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

In recent years, many researchers have tried to
nd a variety of nonlinear optical materials for
laser applications. l-arginine phosphate monohy-
drate (LAP) is one of the nonlinear optical
crystals, which is three times more nonlinear than
potassium dihydrogen phosphate (KDP). Laser
*Corresponding author. Tel.: +91-4565-425215; fax: +91-
4565-425202.
E-mail address: raviganesa@rediffmail.com (G. Ravi).
higher than that of KDP and it is more angularly
sensitive than KDP [15]. In order to nd good
nonlinear optical crystals, Monaca et al. [6] have
attempted in synthesizing a variety of salts of l-
arginine emphasizing their nonlinear optical prop-
erties such as second harmonic intensity, phase
matching, etc., using the crystals of size as small as
50100 mm and reported that l-arginine uoride
(LAF) possesses high NLO coefcient next to
LAP. LAF has a very strong type I position i.e.,
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
crystals make it especially attractive for certain
cascade scheme for producing third harmonic. The
amount of second harmonic generated in a powder
LAF sample at 1064 nm relative to a quartz
standard (I=I0 ) is 5.6. It is also nearly noncritically
phase matched at 950 nm, which make it valuable
for application that required bluegreen light.
In the present work, LAF single crystal of
dimension 4
7
18 mm3 has been grown for the
rst time. The characterization studies like X-ray
powder diffraction (XRD), Fourier transform
infrared (FTIR) and UVVIS spectroscopic ana-
lyses, differential thermal and thermogravimetric
analyses (DTA and TGA) have been carried out
and the results are presented.
2. Experimental procedure
LAF was synthesized by the reaction of l-
arginine (base) with hydrouoric acid. The chemi-
cal reaction is as follows:
H2 NNHCNHCH2 3 CHNH2 COOH HF
-H2 N2 CNHCH2 3 CHNH3 COO F :
Using the above reaction, a required amount of
l-arginine (base) was dissolved in excess of
Nanopure water (resistivity of 18.3 MO cm). The
stoichiometric amount of hydrouoric acid was
slowly added into the aqueous l-arginine solution.
The prepared LAF solution was allowed to
evaporate the excess water present in it into atmo-
sphere at a temperature of about 501C in order to
get the dried salt of LAF. The synthesized material
was further puried by repeated recrystallization
and it was used for the growth of LAF crystals.
Since LAF has very high solubility in water, its
growth under normal condition was difcult.
Hence LAF crystals were grown by slow evapora-
tion of the saturated aqueous solution at ambient
temperature (331C) with the stoichiometric pH.
After attaining supersaturation, a number of thin
plates of LAF crystals were formed by sponta-
neous nucleation. These seed crystals were used for
the growth of bulk LAF crystals by slow
evaporation. LAF crystals were grown at two
different pH values, i.e., 3.5 and 4.2. In order to
compare the effect of microbes and colouration in
317
the growth solutions of LAP and LAF, both
solutions of equal volume in two identical glass
vessels were examined during its growth period.
The powder sample prepared from the as-grown
seed crystals of LAF was used to estimate carbon,
hydrogen and nitrogen contents by chemical
analysis. X-ray diffraction was recorded for
powdered LAF sample by means of a slowly
moving radiation detector with a scan speed of 21/
min in the range of 10501 where monochromatic
wavelength 1.5418 A ( (Cu Ka) was used. For the
spectroscopic study, FTIR and UVVIS spectra
were recorded in the range of 4004400 cm1 and
2001500 nm, respectively. To nd the thermal
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
weight of the sample used in this study was 34 mg.
3. Results and discussion
The weight percentage of carbon, hydrogen and
nitrogen present in the LAF sample is shown in
Table 1 along with the theoretically calculated
values. The synthesized LAF material was quanti-
tatively conrmed. The crystals of LAF grown at
the pH of 3.5 and 4.2 are shown in Figs. 1(a) and
1(b). From Fig. 1(a), the crystal was found to be
platy elongated in both positive and negative c-
axis. The growth rate along the c-axis was greater
than that of a- and b-axis. It grew as thick plates
elongated parallel to the b-axis. The {1 0 0} faces
and (0 1 0) face were well developed. The (1 0 0)
habit face consisted of macro-steps, and the
linear steps along the [0 0 1] direction were
observed when the crystal was tested under optical
microscope. Fig. 1(b) shows the LAF crystal of
Table 1
Chemical analysis of LAF(C6H15N4O2  F) (molecular
wt.194.2 g/mol)
Element Composition (%)
Theoretical Experimental
N 28.86 28.79
C 37.11 37.13
H 7.73 7.87
318 A.S. Haja Hameed et al. / Journal of Crystal Growth 249 (2003) 316320
Fig. 1. The grown crystals of LAF grown at pH: (a) 3.5 and
(b) 4.2.
dimension 4
7
18 mm3 grown under the in-
creased pH of 4.2. The growth habit of grown
LAF in this pH was found to be bulky unlike the
platy LAF crystal grown at stoichiometric pH.
From the morphology of the LAF crystal, it
possessed well-dened (1 0 0), (1 0 0), (0 1 0),
(1 1 0), (1 1 0), (0 1 1), (0 1 1), (1 1 1) and
(1 1 1) planes. The (0 1 0) plane was found
to be perfectly at and perpendicular to (1 0 0).
The (1 0 0) plane of the grown crystal was found to
be cleavable. The grown crystal (at pH=4.2) is
washed for 5 s using water to remove the white
layer formed on the crystal surface. The (1 0 0) face
was viewed through the optical microscope. The
rectangular etch pits aligned along the (1 0 0) plane
were formed. The pits shown in Fig. 2 are in
resemblance with the morphology of the crystal
grown at a pH of 3.5. The calculated etch pit
density (EPD) was about 5
103 cm2. The
growth layers stacked parallel to the (1 0 0) face
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-
tion was examined in both LAP and LAF
solutions for the same growth period. Even after
3 months, microbes and coloration could not be
observed in the LAF solution. This is because of
incorporation of uoride in l-arginine molecule
rather than phosphate. This favourable property
of uorine leaves LAF solution without microbes
and colouration whereas our experimental LAP
solution could withstand only for 2 weeks.
The X-ray diffraction pattern for the sample of
LAF is shown in Fig. 3. The lattice parameter
values of LAF taken from the literature [6] were
used for the simulation of hkl values and
corresponding d values have also been calculated.
Using the simulated hkl values and the experi-
mental d values, the lattice parameters were
estimated and this indicates that LAF crystal
retained its monoclinic structure. The calculated
and reported lattice parameter values are tabu-
lated in Table 2. From the table, it is found that
there is a small variation in a and b lattice
parameter values. This may due to the incorpora-
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
Fig. 5. UVVIS spectrum of LAF crystal.
Fig. 6. DT & TG curves of LAF.
extends to 1000 nm. The percentage of transmis-
sion is about 70%.
DT and TG curves recorded for LAF sample are
shown in Fig. 6. From DTA curve, it is found that
LAF is stable up to 2251C. LAF undergoes an
irreversible endothermic transition at 2251C,
which corresponds to the melting point of the
material. Between 2251C and 2631C, LAF starts to
soften and then nally it melts. Thermogravimetric
analysis shows the softening of LAF at 2501C
accompanied by the loss of material of about 54%.
The material lost its weight due to the decomposi-
tion of two ammonia molecules, in which one
molecule is bonded to an a-carbon and the other is
attached to the carbon atoms of the (N2H)+CNH
group. The material is fully decomposed at 2911C,
and nally LAF becomes volatile. As compared to
LAP, LAF is thermally more stable (LAP decom-
posed at 1111C [11]).
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
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.
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