␮m,
which agrees well with the theoretical prediction ob-
tained from the above-mentioned Sellmeier equa-
tions. Again we also observe the total spectral
acceptance is 0.1 ␮m at 10.6 ␮m, and similar results
are observed at other wavelengths. The slight de- Fig. 5. Phase-matched angular 共type-I兲 tuning characteristics for
parture in theoretical prediction of phase-matching OPO pumped by 2.05 ␮m in ZGP crystal. The smooth curves 共1兲,
angles 共obtained from the Sellmeier coefficients rep- 共2兲, 共3兲, and 共4兲 are from Sellmeier dispersions as in the Fig. 2
caption, whereas 共F兲 and 共■兲 represent the experimental point as
resented in this paper兲 can be accounted for with the
reported by Kato4 and Budni et al.22,24 We do not represent here
large angular bandwidth 共more than 4°, as mentioned the theoretical curves from Sellmeier dispersions of Bhar30 and
above兲 associated near a noncritical phase-matched Barnes et al.,27 which closely following the value of Madrasz et
region, thereby making it difficult to ascertain the al.,28 to avoid clumsiness.
exact phase-matched point. Figure 4共b兲 represents
the expanded phase-matched angular tuning charac-
teristics below 5 ␮m for SHG in ZGP. It can be seen dispersion as claimed by the author appears to be
from Figs. 3 and 4共b兲 that the theoretical prediction better in predicting the measured phase-matched an-
obtained only from Sellmeier coefficients of Kato4 gles, as reported by different investigators, but from
agrees with the experimental values. We observe a Fig. 2 one can see that the birefringence value ob-
departure of approximately 2–3° in a theoretically tained using Kato’s Sellmeier dispersion decreases
predicted phase-matched angle obtained from the with a decrease in wavelength instead of an increase
Sellmeier coefficients presented in this paper and the near and below a wavelength of 2 ␮m, which is not at
experimental values. We also observe an almost all acceptable, as there is no reported isotropic point
similar departure in phase-matched angles obtained 共refractive-index crossing like AgGaS2, AgGaSe2兲 in
with the other Sellmeier coefficients27–30 from the this crystal. This important deviation remains un-
measured values in this region, as represented in Fig. detected, since there is no wavelength, pump, or sig-
4共b兲. nal兾idler near or below 2 ␮m in the reported OPO
We have also checked the other phase-matching experiments.
angles as reported by different investigators for other Figure 9 illustrates the generation of infrared ra-
interactions like OPO; an optical parametric genera-
tor pumped by 2.05,22–24 2.796,18,20 and 2.93 ␮m2; and
also noncritical phase-matched OPO.26 But it is
seen that all of the measured phase-matching angles
reported by the different investigators are not agree-
ing well with the theoretical prediction obtained from
the Sellmeier dispersion available earlier. It can
also be seen by Figs. 5–9 that all of the experimental
reported values could not be explained by any of the
above-mentioned Sellmeier dispersions, including
the ones presented in this paper. For example from,
Fig. 5 it is seen that for pump wavelength at 2.05 ␮m,
the predicted phase-matched angles for OPO from
the Sellmeier coefficients of Kato4 could explain only
his experimental points, but there is a wide depar-
ture from the measured values of others, including
Budni et al.22–24 It is not clear why there is so much
variation in measured phase-matched angles
pumped by the same laser wavelength even though
Fig. 6. Phase-matched angular 共type-II兲 tuning characteristics
the used crystals are from the same source. We ob-
for OPO pumped by 2.796 ␮m in ZGP crystal. The smooth curves
serve from our analysis using all of the available 共1兲, 共2兲, 共3兲, and 共4兲 are theoretical prediction from Sellmeier dis-
Sellmeier coefficients4,27–30 共Figs. 5–9兲 that if one set persions as in the Fig. 2 caption, whereas dots 共F兲 represent the
of Sellmeier coefficients is better for one pump wave- experimental point as reported by Vodopyanov and Voevodin.18
lengths, then that set of Sellmeier coefficients is We do not represent here the theoretical curves from Sellmeier
found to be not good for others. Kato’s Sellmeier dispersions of Bhar30 and Barnes et al.,27 to avoid clumsiness.

4338 APPLIED OPTICS 兾 Vol. 42, No. 21 兾 20 July 2003


Fig. 7. Phase-matched angular 共type-I兲 tuning characteristics for
OPO pumped by 2.93 ␮m in ZGP crystal. The smooth curves 共1兲,
共2兲, 共3兲, and 共4兲 are from Sellmeier dispersions as in the Fig. 2
caption, whereas dots 共F兲 represent the experimental point as
reported by Vodopyanov et al.2 We do not represent here the
theoretical curves from Sellmeier dispersions of Bhar30 and Barnes
et al.,27 to avoid clumsiness.
diation through tuning of the pump radiation in a
ZGP crystal.26 The main advantages of noncritically
phase-matched pump tuning are rapid, flexible, and
wide tuning of output realized through tuning the
pump laser without rotating the crystal. In this
crystal this pump tuning is realized through the
availability of the pump source with the required
threshold energy at 2.2–3.8 ␮m from periodically
poled lithium niobate-OPO.26 From this figure it
can be seen that there is a good agreement between
the experimental points with the theoretical predic-
tion from the Sellmeier dispersion presented in Table
1 of this paper.
In conclusion we have reported some linear and
nonlinear optical properties of ZGP crystal obtained
Fig. 8. Phase-matched angular 共type-II兲 tuning characteristics
for OPO pumped by 2.93 ␮m in ZGP crystal. The smooth curves
共1兲, 共2兲, 共3兲, and 共4兲 are from Sellmeier dispersions as in the Fig. 2
caption, whereas dots 共F兲 represent the experimental point as
reported by Vodopyanov et al.2 We do not represent here the
theoretical curves from Sellmeier dispersions of Bhar30 and Barnes
et al.,27 to avoid clumsiness.
Fig. 9. Noncritically phase-matched 共type-II兲 pump tuning char-
acteristics in a ZGP crystal. The smooth curves 共1兲, 共2兲, 共3兲, and
共4兲 are from Sellmeier dispersions as in the Fig. 2 caption, whereas
dots 共F兲 represent the experimental point as reported by Vodopy-
anov and Schunemann.26 We do not represent here the theoret-
ical curves from Sellmeier dispersion of Bhar30 and Barnes et al.,29
to avoid clumsiness. The main advantage of noncritically phase-
matched pump-tuning devices is that the rapid output 共i.e., signal兾
idler wavelength兲 tuning is available by a simple tuning of the
pump wavelength without altering any situation of the crystal.
from Inrad, Inc. The Sellmeier coefficients pre-
sented in this paper explain fairly the measured
phase-matched angle for different interactions in
ZGP crystal. The marginal departure in the phase-
matched angle particularly near the degenerate re-
gion for OPO can be accounted for with the large
angular bandwidth usually associated with in that
region; the error in the crystal cut and the minute
difference in birefringence arising from the different
crystal growth stoichiometry for different growth
technology may also be the reason for a minor vari-
ation in other region. It is seen that the phase-
matching conditions of Russian crystal for SHG,
sum-frequency generation, and OPO differ consider-
ably from the United States-grown crystal, and Kato4
also noted this. The Sellmeier coefficients presented
here offer a good agreement of the nonlinear phase-
matching properties reported by different authors.
The authors acknowledge the Board of Research in
Nuclear Sciences, Department of Atomic Energy,
Government of India for partial financial support.
The authors also wish to thank John Maffetone of
Inrad, Inc. for supplying the ZGP crystal and the
prism samples.
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