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Optik
journal homepage: www.elsevier.de/ijleo
Department of Physics, Sri Ramanujar Engineering College, Chennai 600 048, India
Department of Physics, B.S.Abdur Rahman University, Chennai 600 048, India
a r t i c l e
i n f o
Article history:
Received 24 May 2013
Accepted 20 October 2013
Keywords:
Slow evaporation
X-ray diffraction
Mechanical strength
a b s t r a c t
The semiorganic crystal of sodium acid phthalate (NaAP) single crystals was grown in the solvent of
water by slow evaporation method at room temperature. The single crystal X-ray diffraction studies
showed the crystal belongs to orthorhombic system. The optical absorption spectrum reveals that the
crystal has good transparency in entire visible region. The hardness number of the material is measured by
microhardness tester. The uorescence green colour emission exhibits is semiorganic. The SHG efciency
of NaAP crystal conrms NLO behaviour of green colour emission to provide frequency doubling process
for photo electronic applications.
2014 Elsevier GmbH. All rights reserved.
1. Introduction
Nonlinear optical materials have attracted many researchers
because of its key functions in frequency doubling, optical modulation, optical switching, optical logic, and optical memory for the
emerging technologies in the areas such as telecommunications,
signal processing and optical interconnections [1]. Organic NLO
materials have large nonlinear optical susceptibilities but possess
poor mechanical and thermal properties. These difculties were
overcome by semiorganic NLO materials [2]. The title materials of
sodium acid phthalate single crystals are semiorganic in nature
which is grown by slow evaporation technique at normal room
temperature. Although the NaAP was already reported, the crystallization has been improved in the present work. Also, the optical,
theoretical and mechanical properties were reported for the rst
time.
2. Experimental
3. Characterization studies
3.1. Single crystal X-ray diffraction analysis
The grown NaAP single crystal was subjected to single crystal
X-ray diffraction analysis using ENRAF NONIUS CAD-4 single crys
tal X-ray diffractometer. The determined cell parameters a = 6.60 A,
c = 25.84 A;
= = = 90 and the cell volume V = 1548
b = 9.08 A,
3 are in close agreement with reported values [3,4]. The grown
title crystal belongs to orthorhombic system. The valence electron
plasma energy, p is given by
Z 1/2
p = 28.8
(1)
p
1
( 1) 2
(2)
2418
80
2852
60
4000
3000
2000
858
1118
1354
3493
1696
1613
20
746
40
538
2457
Transmittance (%)
100
1000
-1
Wavenumber (cm )
and
4
EF = 0.2948(p ) 3
(3)
(p )2 S0
(p )2 S0 + 3Ep 2
M
0.396 1024 cm3
(4)
E
p
4EF
1 Ep
+
3 4EF
2
(5)
3M
4Na
1
(6)
+ 2
All these calculated data for the grown crystal are shown in
Table 1.
3.2. FTIR studies
The presence of functional groups and vibrational frequencies
of NaAP crystal are identied by FTIR spectroscopy. The recorded
spectrum of the grown crystal was carried out between the range
4004000 cm1 using PerkinElmer spectrum one and is shown in
Fig. 2. An absorption band in the range 538858 cm1 appears due
to the C H out-of-plane deformations of the aromatic ring. The
spectral band attributed at 1118 cm1 is due to the C H in-plane
deformation of the aromatic ring. The C O stretching vibrations
was obtained as a peak at 1354 cm1 . The peak at 1613 cm1 was
assigned due to the C C skeletal aromatic ring vibrations. The
carboxyl group C O vibrations appear near 1696 cm1 . All these
assignments are in very good agreement with that of the reported
values [5].
for this measurement. From the spectrum (Fig. 3), it is evident that
the compound has low cut-off wavelength at 312 nm which is sufcient for SHG laser radiation of 1064 nm for frequency doubling
process [5].
The optical absorption coefcient () was calculated from the
transmittance using the following relation,
=
1
log
t
1
T
A(h Eg )
h
1/2
4
(9)
20.37
2.35
16.40
4.78 1023
4.80 1023
(8)
Parameters
(7)
2419
-2
op)
20
Optical Conductivity
x 10 eV cm
3.5
(x10
10
Hz)
4.0
10
( h
3.0
2.5
2.0
1.5
1.0
0.00007
0.00006
op =
0.00004
0.00003
3
Photon Energy (eV)
1 (1 exp(d) + exp(d))
(10)
1 + exp(d)
The refractive index (n) can be derived from the following relations
3R2 + 10R 3
2(R 1)
(10)
Hv =
1.8544P
kg/mm2
d2
(11)
(12)
10
Hz)
1.2
e)
(x10
1.0
0.8
Electrical Conductivity (
Reflectance (R)
n=
(R + 1)
(11)
0.00005
0.00002
nc
4
0.6
0.4
0.2
0.0
2420
50
24
-2
(x10 m)
21
18
n/2
Hv (kg/mm
40
15
30
12
40
45
50
55
60
65
20
40
60
80
100
Fig. 12. Plot of d vs. dn/2 .
Load P
Fig. 9. Plot of load P vs. Hv .
The slope of dn/2 vs. d yields (K2 /K1 )1/2 and the intercept is a
measure of
and is shown in Fig. 12. The fracture toughness (Kc ) is
given by
2.0
Kc =
(15)
where C is the crack length measured from the centre of the indentation mark to the crack tip, P is the applied load and geometrical
constant = 7 for Vickers indenter. The brittleness index (B) is
given by
1.8
n =3.75
Log P
P
c 3/2
1.6
B=
Hv
Kc
(16)
1.4
1.62
1.65
1.68
1.71
1.74
1.77
v =
1.80
Log d
Hv
2.9
12.5(2 n) 2n
1 (2 n)
1 (2 n)
(17)
(13)
K 1/2
2
K1
d+
K
2
K1
(14)
100
Table 2
Several mechanical parameters on the grown crystals.
80
Load P
dn/2 =
The uorescence spectrum was recorded for NaAP crystal sample using Varian Cary Eclipse Fluorescence spectrometer at room
temperature. The sample was excited at 330 nm and is shown in
Fig. 13. A high intense peak at 486 nm is observed and shows that
sodium acid phthalate exhibits green colour uorescence emission
which assigned as * transition due to the interaction between
metal (Na2+ ) and ligand.
60
40
20
6.0
6.2
6.4
6.6
6.8
Parameters
Values
n
K1 (kg/mm)
K2 (kg/mm)
Hp
Hv
Pm
Ps
Kc (mNm3/2 )
B (m1/2 )
v (mPa)
C11 (10 12 Pa)
3.75
0.03727 102
1.354 104
47.65
24.95
100
25
0.0357
6.986 102
231.467 102
278.53
2421
cut-off wavelength at 312 nm. The title crystal has work hardening
coefcient, 3.75, tested by Vickers hardness tester. The emission
spectrum of NaAP is around 486 nm which shows green colour
emission to identify the title material. The second harmonic generation efciency of NaAP crystals was conrmed by green colour
emission for frequency doubling process.
Acknowledgements
We sincerely thank SAIF, IIT Chennai for scientic supports. The
encouragement rendered by Head, Department of Physics, B.S.A.
University is acknowledged.
References
Fig. 13. Plot of wavelength vs. relative intensity.
sample [6,7]. The output wavelength of 532 nm green colour emission was detected by photomultiplier tube. Hence, SHG efciency
of NaAP was found to be 1.57 times than that of KDP reference
material, which conrms the suitability of NLO and semiconducting
applications.
4. Conclusions
The NaAP single crystals were grown in the solvent of water
by slow evaporation method at room temperature. The single
XRD conrmed the grown crystal belongs to orthorhombic system. The grown crystals have good transparency range with UV