Optical Materials 23 (2003) 353356

www.elsevier.com/locate/optmat

Growth of K2Al2B2O7 crystal for UV light generation

a,*
Z.-G. Hu , M. Yoshimura a, Y. Mori a, T. Sasaki a, K. Kato b

a
Department of Electrical Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871,
Japan
b
Chitose Institute of Science and Technology, Bibi 758-65, Chitose, Hokkaido, Japan

Abstract

A new nonlinear optical alumino-borate crystal, K2 Al2 B2 O7 (KAB) with dimensions of 21
18
13 mm3 , has been
grown using a modied middle-seeded solution growth method. The signicant abilities of KAB crystals for the
generation of power ultraviolet (UV) light have been demonstrated. Crystalline KAB has been successfully used to
generate the third harmonics of 1064.2 nm light. The dependence of the average power of the 355 nm third harmonic
radiation on the Nd:YAG laser power has been studied. 200 mW average power UV pulses at 193 nm were generated in
KAB by mixing the Nd:YAG laser and sum-frequency generation of a RbTiOAsO4 (RTA) optical parametric oscil-
lation at 10 kHz. No degradation in the output power was observed after 50 h operation.
2003 Elsevier Science B.V. All rights reserved.

PACS: 81.10; 42.70.M

Keywords: Crystal; Nonlinear optic; Borates; Laser

1. Introduction coecient, moderate birefringence, a short ab-

The performance of high-power solid-state ul-
traviolet (UV) lasers depends on ecient nonlinear
optical (NLO) crystals that are employed for laser
frequency conversion. A series of new UV crystals
have been discovered, including Sr2 Be2 B2 O7
(SBBO) [1] and other related structures:
Ba2 Be2 B2 O7 (TBO), Sr2x Ba212x Be2 B2 O7 (STBO)
[2], BaAl2 B2 O7 (BABO) [35], and SrAl2 B2 O7
(BABO) [6] all of which possess nearly the same
crystal structure as SBBO. Although these crystals
exhibit a large second harmonic generation (SHG)
*
Corresponding author. Tel.: +81-6-6879-7707; fax: +81-6-
6879-7708.
E-mail address: hu@ssk.pwr.eng.osaka-u.ac.jp (Z.-G. Hu).
sorption edge and a high damage threshold. Un-
fortunately up to now, these crystals can not be
grown into suciently large sizes to meet the re-
quirements for proper measurement of linear and
NLO properties up. In 1997, we discovered and
grew a new NLO crystal, K2 Al2 B2 O7 (KAB) [79].
Its structure also belongs to SBBO series. How-
ever, in case of KAB the band strength between
layers is stronger than other crystals in the SBBO
series [10]. The implication is that KAB might be
more easily grown than SBBO and other struc-
turally related crystals. The results of our experi-
ments show that KAB is the rst crystal that can
be grown to large sizes for practical laser appli-
cations in the SBBO series. In addition, due to the
presence of the element Al as one of the compo-
nents of the KAB lattice, the physical properties of

0925-3467/03/$ - see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0925-3467(02)00317-8
354 Z.-G. Hu et al. / Optical Materials 23 (2003) 353356
the borate crystal have been greatly improved.
Crystalline KAB exhibits high chemical stability, is
free of moisture and hygroscopy and has good
mechanical properties. The Mohs hardness of
crystalline KAB is measured to be about 6.0.
These properties make KAB more advantageous
over other borate crystals such as b-BaB2 O4
(BBO), LiB3 O5 (LBO), CsB3 O5 (CBO) and
CsLiB6 O10 (CLBO). However, the viscosity of the
solution is high due to the elements Al in the KAB
crystal that creates trouble during crystal growth.
2. KAB crystal growth
The growth of KAB crystals have been reported
by our group and by Zhang et al. In our previous
work, the KAB crystals were grown by the modi-
ed middle-seeded solution growth (MSSG)
method [11] using K2 CO3 B2 O3 NaF as ux at a
growth temperature of about 900 C, Zhang et al.
reported that they had grown large sized KAB
crystals using an improved top-seeded growth
method with NaF ux and with growth tempera-
tures between 780 and 820 C [12,13]. In the pre-
sent work also, we adopt the growth method as
described in our earlier report. The signicant
dierence is that the cooling rate is lower than used
previously [11], and consequently the growth pe-
riod is made two times longer. We were able to
grow bulk KAB crystals with dimensions of 21

Fig. 1. The photograph of a KAB single crystal with dimensions of 21
18
13 tmm3 .
18
13 tmm3 for UV light generation, as shown in
Fig. 1. We believe that even larger crystals can be
grown using MSSG method provided the size of
crucible is large enough and sucient time is al-
lowed. MSSG has the advantage of avoiding un-
controlled spontaneous nucleation on the solution
surface and thus the method could be a new way to
improve the homogeneity of the growth solution
and promote diusion of the solute.
3. UV light generation
3.1. KAB Type-I for 355 nm generation
Chen et al. [13] reported that the ultraviolet
beam at 266 nm was obtained by fourth harmonic
generation of 1064 nm Q-switched Nd:YAG laser
radiation through a KAB crystal. The conversion
eciency of the fourth harmonic generation with a
KAB specimen of 3.7 mm in length reached 12.3%
and output energy at 266 nm reached 0.281 mJ. In
this work, we obtained 355 nm UV light using
third harmonic generation (THG) of a Q-switched
Nd:YAG laser through a KAB crystal at a repe-
tition rate of 62.5 kHz. The measured value of deff
(THG) is 0.51 pm/V for Type-I and the experi-
mental Type-I phase-matching angle for THG is
36.9, which is comparable with the calculated
value of 36.7. The measured acceptance angle is
0.68 mrad cm, as compared to the calculated value
 Z.-G. Hu et al. / Optical Materials 23 (2003) 353356
Fig. 2. THG output at 62.5 kHz from Type-I KAB crystal.
0.64 mrad cm. The calculated walk-o angle is 49.1
mrad. The theoretical values were calculated using
the following Sellmeier equations [16]:
0:01304
n20 2:3768 2
 0:01317k2
k  0:01932
0:00933
n2e 2:1731 2
 0:00629k2
k  0:01601
where k is in lm. Fig. 2 represents the relationship
between the output power at 355 nm and the
fundamental input power at a repetition rate of
62.5 kHz. The 355 nm output increases as the
fundamental laser power increases. The conversion
eciency of THG with a KAB specimen 5 mm in
length reached 2.4% and the output energy at 355
nm reached 0.125 mJ, but the output of Type-I
KAB operated at room temperature was not sat-
urated at an input of 8.2 mJ in this preliminary
measurement.
Further investigation with these measurements
is in progress.
3.2. KAB for 193 nm generation of Type-I
All-solid-state UV laser sources operating at
193 nm wavelength are important for micro-
lithographic applications, allowing imaging sys-
tems at the ArF exposure wavelength. They are
also in high demand for eye surgery systems be-
cause of their compactness, ease of operation and
short optical wavelength. Conversion eciency of
1.3% from fundamental, 1547 nm, to eighth har-
355
monic (x 7x ! 8x) has been achieved and 0.32
mW average power of 193 nm has also been ob-
tained for LBO crystal [15]. Moreover, in the case
of CLBO crystal, conversion eciency of 7.0% and
2.8 mW average power of 193 nm have been ob-
tained [14]. KAB possesses a larger birefringence
(Dn 0:074) as compared to CLBO, and high-
transparency down to 180 nm. It appears that
KAB could be a superior material for UV gener-
ation below 200 nm. Here we report the attain-
ment of UV generation at 193 nm in KAB. This
was achieved by mixing the Nd:YAG laser at
1064.2 nm with the sum-frequency generation
(SFG) output of an RbTiOAsO4 (RTA) optical
parametric oscillation (OPO) tuned to 235.8 nm
[16].
The schematic diagram of the experimental
setup is shown in Fig. 3. The pump source was the
LD-pumped Nd:YAG laser operating in the
TEM00 mode with 18 W average power at 10 kHz.
Using a 1.5 cm long KTiOPO4 (KTP) crystal, we
generated 11W average power SHG at 532.1 nm
that was used to pump the RTA OPO. The RTA
crystal of 2.5 cm length was cut at h 83 and
u 0 and AR-coated at 850 nm to generate a
signal wavelength of 850 nm near normal inci-
dence. The generated 847 nm pulses were fre-
quency doubled by a 7 mm long, AR-coated BBO
crystal cut at h 24. The generated 423.5 nm
pulses were then mixed with the unmatched pump
beam at 532.1 nm in the second CLBO crystal (cut
with h 90) placed outside the OPO cavity. The
average output power we generated at 235.8 nm
was 0.8 W at 10 kHz. Since the polarization di-
rection of the 235.8 nm beam diers by 45 from
the Nd:YAG laser fundamental beam, a 45 po-
larization rotator was placed in the Nd:YAG laser
beam to align the polarization directions before
entering the KAB crystal. The UV beam generated
at 193 nm was physically separated from the
combined beams by two MgF2 prisms and its
LD-pumped Nd:YAG KTP OPO
1064.2 nm 532.1 nm
CLBO KAB
423.5 nm 235.8 nm 193 nm
Fig. 3. 193 nm prototype system by KAB with mixing the
Nd:YAG laser.
356 Z.-G. Hu et al. / Optical Materials 23 (2003) 353356
output power was monitored by a scientic power
meter. The maximum output power observed at
the phase-matching angle of KAB hPM 68:9 was
220 mW at 20 C. No degradation in the output
power was observed after 50 h of operation. The
measured angle and temperature phase-matching
bandwidths (FWHM) were Dhex l 0:3 mrad cm
and DTl 2:1 C cm. We note that the eective
NLO constant for this process was found to be deff
KAB 0:23  0:02 pm/V from direct com-
parison of the conversion eciencies observed for
fth harmonic generation of the Nd:YAG laser
with CLBO.
4. Conclusion
A large-sized KAB crystal has been grown by
the MSSG method. A THG output of 0.125 mJ
was generated at 62.5 kHz for the KAB crystal and
an average power of 200 mW with UV pulses at
193 nm was generated by mixing the Nd:YAG
laser and SFG of the RTA OPO at 10 kHz. No
degradation in the output power was observed
after 50 h of operation. These properties show that
KAB is a good candidate for UV generation.
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