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Journal of Crystal Growth 249 (2003) 316320

Synthesis, growth and characterization of nonlinear optical


material: l-arginine uoride
A.S. Haja Hameeda, P. Anandanb, R. Jayavelc, P. Ramasamyc, G. Ravia,*
a
Crystal Research Centre, Alagappa University, Karaikudi 630 003, India
b
Department of Physics, Thiruvalluvar College of Engineering and Technology, Vandavasi 604 505, India
c
Crystal Growth Centre, Anna University, Chennai 600 025, India

Received 11 September 2002; accepted 29 September 2002


Communicated by M. Schieber

Abstract

l-arginine uoride (LAF) is one of the potential semi-organic materials for nonlinear optical applications. In the
present study, synthesis, material purication and crystal growth of LAF have been carried out. Since the material has
high solubility in water, the growth parameters have been optimized for the growth of good-quality crystals. X-ray
powder diffraction studies have been carried out in order to calculate the lattice parameter values using its monoclinic
crystallographic equation. From Fourier transform infrared spectroscopic analysis, different modes of vibration due to
various functional groups present in LAF have been observed. In order to nd the range and percentage of optical
transmission, the UVVIS spectrum was recorded for the crystal. The thermal behaviour of the LAF sample has been
investigated from differential thermal and thermogravimetric analyses.
r 2002 Elsevier Science B.V. All rights reserved.

PACS: 81.10.Dn; 42.70.a

Keywords: A1. Characterization; A1. Etching; A1. X-ray diffraction; A2. Growth from solutions; B1. Semiorganic materials;
B2. Nonlinear optical materials

1. Introduction damage threshold of LAP is two or three times


higher than that of KDP and it is more angularly
In recent years, many researchers have tried to sensitive than KDP [15]. In order to nd good
nd a variety of nonlinear optical materials for nonlinear optical crystals, Monaca et al. [6] have
laser applications. l-arginine phosphate monohy- attempted in synthesizing a variety of salts of l-
drate (LAP) is one of the nonlinear optical arginine emphasizing their nonlinear optical prop-
crystals, which is three times more nonlinear than erties such as second harmonic intensity, phase
potassium dihydrogen phosphate (KDP). Laser matching, etc., using the crystals of size as small as
50100 mm and reported that l-arginine uoride
*Corresponding author. Tel.: +91-4565-425215; fax: +91-
(LAF) possesses high NLO coefcient next to
4565-425202. LAP. LAF has a very strong type I position i.e.,
E-mail address: raviganesa@rediffmail.com (G. Ravi). angularly insensitive compared to LAP. LAF

0022-0248/03/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 0 2 ) 0 1 9 7 8 - 4
A.S. Haja Hameed et al. / Journal of Crystal Growth 249 (2003) 316320 317

crystals make it especially attractive for certain the growth solutions of LAP and LAF, both
cascade scheme for producing third harmonic. The solutions of equal volume in two identical glass
amount of second harmonic generated in a powder vessels were examined during its growth period.
LAF sample at 1064 nm relative to a quartz The powder sample prepared from the as-grown
standard (I=I0 ) is 5.6. It is also nearly noncritically seed crystals of LAF was used to estimate carbon,
phase matched at 950 nm, which make it valuable hydrogen and nitrogen contents by chemical
for application that required bluegreen light. analysis. X-ray diffraction was recorded for
In the present work, LAF single crystal of powdered LAF sample by means of a slowly
dimension 4  7  18 mm3 has been grown for the moving radiation detector with a scan speed of 21/
rst time. The characterization studies like X-ray min in the range of 10501 where monochromatic
powder diffraction (XRD), Fourier transform wavelength 1.5418 A ( (Cu Ka) was used. For the
infrared (FTIR) and UVVIS spectroscopic ana- spectroscopic study, FTIR and UVVIS spectra
lyses, differential thermal and thermogravimetric were recorded in the range of 4004400 cm1 and
analyses (DTA and TGA) have been carried out 2001500 nm, respectively. To nd the thermal
and the results are presented. characteristics of LAF, DT and TG analyses were
carried out in the temperature range from ambient
to 5001C with a heating rate of 51C/min. The
2. Experimental procedure weight of the sample used in this study was 34 mg.

LAF was synthesized by the reaction of l-


arginine (base) with hydrouoric acid. The chemi- 3. Results and discussion
cal reaction is as follows:
H2 NNHCNHCH2 3 CHNH2 COOH HF The weight percentage of carbon, hydrogen and
nitrogen present in the LAF sample is shown in
-H2 N2 CNHCH2 3 CHNH3 COO F :
Table 1 along with the theoretically calculated
Using the above reaction, a required amount of values. The synthesized LAF material was quanti-
l-arginine (base) was dissolved in excess of tatively conrmed. The crystals of LAF grown at
Nanopure water (resistivity of 18.3 MO cm). The the pH of 3.5 and 4.2 are shown in Figs. 1(a) and
stoichiometric amount of hydrouoric acid was 1(b). From Fig. 1(a), the crystal was found to be
slowly added into the aqueous l-arginine solution. platy elongated in both positive and negative c-
The prepared LAF solution was allowed to axis. The growth rate along the c-axis was greater
evaporate the excess water present in it into atmo- than that of a- and b-axis. It grew as thick plates
sphere at a temperature of about 501C in order to elongated parallel to the b-axis. The {1 0 0} faces
get the dried salt of LAF. The synthesized material and (0 1 0) face were well developed. The (1 0 0)
was further puried by repeated recrystallization habit face consisted of macro-steps, and the
and it was used for the growth of LAF crystals. linear steps along the [0 0 1] direction were
Since LAF has very high solubility in water, its observed when the crystal was tested under optical
growth under normal condition was difcult. microscope. Fig. 1(b) shows the LAF crystal of
Hence LAF crystals were grown by slow evapora-
tion of the saturated aqueous solution at ambient Table 1
temperature (331C) with the stoichiometric pH. Chemical analysis of LAF(C6H15N4O2  F) (molecular
After attaining supersaturation, a number of thin wt.194.2 g/mol)
plates of LAF crystals were formed by sponta- Element Composition (%)
neous nucleation. These seed crystals were used for
Theoretical Experimental
the growth of bulk LAF crystals by slow
evaporation. LAF crystals were grown at two N 28.86 28.79
different pH values, i.e., 3.5 and 4.2. In order to C 37.11 37.13
H 7.73 7.87
compare the effect of microbes and colouration in
318 A.S. Haja Hameed et al. / Journal of Crystal Growth 249 (2003) 316320

Fig. 2. The rectangular etch pits observed on the (1 0 0) plane of


LAF crystal.

were clearly observed while viewing the (0 1 0)


plane of the crystal.
During the growth of LAP, the common
problems one may face are microbial contamina-
tion and colouration. These microbes affect the
quality of the crystal and end up with poor
nonlinearity and less laser damage threshold. To
suppress these microbes and colouration observed
in the growth solutions of LAP family crystals,
some additives such as H2O2, CHCl3, n-hexane,
sodium azide (NaN3) and sterilization by UV light
have been tried by several authors [710]. In the
present study, the effect of microbes and coloura-
Fig. 1. The grown crystals of LAF grown at pH: (a) 3.5 and
tion was examined in both LAP and LAF
(b) 4.2.
solutions for the same growth period. Even after
3 months, microbes and coloration could not be
dimension 4  7  18 mm3 grown under the in- observed in the LAF solution. This is because of
creased pH of 4.2. The growth habit of grown incorporation of uoride in l-arginine molecule
LAF in this pH was found to be bulky unlike the rather than phosphate. This favourable property
platy LAF crystal grown at stoichiometric pH. of uorine leaves LAF solution without microbes
From the morphology of the LAF crystal, it and colouration whereas our experimental LAP
possessed well-dened (1 0 0), (1 0 0), (0 1 0), solution could withstand only for 2 weeks.
(1 1 0), (1 1 0), (0 1 1), (0 1 1), (1 1 1) and The X-ray diffraction pattern for the sample of
(1 1 1) planes. The (0 1 0) plane was found LAF is shown in Fig. 3. The lattice parameter
to be perfectly at and perpendicular to (1 0 0). values of LAF taken from the literature [6] were
The (1 0 0) plane of the grown crystal was found to used for the simulation of hkl values and
be cleavable. The grown crystal (at pH=4.2) is corresponding d values have also been calculated.
washed for 5 s using water to remove the white Using the simulated hkl values and the experi-
layer formed on the crystal surface. The (1 0 0) face mental d values, the lattice parameters were
was viewed through the optical microscope. The estimated and this indicates that LAF crystal
rectangular etch pits aligned along the (1 0 0) plane retained its monoclinic structure. The calculated
were formed. The pits shown in Fig. 2 are in and reported lattice parameter values are tabu-
resemblance with the morphology of the crystal lated in Table 2. From the table, it is found that
grown at a pH of 3.5. The calculated etch pit there is a small variation in a and b lattice
density (EPD) was about 5  103 cm2. The parameter values. This may due to the incorpora-
growth layers stacked parallel to the (1 0 0) face tion of impurities in LAF crystal.
A.S. Haja Hameed et al. / Journal of Crystal Growth 249 (2003) 316320 319

Fig. 3. X-ray powder diffraction pattern of LAF.

Table 2
Lattice parameter values of LAF

Lattice parameters (
Lattice parameter value in A

Reported Experimental

a 10.24 10.27
b 8.49 8.51
c 5.45 5.45

The FTIR spectrum recorded in the range of


4500400 cm1 for LAF is shown in Fig. 4. The
spectrum was found to be complex as a result of
various functional groups present in the LAF
Fig. 4. FTIR spectrum of LAF.
crystal. The high-frequency range of the spectrum
consists of bands, which are due to the NH2,

NH+ +
2 , NH3 , and COO stretching vibrations.
The bands observed in the lower-frequency regions bending of NH2 and OH out-of-plane deformation
were due to the deformation vibration of various were observed at 706 and 623 cm1, respectively.
functional groups. In LAF, the arginine molecules CH2 rocking and NH+ 3 rocking were observed at
are in ionized form (protonated). LAF did not 1291 and 1178 cm1, respectively.
contain vibration frequency of water molecule, The UVVIS absorption spectrum was recorded
which indicated that LAF is anhydrous. More- for the grown LAF crystal of 2 mm thick as shown
over, rocking mode, symmetric deformation and in Fig. 5. From the spectrum, a strong absorption
asymmetric bending were found from the spec- was observed at 245 nm. It has been observed that
trum. It was observed that scissoring mode of the lower cut-off wavelength is about 340 nm,
COO group was found at 773 cm1. Out-of-plane above which the transparency conveniently
320 A.S. Haja Hameed et al. / Journal of Crystal Growth 249 (2003) 316320

4. Conclusions

l-arginine uoride salt was synthesized and its


chemical composition was found from CHN
chemical analysis. The LAF crystals were grown
by slow evaporation method. During the growth,
the problem of microbial contamination and
colouration was not encountered in LAF solution.
This is the most advantageous property, which was
not observed in the case of LAP solution. From
the XRD pattern, hkl values were simulated and
the lattice parameter values were calculated. The
molecular vibrations of various groups present in
Fig. 5. UVVIS spectrum of LAF crystal.
LAF were observed. The range and percentage of
transmission were found. The decomposition
temperature and weight loss of LAF during
heating were estimated.

Acknowledgements

One of the authors (A.S.H) is grateful to the


Council for Scientic and Industrial Research
(CSIR), Government of India for the award of
Senior Research Fellowship.

References
Fig. 6. DT & TG curves of LAF.
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