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Archives of Applied Science Research, 2011, 3 (1): 357-362

(http://scholarsresearchlibrary.com/archive.html)

ISSN 0975-508X
CODEN (USA) AASRC9

357
Scholar Research Library
Growth and characterization of bismuth lead thiourea chloride
crystals

T.Thaila and S.Kumara Raman

PG & Research Department of Physics, Nehru Memorial College, Puthanampatti, India
______________________________________________________________________________

ABSTRACT

Single crystals of Bismuth Lead Thiourea Chloride (BLTC), a semi-organic nonlinear optical
crystal, have been grown by slow evaporation technique at room temperature. The grown crystal
was confirmed by Single Crystal X-ray diffraction analysis. The functional groups of the grown
crystal were found by FTIR analysis. The UV-Vis NIR transmittance study was performed to
know the optical behaviour of the crystal. The NLO property of the crystal was tested by Nd:YAG
laser.

Key words: Crystal growth, Non linear crystal. X-ray diffraction, FTIR and NLO property.
______________________________________________________________________________

INTRODUCTION

Non-linear optical materials (NLO) exhibiting second harmonic generation have been in great
demand over the last few decades due to technological importance in the fields of optical
communication, signal processing and instrumentation [1-3]. Most of the organic NLO crystals
usually have poor mechanical and thermal properties and are susceptible for damage during
processing even though they have large NLO efficiency. Also it is difficult to grow larger size
optical-quality crystals of these materials for device applications. Purely inorganic NLO
materials have excellent mechanical and thermal properties but possess relatively modest modest
optical nonlinearity because of the lack of extended -electron delocalization [4, 5]. Hence it
may be useful to prepare semi-organic crystals which combine the positive aspects of organic
and inorganic materials resulting in useful NLO properties. In semi-organic materials, the
organic ligand is ionically bonded with inorganics. These crystals have higher mechanical
strength, chemical stability, large nonlinearity, high resistance to laser induced damage, low
angular sensitivity and good mechanical hardness [6,7]. Thiourea is an interesting inorganic
matrix modifier due to its large dipole moment [8].
T.Thaila et al Arch. Appl. Sci. Res., 2011, 3 (1):357-362
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The Present investigation deals with the growth of BLTC single crystal by slow evaporation
technique. The grown crystal was subjected to single crystal XRD, FTIR, UV-Vis-NIR and NLO
studies.
MATERIALS AND METHODS

Synthesis
Raw material of Bismuth Lead Chloride and Thiourea in the ratio of 3:1 were dissolved in
double distilled water to prepare the aqueous solutions of BLTC. The synthesized salt was
obtained by evaporating the solvent.

2.1 Crystal growth
The saturated solution of BLTC was prepared at room temperature. Since thiourea has the
coordination capacity to form different phases of metal-thiourea complexes, the mixtures of the
reactants has to be stirred well to avoid co-precipitation of multiple phases. The product was
purified by repeated recrystallization before it used for the crystal growth. BLTC crystals were
grown from aqueous solution by slow evaporation method. The crystals of BLTC, which are
optically transparent, are obtained after 20 days and the photographs of the grown crystals were
shown in Fig.1.

Characterization
3.1. Single crystal XRD
The grown crystals were subjected to single crystal XRD to confirm the crystallinity and also to
estimate the lattice parameters by employing ENRAF NONIUS CAD4 diffractometer. The single
crystal XRD reveals that the BLTC crystal belongs to tetragonal. The crystallographic
parameters are listed in Table 1.

3.2. FTIR analysis
The FTIR spectrum for BLTC has been recorded in the range 400-4000 cm
-1
. The spectrum
(Fig.2) shows the presence of all the functional group in BLTC crystal and is summarized in
Table 2. When it was compared with the spectra of thiourea, a few peaks were found to be
slightly shifted. The absorption band observed at 3391 cm
-1
in the spectrum of BLTC
corresponds to that of thiourea of about the same frequency 3376 cm
-1
and can be assigned to the
NH
2
asymmetric bending vibration. The absorption bands correspond to 3284 and 3199 cm
-1
in
the spectrum of BLTC and 3280 and 3167 cm
-1
in the spectrum of thiourea and can be assigned
to the NH
2
symmetric bending vibration. The absorption band observed at 1619 cm
-1
in the
spectrum of BLTC corresponds to that of thiourea of about the same frequency 1627 cm
-1
and
can be assigned to the NH
2
bending vibration. The absorption band at 1410 cm
-1
corresponds to
1417 cm
-1
of thiourea and can be assigned to the C=S asymmetric stretching vibration. The
absorption band at 699 cm
-1
corresponds to 740 cm-1 of thiourea and can be assigned to the C=S
symmetric stretching vibration. The absorption band observed at 1108 cm
-1
in the spectrum of
BLTC corresponds to that of thiourea of about the same frequency 1089 cm
-1
and can be
assigned to the C-N stretching vibration. The absorption observed at 527 cm
-1
in the spectrum of
BLTC corresponds to the 497 cm
-1
absorption of thiourea and can be assigned to the N-C-N
stretching vibration.


T.Thaila et al Arch. Appl. Sci. Res., 2011, 3 (1):357-362
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3.3. UV-Vis-NIR spectral analysis
Figure. 3 shows the UV-Vis-IR optical absorption spectra of BLTC crystals. From figure 3, it is
evident that the BLTC crystal has low optical absorption and high transmittance and UV cut off
wavelength is about 280 nm, which is sufficiently low for SHG laser radiation at 1064 nm.

3.4. SHG studies
The Second Harmonic generation (SHG) test on the BLTC crystal was performed by Kurtz
powder SHG method [9]. Nd:YAG laser emits fundamental wavelength at 1064 nm. For this
purpose, the output from Nd:YAG laser was used as a source and it was illuminated to the crystal
specimen. Pulse energy was 300 JS-1 and pulse width was about 10 ns. The output from the q-
switched laser is focused into the crystals. The output could be seen as a bright screen flash
emission from the sample.



Fig.1. Bismuth Lead Thiourea Chloride (BLTC) Crystals








T.Thaila et al Arch. Appl. Sci. Res., 2011, 3 (1):357-362
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Fig.2. FTIR Spectrum of BLTC crystals

T.Thaila et al Arch. Appl. Sci. Res., 2011, 3 (1):357-362
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Scholar Research Library


Fig.3. UV-Vis-NIR Spectrum of BLTC Crystals

Table. 1 Crystallographic parameters BLTC crystal system


Cell parameters a = 7.4652
b = 7.4970
c = 7.5415
= = = 90
0

System Tetragonal

Table 2. FTIR assignments for thiourea and BLTC crystal system.

Thiourea (cm
1
) TBLC (cm
1
) Assignment
494
740
1089
1417
1627
3167
3280
3376

527
699
1108
1410
1619
3199
3284
3391

N-C-N stretching
C=S stretching
C-N stretching
C=S stretching
NH2 bending
NH2 bending
NH2 bending
NH2 bending



T.Thaila et al Arch. Appl. Sci. Res., 2011, 3 (1):357-362
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362
Scholar Research Library
CONCLUSION

Single crystals of thiourea mixed bismuth lead chloride (BLTC) were grown from slow
evaporation method. The lattice parameters were found by single crystal XRD technique. The
FTIR spectrum reveals the functional groups of the grown crystals. BLTC was characterized by
UV-Vis spectra. The SHG conversion efficiency makes the crystal a potential material for NLO
applications.

REFERENCES

[1] R.W. Boyd, Non Linear optics, Academic Press, San Diego, 1992, 155.
[2] B.E. Salch and M.C. Teich, Fundamentals of Photonics, Wiley, New York, 1991, 113.
[3] D.S. Chemla and J. Zyss, Non-linear optical properties of organic molecule and crystals Vol I
and Vol II, Academic Press, New York, 1987, 71 and 123.
[4] M.H.Jiang and Q.Fanng, Adv. Matter. 1999, 11, 1147.
[5] M.D.Aggarwal, J.Choi, W.S.Wang, K.Bhat, R.B. Lal, A.D. Shields, J. Cryst Growth
2004, 179.
[6] G.Xing, M.Jiang, Z.Shao, D.Xu, Chin, J. Lasers 1987, 14, 357.
[7] S.Velsko, Laser Program Annual Report, Lawrence, Lawrence Livermore National
Laboratory, Livermore, CA, 1990.
[8] K.H. Landolt Bornstein in A.M. Hellwege, Numerical data and functional relationship in
Science and Technology, Group II, Springer, Berlin, 1982, 14, 584.
[9] S.K.Kurtz, T.T.Perry, J.Appl.Phys., 1968, 39, 3798-3813.