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Optik xxx (2012) xxxxxx

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Optik
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Synthesis, crystal growth and characterization of a semiorganic material:

Thiosemicarbazide potassium chloride
J. Chandrasekaran a, , P. Ilayabarathi b , P. Maadeswaran c , S. Balaprabhakaran a ,
K. Sathishkumar a , B. Babu a
a

Department of Physics, Sri Ramakrishna Mission Vidyalaya College of Arts and Science, Coimbatore 641 020, Tamil Nadu, India
Research and Development Center, Bharathiyar University, Coimbatore 641 046, Tamil Nadu, India
c
Department of Physics, K. S. Rangasamy College of Technology, Tiruchengode 637215, Tamil Nadu, India
b

a r t i c l e

i n f o

Article history:
Received 1 June 2011
Accepted 3 November 2011
Available online xxx
Keywords:
Thiosemicarbazide potassium chloride
Infrared spectrum
Optical transmission spectrum
Thermal analysis and microhardness

a b s t r a c t
Thiosemicarbazide potassium chloride (K(NH2 NHCSNH2 )ClH2 O) (TSCPC) is one of the potential semiorganic materials for many applications. The crystal growth of TSCPC by slow evaporation method at
ambient temperature and its dimension was found to be (5 mm 3 mm 2 mm). The grown crystals
where characterized by Fourier transform infrared spectroscopic (FT IR) analysis to nd the different
modes of vibration due to various functional groups present in TSCPC. The powder X-ray diffraction pattern of the grown crystal has been studied. Thermal stability of the grown crystal was identied at 185 C
by using TGA/DTA. The dielectric constant of the crystal was studied as a function of temperature with
frequency and the results are discussed. The mechanical property of the grown crystal has been studied using Vickers microhardness tester. The optical transmission spectrum was investigated to study its
linear optical properties using UVvis spectrophotometer.
2011 Elsevier GmbH. All rights reserved.

1. Introduction
The development of optoelectronic functions includes coherent sources for emission, optical ampliers, modulators, switches
etc. These functions and related devices can be operated on the
basis of nonlinear optical phenomena whereby the optical response
medium as driven by the optical elds [1]. In particular the organic
materials have motivated several investigations because of their
attractive properties in high damage threshold, low refractive
indices and easy growth, but in which the molecules are constituted by weak Van der waals and hydrogen bond with conjugated
-electrons and it is difcult to cut and polish such crystals.
In view of this, a new type of NLO materials have been built
from organicinorganic complexes which form stronger ionic bond
than the Van der Waals and hydrogen bonds, which increases the
mechanical strength of material namely, semiorganic crystals [2,3].
In semiorganics materials, polarizable organic molecules are stoichiometrically bound within an inorganic host [4,5]. Organic acid
family crystals have subjected to extensive investigation by several researchers for their excellent characteristics. The physical
properties of organic acids properties made them ideal candidates
for NLO applications. In the recent years, efforts have been made

on the organic acid mixed with inorganic crystals, in order to

improve their properties. Thiosemicarbazone moiety helps the free
thiosemicarbazone ligands and their metal complexes to improve
second harmonic generation (SHG) efciency [6]. In this respect
acetophenone thiosemicarbazone (APTSC), thiosemicarbazide cadmium chloride monohydrate (TSCCCM) and thiosemicarbazide
lithium chlorides [TSLC] have been identied as good semiorganic
nonlinear optical materials [7,8]. In the present work potassium chloride is combined with thiosemicarbazide to form a new
semiorganic (metalorganic) material in this series. Systematic
investigation has been carried out on the growth of TSCPC subjected
to Fourier transform infrared spectroscopy, optical transmission,
thermal study, dielectric constant and microhardness measurement.
2. Synthesis and growth technique
The starting materials were highly pure and the synthesis and
growth process were carried out in aqueous solution. Thiosemicarbazide potassium chloride (TSCPC) has been synthesized by taking
potassium chloride and thiosemicarbazide in a 1:1 stoichiometric
ratio. The reaction responsible for synthesis and crystallization is.
KCl + NH2 NHCSNH2 K(NH2 NHCSNH2 )Cl

Corresponding author. Tel.: +91 422 2692461; fax: +91 422 2693812.
E-mail address: jchandaravind@yahoo.com (J. Chandrasekaran).

The calculated amount of potassium chloride was rst dissolved in

deionized water. Then thiosemicarbazide was added to the solution

0030-4026/$ see front matter 2011 Elsevier GmbH. All rights reserved.
doi:10.1016/j.ijleo.2011.11.023

Please cite this article in press as: J. Chandrasekaran, et al., Synthesis, crystal growth and characterization of a semiorganic material:
Thiosemicarbazide potassium chloride, Optik - Int. J. Light Electron Opt. (2012), doi:10.1016/j.ijleo.2011.11.023

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Table 1
FT-IR data of TSCPC crystal.
Wave number (cm1 )

Assignments

3368
3369
3370
1644
1620
1483
1316
1001
800
503

NH asymmetric stretching vibration of NH2

NH asymmetric stretching vibration of NH2
(CH) stretching
NH3 + asymmetric bending mode
NH2 deformation
C S Asymmetric Stretching
(CNH2 ) mode of vibration
CCl Stretching mode
C S Symmetric Stretching mode
NCS Stretching

Fig. 1. As shown in TSCPC crystals.

8000
7000

Lin (Counts)

slowly. The solution was agitated with a magnetic stirring device

for 8 h continuously and ltered after complete dissolution of the
starting materials. The prepared solution was left standby for several days at room temperature. After 2530 days a good quality
colorless crystals were obtained which is shown in (Fig. 1).

6000
5000
4000
3000

3. Result and discussion

2000
1000

3.1. FT IR analysis

The FT IR spectrum of TSCPC crystal was recorded using a

thermo Nicolet, Avatar 370 spectrometer in the wave length range
of 4004000 cm1 . The resulting spectrum of TSCPC crystal is
shown in Fig. 2. The broad envelope positioned between 3368 and
3176 cm1 which corresponds to the symmetric and asymmetric
stretching modes of NH2 group. A weak absorption is observed at
2969 cm1 due to (CH) stretching mode. The asymmetrical NH3 +
bending mode and NH2 deformation was observed at 1620 cm1
and 1644 cm1 respectively [9]. A sharp peak at 1483 cm1 is due
to asymmetric C S stretching. The band at 1316 cm1 is due to
(CNH2 ) mode of vibration and symmetric NCN stretching at
1000 cm1 [10]. The CCl stretching band was observed at 647 and
600 cm1 respectively. The assignments conrm the presence of
various functional groups are present in the material and is tabulated in Table 1.
3.2. Powder X-ray diffraction analysis
Powder X-ray diffraction studies were carried out to demonstrate the crystallinity using Rich-Seifert X-ray diffractometer
employing Bruker AXS D8 Advance with Ni ltered Cu-K radi in the range 1080 with a scan
ations of wavelength (1.5406 A)

speed of 2 /min. The powder X-ray diffraction spectrum is displayed in the Fig. 3 and the spectrum shows a high degree of
crystallinity of the synthesized compound. From the powder X-ray
diffraction, the 2 and d are given in Table 2.
100

10

20

30

40

50

60

70

80

2-Theta - Scale

Fig. 3. X-ray powder diffraction of TSCPC.

Table 2
X-ray powder diffraction data of TSCPC.
2 ( )

Experimental d value

15.205
17.812
20.134
21.629
24.715
27.463
30.587
35.555
40.476
50.354
51.992
58.819
66.516
73.817

5.82220
4.97569
4.40672
4.10541
3.59933
3.24516
2.92044
2.52292
2.22680
1.81069
1.75744
1.56869
1.40460
1.28869

3.3. Linear optical properties

The optical transmission range of TSCPC crystal was observed
in between wavelength 200 and 800 nm with scanning speed of
200 nm/min using Varian, Cary 5000 instrument and thickness of
crystal was 2 mm used. From the Fig. 4, it is evident that TSCPC
crystal has UV cut-off below 260 nm, which is sufcient for SHG

90
80
70

%T

60
50
40
30
20
10
0
-10
4000

3500

3000

2500

2000

1500

1000

500

Wavenumbers (cm-1)

Fig. 2. FT-IR spectrum of TSCPC crystals.

Fig. 4. Optical transmission spectrum of TSCPC crystals.

Please cite this article in press as: J. Chandrasekaran, et al., Synthesis, crystal growth and characterization of a semiorganic material:
Thiosemicarbazide potassium chloride, Optik - Int. J. Light Electron Opt. (2012), doi:10.1016/j.ijleo.2011.11.023

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Dielectric Constant (r)

J. Chandrasekaran et al. / Optik xxx (2012) xxxxxx

20
18
16
14
12
10
8
6
4
2
0
40

50

60

70

80

90

100

110

120

130

140

150

TemperatureC
100Hz

10KHz

1MHz

Fig. 7. Dielectric constant of TSCPC crystals.

3.6. Microhardness measurement

Fig. 5. TGA/DTA curve of TSCPC crystal.

properties and the transmittance of the crystal is about 90% in the

entire visible region [12].
3.4. Thermal analysis
The thermal stability of TSCPC was identied by the thermogravimetric analysis (TGA), and differential thermal analysis (DTA).
The thermal analyses were carried out using the instrument of
model Q600 SDT and Q20 which is shown in Fig. 5. A crucible
was used for heating the sample and analyses were carried out
in an atmosphere of nitrogen at a heating rate of 20 K/min in the
temperature range 20800 C. The TSCPC sample weighing 25.9 mg
was taken for the analysis. From the DTA curve it is observed that
the material is stable up to 185 C and above which the material
begins to attain an endothermic transition and begins to decompose. The sharpness of this endothermic peak at 205 C shows good
degree of crystallinity of the sample [13]. The TGA curve shows the
weight percentage of about 98.72% observed at 185 C and 59.86%
observed at 385 C which may attribute to the loss of lattice water.
This weight loss is due to release of gaseous product like CO2 , NH3 ,
etc. Thus, the compound undergoes endothermic decomposition
between 205 C and 385 C.
3.5. Dielectric constant (r )

Hardness number(Hv) Kg/mm2

The dielectric property of TSCPC was studied at various temperatures using Agilent A 2484. The dielectric constant (r ) of crystal
was found by measuring the capacitance and dielectric loss, which
is used to calculate the dielectric constant at various temperatures
ranging between room temperature to 150 C for three different
frequencies. The maximum dielectric constant was observed at
150 C and it indicates that the dielectric constant is increased with
increasing the temperature [14]. The variation of dielectric constant
with temperature at three different frequencies 100 Hz, 10 KHz and
1 MHz is shown in Fig. 7.

70
60
50
40
30
20
10
0
25

30

35

50

Load (P)

Fig. 6. Microhardness of TSCPC crystals.

100

The mechanical strength of the TSCPC crystal was found using

HMV 2T, Vickers microhardness tester shown in Fig. 6. The static
indentations were made on the surface of crystal by varying the
load from 25 to 100 g at room temperature. Vickers microhardness number was calculated using Hv = 1.8544 P/d2 kg/mm2 . The
graph indicates at lower load, there is an increase in hardness with
increasing the load up to 50 g, which can be attributed to the work
hardening of the surface and above 50 g load signicant cracking
occurs, which may be due to the release of internal stresses generated by the indentation. Finally the maximum value of hardness for
TSCPC crystal at room temperature was found to be 63.2 kg/mm2
for a load of 50 g [15].
4. Conclusion
A potential semiorganic crystals of thiosemicarbazide potassium chloride (K(NH2 NHCSNH2 )ClH2 O) have been grown by slow
evaporation in mixed solvent of deionized water. The sharp welldened peaks conrm the crystalline nature of the materials. TSCPC
is thermally stable up to 185 C. TSCPC is optically transparent in
the entire visible region with 90% transparency level. The lower cut
off wave-length (260 nm) shows a good optical transparency level
and high melting point makes TSCPC as a new promising material
for many applications. Microhardness value was calculated in order
to understand the mechanical stability of the grown crystals. From
the dielectric studies it is seen that the dielectric constant decreases
with increased frequency.
Acknowledgments
One of the authors (J.C) gratefully acknowledges the nancial support from the DST, Government of India for the major
research project (SR/S2/LOP-07/2008). The authors thank sophisticated analytical Instrumentation facility (STIC), Cochin and Central
Instrumentation Facility (CIF) Pondichery University, for their analytical instrument facilities.
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Please cite this article in press as: J. Chandrasekaran, et al., Synthesis, crystal growth and characterization of a semiorganic material:
Thiosemicarbazide potassium chloride, Optik - Int. J. Light Electron Opt. (2012), doi:10.1016/j.ijleo.2011.11.023

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Please cite this article in press as: J. Chandrasekaran, et al., Synthesis, crystal growth and characterization of a semiorganic material:
Thiosemicarbazide potassium chloride, Optik - Int. J. Light Electron Opt. (2012), doi:10.1016/j.ijleo.2011.11.023