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Optical Materials 23 (2003) 353356

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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-


sorption edge and a high damage threshold. Un-
The performance of high-power solid-state ul- fortunately up to now, these crystals can not be
traviolet (UV) lasers depends on ecient nonlinear grown into suciently large sizes to meet the re-
optical (NLO) crystals that are employed for laser quirements for proper measurement of linear and
frequency conversion. A series of new UV crystals NLO properties up. In 1997, we discovered and
have been discovered, including Sr2 Be2 B2 O7 grew a new NLO crystal, K2 Al2 B2 O7 (KAB) [79].
(SBBO) [1] and other related structures: Its structure also belongs to SBBO series. How-
Ba2 Be2 B2 O7 (TBO), Sr2x Ba212x Be2 B2 O7 (STBO) ever, in case of KAB the band strength between
[2], BaAl2 B2 O7 (BABO) [35], and SrAl2 B2 O7 layers is stronger than other crystals in the SBBO
(BABO) [6] all of which possess nearly the same series [10]. The implication is that KAB might be
crystal structure as SBBO. Although these crystals more easily grown than SBBO and other struc-
exhibit a large second harmonic generation (SHG) 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-
*
Corresponding author. Tel.: +81-6-6879-7707; fax: +81-6- cations in the SBBO series. In addition, due to the
6879-7708. presence of the element Al as one of the compo-
E-mail address: hu@ssk.pwr.eng.osaka-u.ac.jp (Z.-G. Hu). 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. 18  13 tmm3 for UV light generation, as shown in
Crystalline KAB exhibits high chemical stability, is Fig. 1. We believe that even larger crystals can be
free of moisture and hygroscopy and has good grown using MSSG method provided the size of
mechanical properties. The Mohs hardness of crucible is large enough and sucient time is al-
crystalline KAB is measured to be about 6.0. lowed. MSSG has the advantage of avoiding un-
These properties make KAB more advantageous controlled spontaneous nucleation on the solution
over other borate crystals such as b-BaB2 O4 surface and thus the method could be a new way to
(BBO), LiB3 O5 (LBO), CsB3 O5 (CBO) and improve the homogeneity of the growth solution
CsLiB6 O10 (CLBO). However, the viscosity of the and promote diusion of the solute.
solution is high due to the elements Al in the KAB
crystal that creates trouble during crystal growth.
3. UV light generation

2. KAB crystal growth 3.1. KAB Type-I for 355 nm generation

The growth of KAB crystals have been reported Chen et al. [13] reported that the ultraviolet
by our group and by Zhang et al. In our previous beam at 266 nm was obtained by fourth harmonic
work, the KAB crystals were grown by the modi- generation of 1064 nm Q-switched Nd:YAG laser
ed middle-seeded solution growth (MSSG) radiation through a KAB crystal. The conversion
method [11] using K2 CO3 B2 O3 NaF as ux at a eciency of the fourth harmonic generation with a
growth temperature of about 900 C, Zhang et al. KAB specimen of 3.7 mm in length reached 12.3%
reported that they had grown large sized KAB and output energy at 266 nm reached 0.281 mJ. In
crystals using an improved top-seeded growth this work, we obtained 355 nm UV light using
method with NaF ux and with growth tempera- third harmonic generation (THG) of a Q-switched
tures between 780 and 820 C [12,13]. In the pre- Nd:YAG laser through a KAB crystal at a repe-
sent work also, we adopt the growth method as tition rate of 62.5 kHz. The measured value of deff
described in our earlier report. The signicant (THG) is 0.51 pm/V for Type-I and the experi-
dierence is that the cooling rate is lower than used mental Type-I phase-matching angle for THG is
previously [11], and consequently the growth pe- 36.9, which is comparable with the calculated
riod is made two times longer. We were able to value of 36.7. The measured acceptance angle is
grow bulk KAB crystals with dimensions of 21  0.68 mrad cm, as compared to the calculated value

Fig. 1. The photograph of a KAB single crystal with dimensions of 21  18  13 tmm3 .


Z.-G. Hu et al. / Optical Materials 23 (2003) 353356 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
Fig. 2. THG output at 62.5 kHz from Type-I KAB crystal. (SFG) output of an RbTiOAsO4 (RTA) optical
parametric oscillation (OPO) tuned to 235.8 nm
0.64 mrad cm. The calculated walk-o angle is 49.1 [16].
mrad. The theoretical values were calculated using The schematic diagram of the experimental
the following Sellmeier equations [16]: setup is shown in Fig. 3. The pump source was the
LD-pumped Nd:YAG laser operating in the
0:01304 TEM00 mode with 18 W average power at 10 kHz.
n20 2:3768 2
 0:01317k2
k  0:01932 Using a 1.5 cm long KTiOPO4 (KTP) crystal, we
generated 11W average power SHG at 532.1 nm
0:00933
n2e 2:1731 2
 0:00629k2 that was used to pump the RTA OPO. The RTA
k  0:01601 crystal of 2.5 cm length was cut at h 83 and
where k is in lm. Fig. 2 represents the relationship u 0 and AR-coated at 850 nm to generate a
between the output power at 355 nm and the signal wavelength of 850 nm near normal inci-
fundamental input power at a repetition rate of dence. The generated 847 nm pulses were fre-
62.5 kHz. The 355 nm output increases as the quency doubled by a 7 mm long, AR-coated BBO
fundamental laser power increases. The conversion crystal cut at h 24. The generated 423.5 nm
eciency of THG with a KAB specimen 5 mm in pulses were then mixed with the unmatched pump
length reached 2.4% and the output energy at 355 beam at 532.1 nm in the second CLBO crystal (cut
nm reached 0.125 mJ, but the output of Type-I with h 90) placed outside the OPO cavity. The
KAB operated at room temperature was not sat- average output power we generated at 235.8 nm
urated at an input of 8.2 mJ in this preliminary was 0.8 W at 10 kHz. Since the polarization di-
measurement. rection of the 235.8 nm beam diers by 45 from
Further investigation with these measurements the Nd:YAG laser fundamental beam, a 45 po-
is in progress. larization rotator was placed in the Nd:YAG laser
beam to align the polarization directions before
3.2. KAB for 193 nm generation of Type-I entering the KAB crystal. The UV beam generated
at 193 nm was physically separated from the
All-solid-state UV laser sources operating at combined beams by two MgF2 prisms and its
193 nm wavelength are important for micro-
lithographic applications, allowing imaging sys- LD-pumped Nd:YAG KTP OPO
1064.2 nm 532.1 nm
tems at the ArF exposure wavelength. They are
also in high demand for eye surgery systems be- CLBO KAB
423.5 nm 235.8 nm 193 nm
cause of their compactness, ease of operation and
short optical wavelength. Conversion eciency of Fig. 3. 193 nm prototype system by KAB with mixing the
1.3% from fundamental, 1547 nm, to eighth har- Nd:YAG laser.
356 Z.-G. Hu et al. / Optical Materials 23 (2003) 353356

output power was monitored by a scientic power [2] C. Chen, N. Ye, B. Wu, W. Zeng, Q. Zhang, C. Zhang,
meter. The maximum output power observed at Y. Zhang, Proc. Int. Symp. Laser and Nonlinear Optical
Materials, Singapore 1997, p. 103.
the phase-matching angle of KAB hPM 68:9 was [3] X.P. Tang, Master Thesis, Department of Applied Chem-
220 mW at 20 C. No degradation in the output istry, University of Science and Technology of China,
power was observed after 50 h of operation. The Hefei, 1994.
measured angle and temperature phase-matching [4] K. Yamada, Mitsui Petrochemical Ind., Jpn. Kokai
bandwidths (FWHM) were Dhex l 0:3 mrad cm Tokkyo Koho Jp, 09.61, 864.
[5] N. Ye, W. Zeng, B. Wu, X. Huang, C. Chen, Kristallog-
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KAB 0:23  0:02 pm/V from direct com- 204.
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Sasaki, Z. Kristallographie, New Cryst. Struct. 214 (1999)
A large-sized KAB crystal has been grown by 433.
[10] Z.-G. Hu, N. Ushiyama, Y.K. Yap, M. Yoshimura, Y.
the MSSG method. A THG output of 0.125 mJ
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an average power of 200 mW with UV pulses at Y. Mori, T. Sasaki, Jpn. J. Appl. Phys. 40 (2001)
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CPD 9 (2000) 17.
[15] T. Ohtsuki, H. Kitano, H. Kawai, S. Owa, CLEO Proc.
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