Optik 125 (2014) 824827

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Growth and characterization of BTCS and BTZA crystals grown by
slow evaporation method
A. Albert Irudayaraj

, A. Dhayal Raj, G. Illavarasi

Department of Physics, Sacred Heart College, Tirupattur, Vellore District, Tamil Nadu, India
a r t i c l e i n f o
Article history:
Received 12 March 2013
Accepted 10 July 2013
Keywords:
Slowevaporation
BTCS and BTZA crystals
Microhardness
a b s t r a c t
Good quality Bisthiourea Cadmium Sulphate (BTCS) and Bisthiourea Zinc Acetate (BTZA) crystals have
been grown by simple slow evaporation method. From the powder X-ray diffractograms it is found that
BTCS crystal belongs to orthorhombic system, whereas BTZA crystal belongs to Tetragonal system. The
FTIR analysis reveals that the C S stretching frequencies of both BTCS and BTZA shows a shift to lower
frequencies when compared to pure thiourea, which may be attributed to the reduced double bond
character of C S bond on coordination. UVvis spectroscopic studies show that the grown crystals have
high transparency in entire visible region and NIR region. The hardness of the crystals have been studied
using Vickers microhardness test and it was found that the BTZA crystals show better hardness when
compared to BTCS crystals.
2013 Elsevier GmbH. All rights reserved.
1. Introduction
NLOmaterials nda veryvast applicationinthe eldof telecom-
munication, optoelectronics, optical switching an optical signal
processing. Organic crystals have high NLO properties but poor
mechanical strength and growing large size optically transpar-
ent crystals is difcult. Whereas, the inorganic crystals have high
mechanical strengthandbetter thermal properties but modest NLO
properties [1]. In the recent past, research in hybrid NLO materi-
als having the advantages of both organic and inorganic materials
has gained momentum because of the increasing necessities of a
cheap and easily processable material for device applications [2].
Two types of hybrid NLO materials have been explored; organic
and inorganic salts and metal organic coordination complexes
[3]. Hybrid NLO materials fromorganicinorganic complexes with
stronger ionic bond are called as semi-organic NLO materials.
In semiorganic materials the weak forces of organic solids are
replaced by stronger ionic forces forming a complete new class of
semi-organic crystals having large nonlinearity, higher mechanical
strength, high thermal stability, good transmittance, high resis-
tance to laser induced damage and high chemical stability suitable
for electronic industries [4]. Thiourea which has a very good
crystallographic symmetry and large dipole moment is an inter-
esting inorganic matrix modier [5,6]. When thiourea combines
withinorganic salt, it yields noncentrosymmetric complexes which

Corresponding author.
E-mail address: albertirudayaraj@gmail.com(A. Albert Irudayaraj).
results in enhanced NLO activity [7,8]. For this reason, metal com-
plexes of thiourea are considered to be interesting semi-organic
NLO materials, which could play a vital role in optical modulation,
bre optic communication, optical storage devices and optoelec-
tronics [9].
In this work metal complexes of thiourea, Bisthiourea Cad-
mium Sulphate (BTCS) and Bisthiourea Zinc Acetate (BTZA) have
been synthesized by chemical route and crystals of BTCS and BTZA
have been grown from their aqueous solutions by slow evapora-
tion technique. The structural, optical and mechanical properties
of the grown crystals have been studied by powder XRD, FTIR and
UVvis spectroscopy and Vickers microhardness test. The results
are compared.
2. Experimental procedure
2.1. Preparation of raw material
BTCS raw material was synthesized by mixing Cadmium Sul-
phate and thiourea in the ratio of 1:2. in deionized water at room
temperature.
CdSO
4
+2CS(NH
2
)
2
Cd[CS(NH
2
)
2
]
2
SO
4
BTZA rawmaterial was synthesized by mixing Zinc Acetate and
thiourea intheratioof 1:2. indeionizedwater at roomtemperature.
Zn(CH
3
COO)
2
+2CS(NH
2
)
2
Zn[CS(NH
2
)
2
]
2
(CH
3
COO)
2
0030-4026/$ see front matter 2013 Elsevier GmbH. All rights reserved.
http://dx.doi.org/10.1016/j.ijleo.2013.07.063
A. Albert Irudayaraj et al. / Optik 125 (2014) 824827 825
46 44 42 40 38 36 34 32 30 28
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
BTCS
BTZA
S
o
l
u
b
i
l
i
t
y

(
g
/
1
0
0
m
l
)
Temperature (C)
a
b
Fig. 1. Solubility curve of rawmaterials (a) BTCS and (b) BTZA.
2.2. Solubility of BTCS and BTZA
The solubilityof BTCS andBTZAwas determinedat four different
temperatures 30, 35, 40 and 45

C by dissolving the raw materials

of BTCS and BTZA in deionized water at the relevant temperature.
After attaining saturation, the container was kept at desired tem-
peratureinconstant temperaturebathfor 1h. Then, theequilibrium
concentration of the solute was estimated using specic gravity
bottle. The same process was repeated at different temperatures
and the solubility curves of BTCS (Fig. 1(a)) and BTZA (Fig. 1(b))
were drawn. BTCS has a reasonably moderate solubility in water,
while BTZA has a comparatively lower solubility as revealed from
the slope of the solubility curves.
2.3. Method of obtaining seed crystals of BTCS and BTZA
Bisthiourea Cadmium Sulphate and Bisthiourea Zinc Acetate
crystals were grown at room temperature by slow evaporation
method. The super saturated solutions of raw materials of BTCS
and BTZAin deionized water were prepared. The solutions were l-
tered and poured into separate Petri dishes and were kept without
any disturbance for slowevaporation. Seed crystals were obtained
after about 15 days. Recrystallizations were carried out few times
and transparent crystals with good morphology were harvested.
The photograph of the grown crystals of BTCS and BTZA are shown
in Fig. 2(a and b). The insert pictures in Fig. 2(a and b) show the
higher magnied images of the grown crystals. The BTCS crys-
tals show more or less uniform growth along all the directions
(Fig. 2(a)) while, the BTZA crystals show equal growth along two
directions and a rapid growth along the third direction as shown
in Fig. 2(b). The schematics of the growth morphology has been
presented in Fig. 3(a and b). This growth nature has been proposed
Fig. 2. The photographs of (a) BTCS and (b) BTZA crystals.
a
b
c
b
c
a
a b
Fig. 3. (a) BTCS crystals with orthorhombic structure a / = b / = c. (b) BTZA crystals
with tetragonal structure a =b / = c.
based on the XRD results and are compared with their respective
crystal structures. The BTZA crystals are comparatively lengthier
than BTCS crystals. The maximumsize of the BTCS crystal is around
9mm 6mmwhile that of BTZA crystal is around 25mm6mm.
3. Characterization of BTCS crystal
3.1. Structural analysis
The synthesized materials were subjected to powder X-ray
diffraction studies to analyze whether they have a crystalline
nature or not. Powder XRD was recorded using CuK radiation
of wavelength 1.5406

A. The powder X-ray diffraction patterns
of BTCS and BTZA crystals are shown in Fig. 4(a and b). The
peaks of both the samples were indexed using Treor software.
The X-ray diffractogram shows many diffraction peaks and the
sharpness of the diffraction peaks indicates that the material has
a good crystalline nature. The BTCS crystals were found to have
an Orthorhombic structure with lattice parameters a =20.9813

A,
b=7.2000

A and c =5.8035

A, while the BTZA crystals exhibited a
Tetragonal structure with lattice parameters a =b=8.5766

A and
c =11.6097

A.
3.2. Vibrational analysis
To study the inuence of the metal complexation on the vibra-
tion frequencies of thiourea and to conrmthe metal coordination
of thiourea either through S or N, the CN and CS stretching of BTCS
andBTZAwerecomparedwithfreeligand(thiourea). TheFTIRspec-
tra of both the materials showalmost similar peaks (Fig. 5) for N H
stretching vibrations. When compared to thiourea, N Hstretching
15 20 25 30 35 40 45 50 55 60 65
0
100
200
300
400
500
600
700
800
2 (degrees)
I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
n
i
t
s
)
Fig. 4. Powder XRD pattern of (a) BTCS and (b) BTZA crystals.
826 A. Albert Irudayaraj et al. / Optik 125 (2014) 824827
Table 1
Assignments of IR band frequencies (cm
1
) of thiourea, BTCS and BTZA stretching vibrations.
Wavenumber (cm
1
) Assignments
Thiourea BTCS BTZA
3380 3388 3382 N H asymmetric stretching vibration of NH
2
group
3279 3287 3306 N H asymmetric stretching vibration of NH
2
group
3177 3190 3178 N H symmetric stretching vibration of NH
2
group
3090 3070 N H symmetric stretching vibration of NH
2
group
2696 2750 C H stretching vibrations
2354 2354 C H stretching vibrations
1618 1613 1638 N H bending vibration
1412 1401 1398 Asymmetric C S stretching vibration
1089 1117 1128 Symmetric C-N stretching vibration
730 710 680 Symmetric C S stretching vibration
487 482 482 N C N bending vibration
vibrations of both BTCS and BTZA exhibit a shift towards higher
wavenumber. The C H symmetric are observed at 2354, 2696 and
2750cm
1
[10]. The vibrations at 1620 and 1634cm
1
are reported
as vibrations due to N H bending in Cadmium Bis-thiourea Chlo-
ride and Zinc Tris-Thiourea Sulphate [11]. In the present study
of BTCS and BTZA, on coordination of CdSO
4
with thiourea and
Zn(CH
3
COO)
2
with thiourea, this band has been shifted marginally
to 1613 and 1638cm
1
. The C S stretching frequencies of both
materials show a shift towards lower wavenumber when com-
pared to thiourea (Table 1). The metalsulfur bond is assumed to be
responsible for the shifting of the vibration at 1412 and 730cm
1
to lower wavenumber in both materials. The lowering of frequency
canbe attributedto the reduceddouble bondcharacter of C S bond
on co-ordination [8]. The shift in C S stretching frequency is more
for BTZA when compared to BTCS, which indicates that the reduc-
tion in the double bond character of C S is more in the case of
BTZA.
3.3. UVvis spectral analysis
The optical transmission spectra of BTCS and BTZA were
recorded over a wavelength of 200800nm using Varian Cary 50
UVVis-NIR spectrometer. The recorded transmission spectra are
shown in Fig. 6. From the spectra, it is noted that, the UV trans-
parency cut-off wavelength for BTCS occurs at 267nmand that of
BTZAoccurs at 278nm. Boththe materials showgood optical trans-
mittance over the UV and visible regions (267800nm). This also
conrms the colourless nature of the crystals. Higher transmittance
in the visible region is most desirable feature for any non-linear
optical crystal having applications in second harmonic generation
and optoelectronic devices [12,13]. Hence both BTCS and BTZA can
4000 3500 3000 2500 2000 1500 1000 500
0
20
40
60
80
100
%

T
r
a
n
s
m
i
t
t
a
n
c
e
Wavenumber (cm )
BTCS
BTZA
b
a
Fig. 5. FTIR spectrumof (a) BTCS and (b) BTZA crystals.
800 700 600 500 400 300 200
0
20
40
60
80
100
b
%

T
r
a
n
s
m
i
t
t
a
n
c
e
Wavelength (nm)
BTCS
BTZA
a
Fig. 6. UVvis spectrumof (a) BTCS and (b) BTZA crystals.
be used for SHG with laser operating at 1064nm or other optical
applications in the blue region [10,14].
3.4. Microhardness analysis
Mechanical strength of any device material is represented by
its hardness. Hardness of a material is a measure of its resistance
to the local deformation caused by indentation. The indentation
hardness is measured as the ratio of applied load to the surface
area of the indentation. Microhardness measurements were car-
ried out using Mitutoyo Microhardness Tester for applied loads
50 40 30 20 10
35
40
45
50
55
60
65
70
75
b
H
a
r
d
n
e
s
s

n
u
m
b
e
r

H
v

(
k
g
/
m
m
2
)
Load P (g)
BTCS
BTZA
a
Fig. 7. Variation of Vickers microhardness number with applied load (a) BTCS and
(b) BTZA.
A. Albert Irudayaraj et al. / Optik 125 (2014) 824827 827
(P) 10, 25 and 50g. Several indentations were made for each load
and the diagonal lengths (d) of the indented impressions were
measured. Vickers hardness number [11] was determined using
the formula H
v
=(1.854P)/d
2
. The variation of hardness H
v
with
load P for BTCS and BTZA are shown in Fig. 7(a and b). The mea-
sured hardness number of both BTCS and BTZA is found to increase
with the applied load. The harness exhibited by BTZA crystals
(Fig. 6(a)) is morewhencomparedtothat of BTCScrystals (Fig. 6(b)).
This is in agreement with the observation made by Rajesh et al.
[14] in the case of semi-organic crystals ZTS and BTCC that the
hardness value is inversely proportional to the lattice parame-
ter.
4. Conclusions
BTCS and BTZA crystals have been grown by slow evaporation
method. A detailed comparison of vibrational data of BTCS and
BTZA reveals that symmetric C S stretching vibrations are shifted
towards lower frequency region with respect to thiourea which
indicates that the coordination of thiourea with the metal ions
is through sulphur atom. The UVvis optical transmission studies
show that both BTCS and BTZA exhibit high optical transparency
in the entire UVvis region which recommend the crystals for
NLO applications. The Vickers microhardness studies reveal that
the hardness of BTZA crystals is greater than that of BTCS crys-
tals.
References
[1] R. Mohankumar, D. Rajan Babu, G. Ravi, R. Jayavel, Growth and characterization
of 4-dimethylamino-N-methyl-4-stilbazoliumtosylate (DAST) single crystals, J.
Cryst. Growth 250 (2003) 113117.
[2] J. Thomas Joseph Prakash, L. Ruby Nirmala, Synthesis, spectral and thermal
properties of bis thiourea zinc acetate (BTZA) nonlinear optical single crystal,
Inter. J. Comp. Appl. 6 (2010) 711.
[3] H.Q. Sun, D.R. Yuan, X.Q. Wang, X.F. Cheng, C.R. Gong, M. Zhou, H.Y. Xu, X.C.
Wei, C.N. Luan, D.Y. Pan, Z.F. Li, X.Z. Shi, A novel metalorganic coordination
complex crystal: tri-allylthiourea zinc chloride (ATZC), Cryst. Res. Technol. 40
(2005) 882886.
[4] M.M. Khandpekar, S.P. Pati, Growth and characterisation of new non linear
optical material -glycinesulpho-nitrate(GLSN) withstabledielectric andlight
dependent properties, Opt. Commun. 283 (2010) 27002704.
[5] S. Gopinath, S. Barathan, R. Rajasekaran, Growth and characterization of semi-
organic nonlinear optical crystal: urea thiourea zinc sulphate (UTZS), G.J. P&A
Sc. and Tech. 2 (2012) 2733.
[6] W.Q. Zhou, R.D. Lu, X. Wang, Theoretical studies on nonlinear polarizability of
substitution thiourea, J. Mol. Struct. Theochem. 624 (2003) 123127.
[7] S. Anie Roshan, C. Joseph, M.A. Ittachen, Growth and characterization of a
new metalorganic crystal: potassiumthiourea bromide, Mater. Lett. 49 (2001)
299302.
[8] I. Vetha Potheher, K. Rajarajan, M. Vimalan, T. Rajesh Kumar, R. Jeyasekaran, P.
Sagayaraj, Investigationonthegrowthandcharacterizationof nonlinear optical
single crystals of tris-allyl thiourea mercury bromide (ATMB), Arch. Appl. Sci.
Res. 2 (2010) 171182.
[9] G. Senthil Murugan, N. Balamurugan, P. Ramasamy, Growth and characteri-
zation of a new metalorganic crystal: bis-thiourea cobalt chloride (BTCoC),
Mater. Lett. 62 (2008) 30873090.
[10] S. Selvakumar, S.M. Ravi Kumar, K. Rajarajan, A. Joseph Arul Pragasam, S.A.
Rajasekar, K. Thamizharasan, P. Sagayaraj, Growth and characterization of a
novel organometallic nonlinear optical crystal: bis(thiourea) cadmium for-
mate, Cryst. Growth Des. 6 (2012) 26072610.
[11] A. Pricilla Jeyakumari, J. Ramajothi, S. Dhanuskodi, Structural and microhard-
ness studies of a NLO materialbisthiourea cadmiumchloride, J. Cryst. Growth
269 (2004) 558564.
[12] S. Ariponnammal, S. Chandrasekaran, C. Sanjeeviraja, Low temperature pho-
toluminescence study on zinc tris thiourea sulphate single crystal, Dig. J.
Nanomater. Bios. 7 (2012) 947957.
[13] Maria Suszy nska, Load dependence of hardness of the doped soda-lime silicate
glasses, Opt. Appl. 2 (2012) 399406.
[14] N.P. Rajesh, V. Kannan, M. Ashok, K. Sivaji, P. Santhana Raghavan, P. Ramasamy,
A new nonlinear optical semi-organic material: cadmium thiourea acetate, J.
Cryst. Growth 262 (2004) 561566.