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Optik 125 (2014) 24172421

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Optik
journal homepage: www.elsevier.de/ijleo

Optical, theoretical and mechanical studies on sodium acid


phthalate crystal
G. Marudhu a,b , S. Krishnan b, , G.V. Vijayaraghavan b
a
b

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

free atmosphere, at room temperature. After slow evaporation,


the NaAP crystals grown in beaker though they were further
puried by repeated recrystallization carried out to minimize the
impurities of the raw material. After 10 days of growth, the well
transparent with the dimensions 10 8 2 mm3 of NaAP crystals
was prepared and is shown in Fig. 1.

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

2.1. Synthesis and crystal growth


The sodium acid phthalate salt was synthesized by analar grade
of sodium bicarbonate and phthalic acid at 1:1 ratio dissolved in
an aqueous solution using magnetic stirrer which is then ltered
by Wattmann lter paper and covered by a plastic sheet with
some holes at the top to limit the evaporation and kept in dust

Corresponding author: Tel.: +91 44 2751347; fax: +91 44 22751347.


E-mail address: skrishnanjp@gmail.com (S. Krishnan).
0030-4026/$ see front matter 2014 Elsevier GmbH. All rights reserved.
http://dx.doi.org/10.1016/j.ijleo.2014.01.008

p = 28.8

(1)

where Z = ((8 ZC) + (6 ZH) + (1 ZNa) + (4 Zo)) = 63 is the total


number of valence electrons,  is the density and M is the molecular
weight of the grown crystal. Explicitly p dependent Penn gap and
the Fermi energy, is given by
Ep =

p
1

( 1) 2

(2)

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G. Marudhu et al. / Optik 125 (2014) 24172421

80
2852

60

4000

3000

2000

858
1118

1354

3493

1696
1613

20

746

40

538

2457

Transmittance (%)

100

1000
-1

Wavenumber (cm )

Fig. 1. Photograph of as grown crystal.

Fig. 2. FTIR spectrum of the grown crystal.

and
4

EF = 0.2948(p ) 3

(3)

Polarizability obtained using the relation

(p )2 S0
(p )2 S0 + 3Ep 2

M
0.396 1024 cm3


(4)

where S0 is a constant for a particular material which is given by


S0 = 1

E 
p
4EF

1 Ep
+
3 4EF

2

(5)

The value of so obtained agrees with that obtained using


ClausiusMossotti equation which is given by,
=

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

where T is transmittance, and t is thickness of the crystal.


Owing to the direct band gap, the crystal under study has an
absorption coefcient () obeying the following relation for high
photon energies (h);
=

A(h Eg )
h

1/2

3.3.1. Determination of optical constants


The optical behaviour of materials is important to determine its
usage in optoelectronic devices. Knowledge of optical constants of a
material such as optical band gap and extinction coefcient is quite
essential to examine the materials potential optoelectronic applications. Further, the optical properties may also be closely related
to the materials atomic structure, electronic band structure and
electrical properties. The extinction coefcient (K) for the grown
crystals can be determined using formula.
K=


4

(9)

An optical absorption spectrum of NaAP crystal was recorded in


the range of 2001100 nm using Varian Cary 5E UVvis-NIR spectrophotometer. A transparent crystal of 2 mm thickness was used
Table 1
Some theoretical parameters on NaAP crystals.
Values

Plasma energy (eV)


Penn gap (eV)
Fermi energy (eV)
Polarizability (cm3 )
Penn analysis
ClaussiusMosotti equation

20.37
2.35
16.40
4.78 1023
4.80 1023

(8)

where Eg is optical band gap of the crystal, and A is a constant. The


plot of variation of (h)2 vs. h is shown in Fig. 4. Eg is evaluated
by the extrapolation of the linear part, and the band gap is found to
be 4.01 eV.

3.3. Optical absorption studies

Parameters

(7)

Fig. 3. Optical absorption spectrum of the NaAP crystal.

G. Marudhu et al. / Optik 125 (2014) 24172421


30

2419

-2

op)

20

Optical Conductivity

x 10 eV cm

3.5

(x10

10

Hz)

4.0

10
( h

Band gap = 4.01 eV

3.0
2.5
2.0
1.5
1.0

Photon Energy (eV)

Photon Energy (eV)

Fig. 7. Plot of photon energy vs. optical conductivity.

Extinction Coefficient (K)

Fig. 4. Plot of photon energy vs. (h)2 .

0.00007

The optical conductivity ( op ) is a measure of the frequency


response of the material when irradiated with light (Fig. 7)

0.00006

op =

0.00004

0.00003

3.4. Microhardness studies

The microhardness of NaAP crystal was carried out by a


LeitzWetzler microhardness tester with a diamond pyramidal
indenter. The indentations were made using a Vickers pyramidal
indenter for various loads from 25 to 100 g in the steps of 25 g with
a constant indentation period of 25 s for all loads. Vickers hardness
number (Hv ) were calculated using the relation

3
Photon Energy (eV)

Fig. 5. Plot of photon energy vs. K.

The plot of K vs. photon energy (h) is shown in Fig. 5. It is


observed that K decreases with increase in energy.
The reectance (R) in terms of photon energy (Fig. 6) is derived
from the relation,
R=

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)

where P is applied load in kg, and d is the diagonal length in mm.


The variation of Hv with applied load P is shown in Fig. 9. From
the graph, it becomes clear that the hardness value increases with
increasing load, thus satisfying the normal indentation effect. A plot
of log p vs. log d (Fig. 10) yields a straight line graph, and its slope
gives the work hardening index n and is found to be 3.75, according
to Meyers relation
P = K1 dn

(12)

where K1 is the standard hardness value, which can be found out


from the plot of P vs. dn (Fig. 11). As the material takes some time
5

10

Hz)

1.2

e)

(x10

1.0
0.8

Electrical Conductivity (

Reflectance (R)

n=

(R + 1)

(11)

where c is the velocity of light.


Initially, it is observed that the refractive index decreases with
increase in the photon energy. Also, the electrical conductivity has
been determined for the grown crystal and is shown in Fig. 8.

0.00005

0.00002

nc
4

0.6
0.4
0.2
0.0

Photon Energy (eV)

Fig. 6. Plot of photon energy vs. R.

Photon Energy (eV)

Fig. 8. Plot of photon energy vs. electrical conductivity.

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G. Marudhu et al. / Optik 125 (2014) 24172421

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)

Yield strength v of the material can be found out using the


relation

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)

All the determined mechanical parameters are shown in Table 2.


Fig. 10. Plot of log d vs. log p.

3.5. Fluorescence studies


to revert to the elastic mode after every indentation, a correction

is applied to the d-value, and Kicks law is related as


P = K2 (d + x)

(13)

From Eqs. (12) and (13), we get

 K 1/2
2

K1

d+

K 
2

K1

(14)

3.6. Nonlinear optical studies


The SHG efciency of NaAP crystal was determined by the Kurtz
and Perry technique. A Q switched Nd:YAG laser emitting fundamental wavelength of 1064 nm was allowed to strike the powder

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

Fig. 11. Plot of dn vs. P.

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

G. Marudhu et al. / Optik 125 (2014) 24172421

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

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