CHIN. PHYS. LETT. Vol. 28, No.

3 (2011) 034201

*
Terahertz Generation in Nonlinear Crystals with Mid-Infrared CO2 Laser
LU Yan-Zhao(卢彦兆), WANG Xin-Bing(王新兵)** , MIAO Liang(苗亮), ZUO Du-Luo(左都罗),
CHENG Zu-Hai(程祖海)
Wuhan National Laboratory for Optoelectronics, School of Optoelectronic Science and Engineering, Huazhong
University of Science and Technology, Wuhan 430074

(Received 14 October 2010)

The terahertz (THz) generation based on difference frequency generation in nonlinear optical crystals pumped
by mid-infrared CO2 laser has been investigated. We present a comprehensive study of the phase-matching
conditions in the GaSe, ZnGeP2 and GaAs crystals. A comparison of the characteristics of these crystals as the
THz frequency generator is also presented. The investigation of the conversion efficiency shows that GaSe and
GaAs are the most promising nonlinear crystals for the efficient and widely tunable THz generation.

PACS: 42.65.Ky, 42.79.Nv, 42.55.Lt DOI: 10.1088/0256-307X/28/3/034201

A tunable, coherent and narrow-linewidth tera-
hertz source has attracted great attention for its
potential applications in chemical identifications,
biomedical diagnostics and THz spectroscopy.[1−3] To
realize these applications, an efficient, compact and
widely tunable THz source is essential. Although the
free-electron laser (FEL) can cover an extremely wide-
tuning range and deliver high power, it is too bulky
and complex to be employed. Quantum cascade laser
(QCL) is respected as the most promising THz source,
but it should still be operated at the cryogenic tem-
perature and its frequency tuning is quite challenging.
Among most of the THz sources, difference-frequency
generation (DFG) in nonlinear crystals is one of the ef-
fective ways to generate high-power, tunable and nar-
rowband THz radiation.
In the past, THz generations based on DFG
have been demonstrated in many nonlinear optical
(NLO) crystals, such as GaSe,[4] ZnGeP2 ,[5] GaP,[6,7]
LiNbO3 ,[8] GaAs[9] and DAST,[10] but most of them
were pumped by near-infrared lasers at the wavelength
around 1 µm. According to the Manley–Rowe relation,
the maximum conversion efficiency can be improved
by an order of magnitude when using CO2 laser with
a longer wavelength running at 10 µm. Even though
the DFG terahertz sources pumped by CO2 lasers have
been reported since the 1970s,[9] the advantage of us-
ing these lasers has not been fully exploited. Recently,
the kW level of THz peak power was demonstrated
for conventional nanosecond CO2 lasers[11] and MW
power for shorter 250 ps pulses in GaAs crystal.[12]
By mixing the two Q-switched CO2 lasers, an aver-
age power of 260 µW was obtained in GaSe crystal.[13]
On the other hand, among the variety of NLO crys-
tals, high transparency in both the pump wavelength
and THz regions is the most crucial factor. Addition-
ally, large nonlinear coefficient, high damage threshold
and good optical quality also determine the conversion
efficiency. Several crystals such as GaAs, GaSe and
ZnGeP2 satisfy these requirements.
Considering the maturity of CO2 laser technol-
ogy and noticing that large-aperture infrared crystals
are commercially available, it will be an effective way
to generate THz radiation based on DFG with CO2
lasers. However, most of the studies reported before
were mainly focused on the DFG of THz radiation
pumped by near-infrared lasers. The investigation
of conversion in NLO crystal pumped by CO2 laser
has not been reported in detail before. In this Let-
ter, we discuss the characteristics of GaSe, GaAs and
ZnGeP2 , which can be used as the frequency convert-
ers in the THz generation pumped by CO2 laser, and
investigate the phase-matching (PM) conditions and
the conversion efficiencies in the DFG process with
these crystals.
In our laboratory, we have established a dual-
wavelength CO2 laser for the tunable terahertz
generation.[14] This CO2 laser can be tuned to gen-
erate more than 60 vibration-rotational transitions in
the wavelength region from 9.2 µm to 10.8 µm. When
radiation from this dual-wavelength laser is mixed in
a crystal, more than 2000 different frequencies can be
generated in the terahertz region, which could cover
from 70 µm to 9 mm (0.03–4.28 THz) with an average
spacing of 0.04 cm−1 between neighbouring lines.
In the past, GaSe crystal was successfully used
for the frequency conversions in the mid-infrared
region[15] and DFG of THz radiation with pumped
beams at 1 µm.[4] It has an extremely wide trans-
parency in the range of 0.65–18 µm and THz region
from 60 µm to several millimeters. Ding et al.[16]
has shown that GaSe has the lowest THz absorp-
tion coefficient among many NLO crystals. Nev-
ertheless, GaSe will suffer large Fresnel losses be-

* Supported
in part by the Creative Foundation of Wuhan National Laboratory for Optoelectronics (No Z080007).
** To
whom correspondence should be addressed. Email: xbwang@mail.hust.edu.cn
© 2011 Chinese Physical Society and IOP Publishing Ltd

034201-1

cause of its soft layer structure of the pure crystal,
which makes it difficult to be cut or polished. GaSe
possesses a large second-order nonlinear coefficient
(𝑑22 (10.6 µm) = 54 pm/V).[17] In addition, its large
birefringence makes it feasible that the generated THz
wavelength could be easily tuned in an ultrabroad
range by rotating the crystal. For the negative uniax-
ial GaSe crystal, only collinear type II phase-matching
oe-o and oe-e (the first and second letters represent the
polarizations for the pump beams, while the third let-
ter corresponds to the polarization for the THz beam)
configurations can be phase-matched.
When GaSe is pumped by CO2 laser, the theoret-
ical internal and external phase-matching curves for
collinear DFG are shown in Fig. 1. They were calcu-
lated by using the Sellmeier equations from Ref. [18].
From Fig. 1, we can see that for the type oe-e PM
configuration, the internal PM angle ranges from 2∘
to 27.6∘ and the corresponding external angle ranges
from 5.4∘ to 90∘ . The internal and external PM angles
of type oe-o configuration are in the range of 2∘ –50.1∘
and 5.4∘ –90∘ , respectively. Obviously, the PM angles
of type oe-o are larger than those of type oe-e. It can
not be collinearly phase-matched inside a 𝑍-cut GaSe
crystal when the generated THz wavelength is shorter
than 103 µm, since the calculated external PM angle
is larger than 90∘ . By using the two type interactions,
the output THz radiation could cover a tuning range
of 103–9734 µm (0.03–2.91 THz).
Phase-matching angle (deg)
80
60
40
in
20
0 However, it suffers increasing photon absorption be-
50 100
THz wavelength (mm)
Fig. 1. Phase-matching angle versus the generated THz
wavelength with GaSe crystal.
ZnGeP2 crystal is another effective crystal for
frequency mixing in the mid-infrared range, it has
also been used to generate THz radiation by DFG
with CO2 lasers and near-infrared lasers before.[5,19,20]
ZnGeP2 possesses the largest nonlinear coefficient
(𝑑36 (9.6 µm) = 75 pm/V)[17] among the infrared bire-
fringence crystals and its THz absorption is also
smaller than most of the others.[16] Considering mix-
ing of the CO2 laser beams in the positive ZnGeP2
crystal, only collinear interaction type eo-e and type
eo-o configurations can be phase-matched.
The theoretical predictions of the PM angles are
CHIN. PHYS. LETT. Vol. 28, No. 3 (2011) 034201
shown in Fig. 2. Obviously, the PM angles are much
larger than those of GaSe crystal, which is because of
its small birefringence. In this case, the PM conditions
can only be achieved when the generated THz wave-
length is longer than 407 µm for an uncut ZnGeP2
crystal. This short wavelength end is much longer
than that of GaSe crystal. We can see from Fig. 2 that
the internal angles for the type eo-e and type eo-o are
in the ranges of 3.8∘ –77.5∘ and 3.8∘ –67∘ , respectively.
The PM angle decreases when the THz wavelength in-
creases. For the two type interactions, tunable THz
radiation in the range of 407–9734 µm (0.03–0.74 THz)
can be achieved. For achieving shorter THz wave-
length generation, crystal cutting should be needed
for ZnGeP2 .
Phase-matching angle (deg)
80 eo-e
eo-o
60
40
in ext
20
0
100 1000 10000
THz wavelength (mm)
Fig. 2. Phase-matching angle versus the generated THz
wavelength with ZnGeP2 crystal.
oe-e Optically isotropic semiconductor GaAs is also an
oe-o
efficient THz frequency generator, because of its large
nonlinear coefficient (𝑑36 (10.6 µm) = 83 pm/V)[21]
and small absorption loss. Johnson et al.[22] have
measured the THz absorption of high-resistivity GaAs
ext
crystal (3.5×108 Ω·cm). It has been shown that GaAs
has a small absorption coefficient and a wide trans-
parency ranging from 60 µm to several millimeters.
1000 10000
low 200 µm.
For isotropic GaAs crystal, it is possible to ob-
tain phase-matched DFG by noncollinear mixing of
two CO2 laser beams.[9,11,12] The simple geometry of
noncollinear phase matching is shown in the inset of
Fig. 3. As depicted in the figure, one of the pump laser
beams is incident along the normal to the input face
of the GaAs crystal. The other beam is ensured by a
noncollinear geometry to overlap the first beam with
an angle 𝜃ext , with the corresponding angle inside the
crystal 𝜃in .[9]
The calculated PM angles 𝜃in , 𝜃ext and the output
angle 𝜙 by using the Sellmeier equation from Ref. [23]
are shown in Fig. 3. It can be seen that the PM angles
of GaAs are very small. The internal and external an-
gles vary in the range of 0.02–4.9∘ and 0.07–16.2∘ . In
034201-2
 CHIN. PHYS. LETT. Vol. 28, No. 3 (2011) 034201

order to achieve THz wavelength shorter than 120 µm,
the PM angle is larger than 5∘ , which will sacri-
fice the spatial overlap among the three participating
beams. The two pump beams will almost propagate
collinearly inside the crystal when generating millime-
ter wave. It is shown in Fig. 3 that the THz output
angle 𝜙 is ∼ 22∘ throughout the THz region, which
is larger than the THz total-reflection angle in the
GaAs crystal. Consequently, the output face of GaAs
crystal is often cut at an angle of 10–20∘ as shown in
Fig. 3, which can also been used to decouple both the
pump beams and the output THz wave. GaAs crys-
tal could cover the tuning range of 60–9734 µm (0.03–
5 THz) when being perfectly phase-matched, but it
suffers larger absorption below 200 µm.
the order of the THz wavelength and increases with
the output wavelength. While the maximum 𝐿𝑐 is
19 mm when generating at the wavelength of 9.74 mm.
This may suggest that it is impossible to be perfectly
phase-matched inside the GaAs crystal for collinearly
mixing of CO2 laser beams, but it can still be utilized
to generated THz radiation within this characteristic
thickness of GaAs crystal. For example, GaAs wafers
with a thickness of the order of coherence length can
be stacked to form a periodic structure, which can
also be utilized for generated THz radiation by quasi-
phase-matched DFG using two collinearly propagated
CO2 laser beams.[25,26]
1
GaSe, oe-o Pump GaSe, oe-e Pump

Walk-off angle (deg)

GaSe, oe-e THz ZnGeP2, eo-o Pump

25 ZnGeP2, eo-e Pump ZnGeP2, eo-e THz

Phase-matching angle (deg)

0.1

20
GaAs

15 ext 0.01

THz
10
THz
ext
100 1000 10000
5 in
THz wavelength (mm)
in

0 Fig. 5. Walk-off angle versus the THz wavelength in

GaAs, GaSe and ZnGeP2 crystals.
100 1000 10000
THz wavelength (mm) 10
Fig. 3. Noncollinear phase-matching angle versus the gen- GaSe oe-o
GaSe oe-e
erated THz wavelength. 8
ZnGeP2 eo-o
(degScm)

ZnGeP2 eo-e
6 GaAs
Coherence length (mm)

10
4
S

2
D

0.1 100 1000 10000

0
50 100
THz wavelength (mm)
Fig. 4. Coherence length for collinear phase-matching in
GaAs crystal.
The DFG process can also be phase-matched by
collinear mixing of near-infrared pump waves even
in the isotropic crystals without birefringence.[25] For
some THz wavelengths, the coherence lengths for DFG
are long enough for perfectphase-matching. Accord-
ing to Herman’s theory, we calculated the coherence
length 𝐿𝑐 for the collinear interaction with CO2 laser
pump beams in the GaAs crystal, which is defined as
𝐿𝑐 = 𝜋/(𝑘1 − 𝑘2 − 𝑘3 ).
As is shown in Fig. 4, the coherence length is of
THz wavelength (mm)
1000 10000
Fig. 6. Acceptance angle versus the THz wavelength in
GaAs, GaSe and ZnGeP2 crystals.
Considering the walk-off effect on conversion effi-
ciency, we also calculate the accurate walk-off angles
for the extraordinary waves of the pump and gener-
ated THz beams. The results for each type of PM op-
erations in GaSe and ZnGeP2 are shown in Fig. 5. It
can be seen that all the extraordinary waves of pump
and THz beams have very small walk-off angles inside
the GaSe and ZnGeP2 crystals. The effect of walk-off
can be ignored when the DFG interactions are per-
fectly phase-matched.
In addition, we also give the numerical results for
the acceptance angles in the DFG processes within the
034201-3
 CHIN. PHYS. LETT. Vol. 28, No. 3 (2011) 034201
three crystals. The phase-mismatch parameter can be
characterized as |∆𝑘𝐿/2| < 𝜋/2, the corresponding
acceptance angles inside the crystals are represented
in Fig. 6 by the factor of ∆𝜃 · 𝑙, where 𝑙 is the crystal
length 1 cm. It is shown that ZnGeP2 crystal has the
largest acceptance angle, which is more beneficial for
the experimental operation. It is mainly caused by
its very large PM angles. The ∆𝜃 · 𝑙 values for two
type interactions in GaSe are almost in coincidence,
while the noncollinear DFG in GaAs crystal suffers
from the smallest acceptance angle. It is about 0.05∘
inside a 1-cm-long crystal and external tuning angle
is approximately 0.15∘ . Therefore, accurate control of
PM angle for experimental noncollinear DFG in GaAs
is important.
10-1
10-2
Conversion efficiency
10-3
10-4
10-5
10-6
10-7
10-8
100 1000
THz wavelength (mm)
Fig. 7. Conversion efficiency versus the THz wavelength
in GaAs, GaSe and ZnGeP2 crystals without absorptions.
To evaluate the performances for using these crys-
tals as THz frequency converters, we calculate the
spectral dependence of the DFG conversion efficiency
(CE), when all the interactions can be perfectly phase-
matched. One can estimate the conversion efficiency
without considering the THz absorption by using
the following expression in the plane-wave fixed-field
approximation:[17]
𝑃3 8𝜋 2 𝑑2eff 𝐿2 𝑃2
𝜂= = ,
𝑃1 𝜀0 𝑐𝑛1 𝑛2 𝑛3 𝜆23 𝐴
where 𝐿 is the crystal length 10 mm, the pump in-
tensity 𝑃2 /𝐴 = 10 MW/cm2 . The effective nonlinear
coefficients 𝑑eff is calculated with respect to the PM
angles of each crystal.
We can see from Fig. 7 that for the same pump
intensity, the GaAs crystal leads to the largest con-
version efficiency. The CE of GaSe crystal is larger
than that of ZnGeP2 crystal in the range from 200 µm
to 9.7 mm. While the ZnGeP2 crystal with type eo-
e PM configuration has a larger CE below 200 µm,
but it should be cut due to the large PM angle, which
would be inconvenient for the THz wavelength tuning.
Consequently, GaSe and GaAs are the most promising
NLO crystals for the efficient and widely tunable THz
generation.
In conclusion, we have investigated the conver-
sion characteristics of the three NLO crystals GaSe,
ZnGeP2 and GaAs, which can be utilized as the THz
frequency generator based on DFG pumped by CO2
laser. The GaAs crystal could cover the broadest tun-
ing range of THz frequencies with high CE when being
perfectly phase-matched, while it suffers larger pho-
ton absorption in the high frequency region (below
200 µm). ZnGeP2 crystal will need to be cut because
of its large incidence PM angle. In addition, GaSe
crystal has a small incidence angle and could cover
a wide tuning range by rotating the crystal. Taking
into account the maturity of CO2 lasers and availabil-
ity of large-size infrared crystals, it is an effective way
GaAs
to generate THz radiation based on DFG with CO2
GaSe oe-e
laser.
GaSe oe-o
ZnGeP2 eo-e
ZnGeP2 eo-o
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034201-4