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Journal of Crystal Growth 236 (2002) 318322

Growth and characterization of a new nonlinear optical


mixed borate crystal
S. Ishwar Bhat, P. Mohan Rao*, V. Upadyaya, H.S. Nagaraja
Department of Physics, Mangalore University, Mangalagangotri 574199, Karnataka, India

Received 20 August 2001


Communicated by M. Schieber

Abstract

Single crystals of nonlinear optical (NLO) material barium strontium borate were grown in our laboratory by
employing the low-temperature solution technique for the rst time. Crystals were grown upto a size of
20 mm  10 mm  1 mm. These crystals show good second-harmonic generation eciency. Single crystals of barium
strontium borate is a promising NLO crystal which can be possibly used for fabrication of photonic devices. The grown
crystals are characterized by employing UVvisible spectroscopy, powder XRD, IR spectroscopy, microhardness and
refractive index measurements. r 2002 Elsevier Science B.V. All rights reserved.

Keywords: A2. Growth from solutions; B1. Borates; B2. Nonlinear optic materials

1. Introduction wide applications have been reported such as b-


BaB2O4 [3], LiB3O5 [4], CsB3O5 [5], KBe2BO3F2
The development of highly ecient nonlinear [6], Sr2B2Be2O7 [7], and CsLiB6O10 [8,9]. All
optical (NLO) crystals is of great importance to borate crystals reported earlier have been grown
extend the frequency range provided by normal by using high-temperature ux methods. In this
laser sources into the ultraviolet and infrared paper, the growth of single crystals of mixed
regions. Since the basic work by Bloembergen [1], barium strontium borate by slow evaporation
harmonic generation by NLO materials has gained method and its optical properties are reported.
technical importance over the years. It is well
known that the inorganic borates exist in numer-
ous structural types and some crystals such as 2. Crystal growth
KB5 KB5 O8  4H2 O and BBO (b-BaB2O4) are
excellent NLO materials, particularly in the UV The used crystals were obtained by the slow
region [2]. A series of borate NLO crystals with evaporation of supersaturated solution by mixing
equal proportion of AR grade barium borate and
strontium borate in double-distilled water. The
*Corresponding author. Tel.: +91-0824-742363; fax: +91-
0824-742367.
solution was allowed to evaporate at constant
E-mail address: padakannayamrao@yahoo.com temperature (301C) for about a week which
(P. Mohan Rao). resulted in the formation of seed crystals. Good
0022-0248/02/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 0 1 ) 0 1 7 6 6 - 3
S. Ishwar Bhat et al. / Journal of Crystal Growth 236 (2002) 318322 319

101

220
Intensity (a.u.)

110

221
111
001

301
211
010

123
210
100

300

312
410
330
320
400
Fig. 1. Photograph of barium strontium borate crystals.

310

332
020
seed crystals were selected and suspended in the
10 20 30 40 50 60 70
original solution and placed for about a month 2 (Degrees)
without disturbing. This resulted in the formation
of good single crystals of dimension upto Fig. 2. Powder X-ray diractograph of barium strontium
borate.
20 mm  10 mm  1 mm. A few typically grown
crystals are shown in Fig. 1. band at 707 cm1 (Fig. 4) must be due to the
breathing vibrational mode of (B3O6)3 ring. It is
generally accepted that the ring-breathing mode of
3. X-ray powder diraction the six-membered borate ring with BO4 tetrahedra
gives rise to Raman lines in the 760780 cm1
The powder X-ray diractograph of barium region [10]. This is considered to be the most
strontium borate crystals is obtained from a characteristic line for all triborate crystals. The
Rigaku X-ray diractometer using a copper Ka absorption bands at 1658 and 1346 cm1 can be
( The X-ray spec-
target of wavelength 1.5414 A. assigned to the stretching vibration of the extra-
trum is depicted as shown in Fig. 2. ring BO bonds. The infrared bands at 1131, 1002
and 946 cm1 should belong to the stretching
3.1. Infrared spectroscopy vibrational modes of intra-ring BO bonds.
Kamitsos et al. [10] have demonstrated that in a
Vibrational spectroscopy can be a important number of borate crystals with BO4 tetrahedra the
tool in understanding chemical bonding and may wavenumbers of the symmetric stretching vibra-
provide useful information in studying the micro- tion gs and asymmetric stretching vibration gas of
scopic mechanism of the nonlinear optical proper- the BO4 tetrahedra are at about 545 and 900 cm1,
ties of borates. The infrared absorption spectrum respectively. In the infrared spectrum of barium
of barium strontium borate was recorded by using borate (Fig. 4) the strong band near 463 cm1 can
a BRUKER 66 V Fourier transform infrared be assigned to gs of BO4 tetrahedra and the band
spectrometer in the range 4004000 cm1 and is at 824 cm1 can be assigned to gas of BO4
shown in Fig. 3. The IR spectrum of barium tetrahedra.
borate recorded with the same instrument is also The characteristic vibrational bands mentioned
given in Fig. 4 for comparison. above in the IR spectrum of barium borate (Fig. 4)
The observed spectral bands are assigned to may be compared with the corresponding bands
vibrations of the (B3O6)3 ring and BO4 tetrahedra obtained for barium strontium borate crystals
cited in the earlier works [1014]. (Fig. 3). It is observed that most of the above
The characteristic vibrational modes of the referred bands are split into two indicating the
(B3O6)3 ring are assigned as follows. The strong mixed nature of barium strontium borate crystals.
320 S. Ishwar Bhat et al. / Journal of Crystal Growth 236 (2002) 318322

Fig. 3. FTIR spectrum of barium strontium borate.

Fig. 4. FTIR spectrum of barium borate.

The assignments of the observed IR bands for The crystals do not show any degradation in an
barium strontium borate as well as barium borate atmosphere with relative humidity upto 70%
crystals are presented in Table 1. The determina- indicating good moisture resistance. Also crystals
tion of the crystal structure of mixed barium are free of any cleavage. The chemical stability and
strontium borate may help to establish denitive good mechanical properties of these crystals make
vibrational assignments. it easy to cut and polish.

3.2. Microhardness 3.3. UVvisible spectra

The michrohardness of barium strontium borate To determine the transmission range and hence
is measured with a miniload hardness tester to know the suitability of barium strontium borate
(ERNST LEITZ GMBIH WETZLAR). Indenta- single crystals for optical application, the UV
tions are made for dierent loads and the value of visible spectrum was recorded. The spectrum in the
VHN is measured after averaging a large number wavelength range 2001000 nm is shown in Fig. 5.
of observations. The dwell time was 1015 s for all It can be seen from the transmission curve that
indentations. VHN measured at room temperature barium strontium borate crystal is transparent in
is 56 kg/mm2. the range between 200 and 1000 nm. This valuable
S. Ishwar Bhat et al. / Journal of Crystal Growth 236 (2002) 318322 321

Table 1 Table 2
Wave numbers (g) of the vibrational modes and their assign- Refractive indices of barium strontium borate
ments in barium borate and barium strontium borate crystals
Wavelength (nm) nx ny nz
For barium For barium Assignments
borate strontium borate 633 1.528 1.539 1.603
crystal g% cm1 crystal g% cm1

3359.4 3581 F axes by Brewsters angle technique with an HeNe


3506 laser (l 633 nm). The reected light is scanned
2694 by a photodetector. The refractive indices mea-
2160
sured are tabulated as shown in Table 2.
1658 1683 g1B0 B3 O6 3 ring
1643
1346 1419
1356
3.5. Second-harmonic generation (SHG)
1131 1154 gB0 B3 O6 3 ring
1074
The SHG property of the grown crystals is
1002 997 observed using a Q-switched Nd-YAG laser. The
947
crystal is mounted on a crystal holder and infrared
824 833 gas BO4 tetrahedral radiation (l=106 nm) is made to incident on the
811
crystal from the Nd-YAG laser. The beam is well
707 623 Breathing vibration focused before it is made to incident on the crystal
mode of (B3O6)3 ring
surface. It is observed that second-harmonic green
536
signal (l 532 nm) is generated by the crystal in
463 451 gs BO4 tetrahedral
addition to the original infrared wavelength. Using
a suitable dichroic mirror, infrared wavelength is
1.4 ltered and the second-harmonic green signal is
recorded using a uorescence spectroscope. The
1.2
wavelength is scanned with the aid of a mono-
1 chromator in the spectroscope (Princeton instru-
ment Inc, spectroscopy Instruments GmbH, model
Absorbance

0.8
DIDA-512 G/R). Fig. 6 depicts the second-har-
0.6

0.4

0.2

0
200
241
282
323
364
405
446
487
528
569
610
651
692
733
774
815
856
897
938
979

Wavelength (nm)

Fig. 5. UVvisible absorption spectrum of barium strontium


borate.

property is very important for photonic applica-


tions of this variety of borate crystals.

3.4. Refractive index measurement

The bulk refractive index of barium strontium


borate crystal is measured along the three crystal Fig. 6. Second-harmonic green signal at 532 nm.
322 S. Ishwar Bhat et al. / Journal of Crystal Growth 236 (2002) 318322

monic green signal at 532 nm from barium References


strontium borate crystal.
[1] N. Bloembergen, Non-linear Optics, Benjamin, New York,
1965.
4. Conclusions [2] Chuangtian Chen, Yicheng Wu, Rukang, LI, J. Crystal
Growth 99 (1990) 790.
[3] C.T. Chen, B.C. Wu, A.D. Jiang, G.M. You, Sci. Sinica B
Our preliminary studies show that good-quality
18 (1985) 235.
barium strontium borate single crystals can be [4] C.T. Chen, et al., J. Opt. Soc. Am. B 6 (1989) 616.
grown by slow evaporation technique. Owing to its [5] Y.C. Wu, T. Sasaki, S. Nakai, A. Yokotani, H. Tang, C.T.
good transparency, chemical stability and hard- Chen, Appl. Phys. Lett. 62 (1993) 2614.
ness, barium strontium borate crystal seems to be [6] L.F. Mei, C.T. Chen, B.C. Wu, J. Appl. Phys. 74 (1993)
a promising material for NLO application. 7014.
[7] C.T. Chen, Y. Wang, B.-C. Wu, K.-C. Wu, W. Zeng, L.H.
Further, studies on structural analysis and SHG Yu, Nature 373 (1995) 26.
eciency measurements are in progress. [8] T. Sasaki, I. Kuroda, S. Nakajima, K. Yamaguchi, S.
Watanabe, Y. Mori, S. Nakai: Proceedings of the
Advanced Solid State Lasers Conference. January 1995.
Acknowledgements [9] Y. Mori, I. Kuroda, S. Nakajima, T. Sasaki, S. Nakai,
Appl. Phys. Lett. 67 (1995) 1818.
[10] E.I. Kamitsos, M.A. Karakassides, G.D. Chryssikos,
We are grateful to IUC-DAEF Indore for Phys. Chem. Glasses 30 (1989) 229.
providing the facilities to carry out powder XRD [11] G.S. Xiong, G.X. Lan, H.F. Wang, J. Raman Spectrosc.
analysis. We thank Dr. S.R. Inamdar, Department 34 (1993) 785.
of Physics, Karnataka University, Dharwad for [12] T.W. Brill, Philips Res. Rep. 31(2) (Suppl.) (1976) 1.
[13] S.F. Lu, M.Y. Ho, J.L. Huang, Acta Phys. Sinica 31 (1982)
helping in obtaining SHG signal and chairman 948.
and sta, Department of Chemistry, Mangalore [14] Y.F. Wang, G.X. Lan, H.F. Wang, Spectrochim. Acta,
University for providing the IR facility. Part A 48 (1992) 181.