Materials Science for Energy Technologies 2 (2019) 234–245

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Materials Science for Energy Technologies

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A new class semi-organic nonlinear optical materials: Mono(4-sulfo

benzene aminium) tri nickel(II) bis(dihydrogen phosphate) for photonic
applications
E. Vinoth, S. Vetrivel ⇑, S. Gopinath, R. Aruljothi, T. Suresh, R.U. Mullai
Raman Research Laboratory, Post Graduate and Research Department of Physics, Government Arts College, Tiruvannamalai, Tamilnadu 606 603, India

a r t i c l e i n f o a b s t r a c t

Article history: This article is discussing the growth of a new class semi-organic nonlinear crystal (4-sulfo benzene ami-
Received 1 October 2018 nium) tri nickel(II) bis(dihydrogen phosphate) (4-STNBDHP) grown by slow evaporation solution growth
Revised 31 December 2018 technique at ambient temperature. The purity of the crystal was achieved by recrystallization and the
Accepted 8 January 2019
size of the crystal is 3
3
7 mm3. It was harvested over the period of 85 days. The solubility of the
Available online 14 January 2019
4-STNBDHP crystal is done at different temperatures from 30 °C to 80 °C in steps of 10 °C. Lattice param-
eters, obtained from the result of single crystal X-ray diffraction study, indicate that the grown crystal is
Keywords:
an orthorhombic crystal. FTIR spectral investigations indicated the formation of bonds like N–H  O,
Crystal growth
NMR
O  Ni–O and Ni–O–P and these bonds are arising because of doping. The UV–visible spectrum demon-
EDAX strates that the grown crystals are transparent and an absorption peak at 768 nm indicates the presence
Optical properties of Ni2+ ions. TGA/DTA investigations were made to study the decomposition of the title compound.
AC conductivity property Nonlinear optical (NLO) efficiency of the crystal was tested through second harmonic generation effi-
ciency test. Photoluminescence study shows the green light emission. The microhardness analysis con-
firms that the grown crystal belongs to the soft material. From tis study, the mechanical properties
such as stiffness constant (C11), yield strength (dy), hardness (Hv), and hardening coefficient (n) were cal-
culated. The dielectric constant (e), dielectric loss (e0 ), imaginary dielectric constant (e00 ), AC conductivity
(rac) and Cole-Cole graphs were plotted. From this study, it is concluded that the 4-STNBDHP shows
higher conduction at a higher temperature and at low frequency. The elemental analysis was carried
out by energy dispersive X-ray analysis and it confirms the presence of the different elements in the
4-STNBDHP crystal.
Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-
nd/4.0/).

1. Introduction The optical properties of non-centro symmetry materials dis-

The research for new single crystals with better properties has
been increased in the past four decades due to their different
potential applications in industries like microelectronics, semicon-
ductors, photonics, sensors, telecommunications. Now-a-days,
researchers put their attention to the invention of semi-organic
family crystals using sulphanilic acid (SAA) with inorganic and
metal complexes for improving their quality and quantity of crys-
tal properties [1,2]. The semi-organic compounds are optically
more nonlinear than metal-organic coordination materials due to
the weak Vander walls force, hydrogen bond with a high degree
of delocalization [3].
Peer review under responsibility of KeAi Communications Co., Ltd.
⇑ Corresponding author.
E-mail address: vetrivelsivaraman@yahoo.com (S. Vetrivel).
play an extensive variety of physical properties like piezoelectric-
ity, ferroelectricity, and nonlinear optical properties. The well-
known process of non-linear optical properties is widely employed
in optoelectronics, media transmission, surface characterization,
microscopy, optical information stockpiling and rapid data han-
dling [4–12].
A numerous amount of research work has been carried out
based on sulphanilic acid and reported [13–32]. Pure sulphanilic
acid shows in centrosymmetric properties, but when embedded
with metals/metal ion becomes a non-centrosymmetric material
demonstrated nonlinear optical activity.
The amorphous nickel phosphate [Ni3(PO4)4] is a good nonlin-
ear crystalline material and its interesting electrical, optical prop-
erties, structural phase transitions, its ease crystallization has
been reported [33]. This inorganic metal compound of phosphate
forms in a tetrahedron (PO34 ) that shares each of its corners with

https://doi.org/10.1016/j.mset.2019.01.002
2589-2991/Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 E. Vinoth et al. / Materials Science for Energy Technologies 2 (2019) 234–245
one oxygen atom and forms Ni–O–P bonds [34] and the formation
of strong P–O bonds. The electron charges move from the Ni centre
and subsequently reduces the covalence of the Ni–O bonds, which
results in the high potential of Ni3(PO4)2 [35,36].
In this present study, sulphanilic acid based crystals were syn-
thesized with amorphous Ni3(PO4)2 by slow evaporation. The syn-
thesis of 4-STNBDHP crystal from amorphous Ni3(PO4)2 is
embedded in the parent compound of SAA. The influence of some
analytical physicochemical parameters such as nonlinear optical
efficiency, mechanical and dielectric performance were investi-
gated, which are in good agreement with reported data [36,37],
2. Experimental procedures
The chemicals nickel phosphate AR grade (99%) and sulphanilic
acid AR grade (99%) were purchased from Sigma-Aldrich and
Merck chemical company respectively. The single crystal X-ray
diffraction data of the 4-STNBDHP crystal were recorded using
Nonius CAD4/MACH3 single crystal X-ray diffractometer with Mo
Ka radiation (k = 0.71023 Å). The infrared spectrum was recorded
using Alpha Bruker FT-IR, with a resolution of 2 cm1. Samples
were prepared by adding a few amounts of crystals on a pressed
KBr pellet and the measurements were carried out at room tem-
perature. 1H & 13C NMR spectra of the crystals were run on a Bruker
FT-NMR spectrophotometer at room temperature using dimethyl
methoxide (DMSO) as a solvent and tetramethylsilane (TMS) as
Fig. 1. As-grown 4-STNBDHP crystals.
Scheme 1. Growth of the 4-STNBDHP crystal.
235
an internal reference. Thermal stability of the crystal was done
using thermogravimetric analysis (TGA), using Dupont 951 ther-
mogravimetric analyzer. The sample weight was 8–10 mg. The test
was performed from 30 to 600 °C at the heating rate of 10 °C min1
in a nitrogen atmosphere with a gas flow rate of 100 ml min1. The
surface morphology and particle sizes of the samples were deter-
mined by field emission scanning electron microscopy (FESEM;
Hitachi S4800; Japan).
2.1. Synthesis and growth
The 4-STNBDHP crystal was synthesized by taking 1:1 equimo-
lar ratio of sulphanilic acid and nickel phosphate. The estimated
amount of SAA was first dissolved in double distilled water at
70 °C. Nickel phosphate was then added to the mother solution
gradually and mixed well with the help of a temperature con-
trolled magnetic stirrer around ten hours in order to get a homoge-
neous mixture of the solution. Now the solution was filtered four
times with Whatmann filter paper to remove the impurities. Then
the filtered solution was permitted to evaporate at room tempera-
ture without any disturbance. The solution was kept in dust free
area and it was covered with a sheet. The 4-STNBDHP crystal
was obtained by the slow evaporation technique. Re-
crystallization improves the purity of the crystal. The seed acquired
by this technique has been utilized for the huge size development.
The transparent single crystals with an average size 3
3
7 mm3
was reaped within 85 days with the appropriate growth rate of
0.7 mm/day. The photo of as-grown crystal 4-STNBDHP is shown
in Fig. 1.
The chemical reaction path was depicted in Scheme 1 and the
crystal growth informations are given in Table 1.
Using the ‘‘Mercury” software the structure was analysed. The
ORTEP and slicing 3D structure of 4-STNBDHP crystals are shown
in Fig. 2(a) and (b). It is observed that the grown 4-STNBDHP crys-
tal has nitrogen (N), hydrogen (H) and oxygen (O) which makes as
N–H  O bond. Similarly metal ion (Ni2+) formed a new coordinate
bond with oxygen (O) and phosphorus like a monodentate, biden-
tate ligands (Ni2+  P@O, O–P–O, Ni2+  O–P and O  Ni2+  O).
236 E. Vinoth et al. / Materials Science for Energy Technologies 2 (2019) 234–245

Table 1
The growth parameters of the 4-STNBDHP crystal.
30
S. No. Technique Slow evaporation
1 Solvent Double distilled water
2 Nickel phosphate and sulphanilic acid 1:1 M ratio 25
3 Temperature Room temperature

Solubility g/100ml
4 Period of growth 85 days
5 Crystal size (dimension) 3
3
7 mm3
6 Color of crystal Colorless 20
7 Rate of growth 0.7 mm/day

15

The formation of the chain and the bonding process is possible

because of embedded metal ion in the zwitterionic compound SAA.
10

2.2. Solubility of 4-STNBDHP crystal

5
Solubility data are the most important one for a slow evapora- 40 45 50 55 60 65 70 75 80
tion method to know about the solvent supersaturation of the
solution.
Temperature °C
The solubility of the 4-STNBDHP crystal was tested at five dif- Fig. 3. The solubility curve of the 4-STNBDHP crystal.
ferent temperatures viz, 30, 40, 50, 60 and 80 °C by dissolving
grown crystal in double distilled water in sealed shut compartment
kept up at a steady temperature with continuous stirring. After Table 2
supersaturation was achieved, the equilibrium concentration of Crystallographic data of the 4-STNBDHP crystal.
the solute was examined gravimetrically. The same methodology Parameter SAA [10] 4-STNBDHP*
was repeated to estimate the solubility for the above mentioned
Chemical formula C6H7NO3SH2O C6H9NNi3O11P2S5+
temperature. Fig. 3 demonstrates the solubility curve of 4- Molecular weight 191.2 541
STNBDHP crystal in aqueous solution. The solubility is higher at aÅ 6.16 7.36
high temperature and lower at low temperature. bÅ 6.96 7.62
cÅ 18.32 14.06
Α 90° 90°
3. Results and discussion Β 90° 90°
c 90° 90°
3.1. Single crystal X-ray diffraction analysis V (Å3) 786 Å° 790 Å°
Crystal system Orthorhombic Orthorhombic
Space group P212121 P212121
The grown transparent crystal was subjected to single crystal X- hkl index – 302, 023, 180
ray diffraction examination. The unit cell parameters of the grown 2theta – 19.61
4-STNBDHP crystal are a = 7.36 Å, b = 7.62 Å and c = 14.06 Å with *
Present work.
a = 90, b = 90, c = 90 and volume is 790 Å3. It is understood that
the grown crystal 4-STNBDHP is of an orthorhombic system.
Table 2 reveals the cell parameters of the as-grown 4-STNBDHP six very much created faces as like stacking structure of crystal
crystal and that is compared with unadulterated SAA [10]. appeared in Figs. 4a–4c. Fig. 4a confirms the formation of a metal
From the table, it is concluded that the grown crystal retains in oxide bond (bidentate ligand), Figs. 4b and 4c showed the hydro-
the orthorhombic system with changes in a, b, and c value. It is gen bond and monodentate ligand.
because of the influence of additives on the crystal habit [37].
Using ‘‘Chemdraw” software the bond structures were drawn and
picturised as Figs. 4a–4c. The different bonds present in SAA are 3.2. Fourier transform infrared spectroscopic analysis (FT-IR)
i) hydrogen bonding (N–H  O) [38]. ii) monodentate ligand (Ni2+-
  O–P) (H  O–H) and (O–P  O) [39,40]. iii) bidentate ligand The FT-IR is used to distinguish the functional groups in the
(O  Ni2+  O) [41]. The crystal is an orthorhombic structure with grown crystal. The FT-IR spectrum of the 4-STNBDHP crystal was

A B

Fig. 2. (a and b) ORTEP and slicing 3D structure of the 4-STNBDHP crystal.

 E. Vinoth et al. / Materials Science for Energy Technologies 2 (2019) 234–245
Fig. 4a. bidentate ligand (O  Ni2+  O).
2
+
N
Ni2+ i
O
O P O
O where Eg is the optical band gap energy and A is a constant. The plot
O
O P O
H H
O
N S
HO H H
2+Ni O S N
O
OH H H
O O P O
O pared in Table 4. From the table, the band gap energy and cutoff
O P O
O
2+Ni
Ni2+
Fig. 4b. Hydrogen bond (N–H  O) with bidentate ligand (O  Ni   O).
recorded in the region of 500–4000 cm1. The FT-IR spectrum of
the 4-STNBDHP crystal is depicted in Fig. 5 and the assigned peaks
are presented in Table 3. The peak at 3317 cm1 is due to NH+3
(anilinium) stretching frequency and this confirmed that all the
NH2 groups are converted into N–H in the lattices.
Furthermore, the peak appears at 2862 cm1 indicates N–H
stretching frequency. The characteristic peak observed at
1597 cm1 is due to N–H bending frequency. The peaks observed
at 1296 cm1 and at 1203 cm1 are the symmetric and asymmetric
frequency of SO 2 group respectively. In-plane distortion and
straight vibration of N–H results the peaks at 619 cm1,
538 cm1. The wave number appearing in 557 cm1 is due to metal
doped phosphate atom. The weak broad absorptions observed in
the spectrum at 2773, 2673 and 1434 cm1 are attributed due to
N–H  O in-plane deformation [38]. The vibration of O–H  O
hydrogen bond of grown crystal in a dimeric form causes a weak
peak at 1669 cm1 [39]. The interaction of SAA and phosphate
group through nickel (O  Ni–O) is confirmed by the peaks
appeared at 540 cm1 and 752 cm1 [40]. The peak at 450 cm1
attributes to symmetrical bending vibrations of PO34 [41].
3.3. UV–Visible spectrum analysis
A well polished 4-STNBDHP crystal was subjected to UV–visible
studies in the range of 200–1400 nm respectively. The resultant
absorption spectrum of the 4-STNBDHP is shown in Fig. 6. The
absorption was observed to be low in the UV–visible and IR regions
with lower cutoff wavelength at 250 nm. It may attribute the elec-
tronic transition in the aromatic ring of 4-STNBDHP crystal. The
broad peak appeared at 768 nm confirms the formation of a new
237
bond between the oxygen of sulphanilic acid and phosphate
A
through nickel metal O  Ni2+  O [42,43]. The transmittance spec-
trum uncovers that the 4-STNBDHP have good transparency region
between (98%) 250 nm and 1400 nm. This kind of the optical beha-
viour of a material is vital to decide its utilization in optoelectronic
gadgets.
3.3.1. Optical band gap of 4-STNBDHP crystal
The data obtained from UV–visible spectrum is used to calcu-
late the band gap and to analyze the type of electron transition
of grown crystal. The optical absorption coefficient (a) was calcu-
lated from the transmittance spectrum using the following
relation.
1



2:3026 log
a¼ T
ð1Þ
t
where T is the transmittance and t is the thickness of the crystal. For
high photon energies,
B
ahm ¼ Aðhm  Eg Þ1=2 ð2Þ
O of the variation of (ahm)2 versus hm is shown in Fig. 8. Optical band
O Ni2+ gap energy was estimated by extrapolation of the linear part and
O the band gap energy is Eg = 4.3 eV. Reported UV cut-off wavelength
and band gap energy of sulphanilic acid based crystals are com-
wavelength of grown crystal are slightly varied from reported work.
3.4. Photoluminescence
The PL spectroscopy is a non-destructive method of testing to
study the electronic structure of materials [8]. The PL is widely
2+
used in the field of medical, biochemical and chemical research
for finding out the chemical compounds. The PL spectral details
of pure and doped crystal are shown in Table 5. Fig. 7 demonstrates
the PL emission spectrum recorded in the range of 350–800 nm
with an excitation wavelength of 537 nm. The emission peaks at
410 nm and 667 nm indicates the emission from green to red light.
3.5. NMR analysis
Nuclear magnetic resonance spectral analysis helps us to under-
stand the number of hydrogen atoms exist for a particular hydro-
gen or group of equivalent hydrogens. Generally an NMR spectral
lines split in to N + 1 peaks where N = number of hydrogens on
the adjacent atom or atoms. For example If there are no hydro-
gens on the adjacent atoms, then there will be single peak called
as a singlet. If there is one hydrogen on the adjacent atoms, the res-
onance will be split into two peaks of equal size and is known as a
doublet.
The proton NMR spectrum of the 4-STNBDHP was shown in
Fig. 8. The characteristic peak appeared at 7.8 and 7.4 ppm are
due to the presences of four hydrogens of C6H4N aromatic ring.
The doublet at 7.8 and 7.7 ppm are due to the aromatic C–H hydro-
gen ortho to –SO3. The singlet appears at 4.72 ppm is due to the N–
H proton connected to the benzene sulfonate. The singlet observed
at 4.72 ppm is attributed to the –NH+3 hydrogens of anilinium ion
structure. The 13C NMR spectrum of the 4-STNBDHP crystal is given
in Fig. 8 and demonstrates the resonance signals of aromatic car-
bons appear between 123 and 143 ppm. A signal appeared at
d = 143 allocated to the carbon atom of C2 and C6 and medium
intensity peak shown at 132 ppm is attributed to C3 and C5 carbon
atom of the sulphanilic moiety. The 4-STNBDHP crystal moiety
appears as resonance signal at 143 ppm is the character of C1
and C4 carbon bearing SO3 and NH2.
238 E. Vinoth et al. / Materials Science for Energy Technologies 2 (2019) 234–245

Fig. 4c. Packing structure of hydrogen bonds with mono and bidentate bonds.

Table 3
100 The functional groups and vibrational assignments.

%T Wavenumber (cm1) Assignment Reference

3317 and 1629 NH+3 [25]
2594.26

80
1739.79

1002.98
2673.34

2862 and 2673 N–H stretching [24]

2773.64
3317.56

2939.52
2862.36

2862, 2773 and 2673 N–H–O [38]

877.61
1203.58
1597.06

1669 H  O–H [39]

1095.57
1381.03
1296.16

60 1597 N–H bending [18]

1669

752.24
1550.77

1296 and 1203 SO2 [16]

619.15
538.14

752 and 530 O  Ni–O [40]

815.89

450 PO3
4 [41]
40
1434

450

this temperature. In the DTA curve, the endothermic peak observed

20
at 210 °C indicates the start of decomposition and the material is
fully decomposed at 381 °C and therefore the melting point is
381 °C.
0
4000 3500 3000 2500 2000 1500 1000 500 This may be due to the presence of hydrogen bonds in the main
1/cm chain of metal atom to the oxygen atom and hydrogen atom to
phosphate atom. This curve clearly indicates the formation of the
Fig. 5. FTIR spectrum of the 4-STNBDHP crystal.
crystal is pure and without moisture as it shows higher stability.

3.6. Thermal analysis 3.7. SHG efficiency

The thermal stability of 4-STNBDHP was understood by thermo- The modified Kurts-Perry powder technique initially screens
gravimetric analysis (TGA) and differential thermal analysis (DTA). the materials for second harmonic generation using a Q-switched
The TG-DTA curves are shown in Fig. 9. Since there is no endo-or Nd: YAG laser (Quanta ray series) with a pulse repetition rate of
exothermic transition below 200 °C, the material is stable up to 10 Hz [43]. Fine powder of grown crystal sample tightly packed
 E. Vinoth et al. / Materials Science for Energy Technologies 2 (2019) 234–245 239

Table 5
The PL spectral details of pure and doped crystals.

Crystals Absorption Absorption color Reference

Sulphanilate ion 540 Green [44]
SSDH 560 Yellow [17]
Potassium carbonate with 546 Green [20]
sulphanilic acid
Poly(sulphanilic acid) 412–451 Blue shift [45]
4-STNBDHP 537 Green Present work

and metal hydrogen bonding in the crystal structure. So the crystal

has supramolecular network and it shows high second harmonic
generation efficiency.

3.8. Microhardness

In the present examination, Vickers microhardness study was

done to the grown 4-STNBDHP crystal. The experiment was carried
out using SHIMADZU HMV microhardness tester fitted with the
diamond pyramidal indenter [45,46].
Fig. 6. UV–vis absorption spectrum of the 4-STNBDHP crystal.
The indentation time was kept constant for 10 s and the micro-
hardness measurement was taken between the different applied
load (p) varies from 25 to 100 g. The average diagonal length was
calculated and the diagonal length was measured at each time.
The Vicker’s hardness number was determined using the formula
2

Ht ¼ 1:8544 P=d kg=mm2 ð3Þ
A graph was plotted between Ht versus load (p) and appears in
Fig. 10. It is concluded that Ht increase with the applied load which
is known as reverse indentation size effect (RISE). For an indenta-
tion load of 100 g, crack was initiated on the crystal surface around
the indent and it is due to the release of inside stress locally initi-
ated by indentation. The work hardening coefficient (n) has been
computed from the slope of a straight line between log p and log
d from Fig. 11 and it is found to be 3.7. It indicates that the grown
crystal possesses the soft nature of the material. The yield strength
of the material can be elucidated by the relation [46,47].

Fig. 6a. Tauc’s plot of 4-STNBDHP crystal.
between two transparent glass slides and kept in the path of the
Monochrometer laser beam of 3.1 mJ pulse range. The emission
of green light of wavelength k = 532 nm by the sample after filtra-
tion of the incident radiation, confirms second harmonic genera-
tion (2x). So the grown 4-STNBDHP is a non-centrosymmetric
crystal. The SHG efficiency of the as-grown 4-STNBDHP crystal
was found 1.3 times as that of KDP and it is shown Table 6. The
increase in SHG efficiency may be due to the intermolecular charge
transfer between nickel metal to SA hydrogen bonds and parallel
pairing dipole moments between the phosphate oxygen atom
Hv
ry ¼ ð0:1Þn  2 ð4Þ
3
where n0 = n + 2, ry is the yield strength of the material, Hv is the
hardness number and n is the work hardening coefficient. The graph
drawn for load P versus yield strength appears in Fig. 12.
It is shown that yield strength increases with the load and
therefore the grown crystal has moderate mechanical strength.
According to Wooster’s, the stiffness constant (C11) can be found
from the relation,
C 11 ¼ H7=4
v ð5Þ
A graph is plotted between load P and stiffness constant as rep-
resented in Fig. 13. From the graph stiffness constant increments
with the load. The calculated stiffness constant C11, yield strength
ry and Vickers’s hardness value for different loads are compiled in
Table 7.

Table 4
Comparison of UV cut-off wavelength and bandgap of sulphanilic based crystal.

S. No. Name of the crystal Band gap in eV UV cut-off wavelength (nm) Reference
1 Lithium sulphanilic acid (LS) 3.83 310 [19]
2 SAM crystal 4.50 249 [25]
3 SSDH 3.75 415 [21,17]
4 4-STNBDHP 4.3 250 Present work
240 E. Vinoth et al. / Materials Science for Energy Technologies 2 (2019) 234–245

Fig. 7. PL emission spectrum of the 4-STNBDHP crystal.

3.9. Dielectric analysis cd

e¼ ð6Þ
Aeo
The dielectric constant and the dielectric loss of 4-STNBDHP
sample were measured using HIOKI 3532-50 LCR HITESTER. The e0 ¼ etand ð7Þ
sample of grown crystal has been placed inside a dielectric cell
whose capacitance is estimated at different temperature (308– here d is the thickness, A is the area of the sample. Figs. 14 and 15
368 K) and at different frequencies (100 Hz to 5 MHz). Dielectric demonstrate the variation of dielectric constant and dielectric loss,
constant and dielectric loss of the sample has been calculated using respectively, as a function of frequency at different temperatures. It
the equation [48]. is observed from Fig. 14 that the dielectric constant decreases with
increase in frequency from 50 Hz to 5 MHz and then attain almost

1
H- NMR

Fig. 8. 1H and 13
C NMR spectrum of 4-STNBDHP crystal.
 E. Vinoth et al. / Materials Science for Energy Technologies 2 (2019) 234–245 241

Fig. 9. TG-DTA curves of the 4-STNBDHP crystal.

Table 6
Comparison of SHG output signal. 2.0

Sl. No. Name of the Sample Output Energy (mJ) Input Energy (mJ)
1.9
1 TSBA crystal. [24] 11.8 3.1
2 KDP (Reference) [25] 5.82 0.70
1.8
3 4-STNBDHP* 10.3 0.70

1.7
Log P

110
1.6

100 1.5

1.4
90
Hv (Kg/mm )

1.3
2

80 1.46 1.48 1.50 1.52 1.54 1.56 1.58 1.60 1.62 1.64
Log d

70 Fig. 11. Log p and log d for 4-STNBDHP crystal.

60

The variation of the imaginary part of the dielectric constant

50
with frequency also shows similar behaviour with temperature
20 30 40 50 60 70 80 90 100 110 and frequency to that of the real parts of the dielectric constant.
Load P (g) The variation of the imaginary part of the dielectric constant with
frequency is shown in Fig. 16. The imaginary part of the dielectric
Fig. 10. Hardness Hv versus load (p) for 4-STNBDHP crystal. constant is found to be strongly temperature dependent because of
low temperature and high frequency. Similarly, at high tempera-
ture and low-frequency break up the hydrogen bond in the crystal
constant. The similar trend is measured for other temperatures. It is system exists. The dielectric loss factor depends on changing the
additionally observed that the value of dielectric constant increases value at all temperatures in the high-frequency region.
with temperature. Such variations in higher temperature might be
ascribed to the hindering of charge carriers at the electrodes. The
decrease of dielectric constant at low-frequency region may be 3.9.1. Electrical conductivity studies
because of space charge polarization. Fig. 15 demonstrates that as The study of electrical conductivity of grown crystals gives an
the frequency increases, the dielectric loss decreases exponentially approach to the material properties with respect to the mobility
and then attains constant. The low value of the dielectric loss of charged ions and electrons. This gives information on relaxation
affirms that the sample possesses lesser defects. time and temperature dependence of these studies. The alternating
242 E. Vinoth et al. / Materials Science for Energy Technologies 2 (2019) 234–245

3.0
130
2.8

2.6 125 40
50
Yield strength (Kg/mm )
2

2.4 60
120

D ie le c r ic c o n s ta n t ( ε )
70
2.2
115
2.0

1.8 110

1.6
105

1.4

100
20 30 40 50 60 70 80 90 100 110
Load P (g)
95
Fig. 12. The graph between load P versus yield strength.

2 3 4 5 6 7

Log (Hz)

3500 Fig. 14. Variation of dielectric constant with frequency.

3000
0.35
Stiffness constant (C11)

2500 0.30 40
50
0.25 60
2000
70
D ie le c tric L o s s ( ε ' )

0.20

1500
0.15

1000
0.10

20 30 40 50 60 70 80 90 100 110 0.05

Load P (g)
0.00
Fig. 13. The graph between load P and stiffness constant.

current (AC) conductivity rac is calculated using the equation [48– -0.05
50], 2 3 4 5 6 7

rac ¼ 2pf e0 e0 tan d ð8Þ Log F(Hz)

where tan d is the dielectric loss estimated directly from the impe- Fig. 15. Variation of dielectric loss with frequency.

dance analyzer and f is the frequency of the applied ac field (Hz).

The graph is plotted with ac conductivity (rac) versus log f and it
is shown in Fig. 17. the ac conductivity was found to be increasing feebly up to 4 MHz.
It was observed that the crystal has very low conductivity in the This indicates the dielectric breakdown frequency of the material.
low-frequency region up to 40 kHz for all temperatures. Thereafter, The value of the total electrical resistance is evaluated from the

Table 7
The mechanical properties of 4-STNBDHP crystal.

Load P (g) Hv (kg/mm2) D (lm) Yield Strength (ry) (kg/mm2) Elastic Stiffness constant (C11) Fracture toughness (Kc) 104 kg/m3/2 Brittleness index
(Bi) (m1/2)
25 54.5 29.16 1.506 1093.18 6.415 849.55
50 75.55 34.85 2.087 1936.02 9.816 769.59
100 103.5 42.58 2.860 3358.50 14.542 711.70
 E. Vinoth et al. / Materials Science for Energy Technologies 2 (2019) 234–245 243

7
50 5x10
Imaginary Dielectric constant( ε '')

0
40 C 7
40 0
4x10
50 C
0
60 C
0 7
70 C 3x10
30
40°C

II
Z
50°C
7
2x10 60°C
20
70°C
7
1x10
10

0
0
6 6 6 6 6 7 7 7
-2.0x10 0.0 2.0x10 4.0x10 6.0x10 8.0x10 1.0x10 1.2x10 1.4x10
I
2 3 4 5 6 7 Z
Log f (Hz)
Fig. 18. Cole-Cole plots of the 4-STNBDHP crystal.
Fig. 16. Variations between imaginary dielectric constant with frequency.
Cole-Cole plots shown in Fig. 18, plotted between Z00 = Z0 cos h (real
part of impedance) and Z00 = Z sin h (imaginary part of impedance).
From these plots, the bulk resistance measured was found to be
0.0025 decreased with increasing temperatures resulting in the enhance-
ment of electrical conductivity at higher temperatures. The graph
40°C evaluates the gradual increase in the conductivity with the slow
0.0020
50°C increase in the temperature because of the increase in mobility
AC Conductivity( σv)

60°C and release of ions at prominent temperatures.

70°C
0.0015

3.10. EDAX analysis of 4-STNBDHP crystal

0.0010

The basic investigation about the compounds present in a mate-

0.0005
rial is carried out by using the Oxford INCA Energy Dispersive
Atomic X-ray Fluorescence Spectrometer (EDAX) [50]. This tech-
nique is widely used in the quantitative analytical method and
0.0000 the presence of nickel metal embedded into the crystal is shown
in Fig. 19. The atomic percentage and weight percentage of ele-
2 3 4 5 6 7 ments present in the crystal lattices are shown in the correspond-
Log f (Hz) ing table.

Fig. 17. AC conductivity (dac) versus log f.

3.11. FESEM analysis

The surface morphology and the particle size of the 4-STNBDHP

crystal were evaluated through FESEM analysis and the images are

Element Weight% Atomic%

O 67.93 79.00

S 31.20 20.80

Ni 0.88 0.20

Total 100.00 100.00

Fig. 19. EDAX spectrum and data of the 4-STNBDHP crystal.

244 E. Vinoth et al. / Materials Science for Energy Technologies 2 (2019) 234–245
Fig. 20. FESEM image of the 4-STNBDHP crystal.
appearing in Fig. 20. The incorporation of nickel in the crystal lat-
tices is observed (17, 28).
4. Conclusion
The semi-organic 4-STNBDHP crystal has been grown by slow
evaporation technique. Optically transparent crystals have grown
in an average period of 85 days and have dimensions
3
3
7 mm3. The unit cell parameters of the grown 4-
STNBDHP crystal are a = 7.36 Å, b = 7.62 Å and c = 14.06 Å, a = 90,
b = 90, c = 90 and volume is 790 Å3. The sample showed high crys-
tallinity. UV–visible spectrum was recorded and the lower cut-off
wavelength is at 250 nm All the functional groups and hydrogen
bonding were confirmed by FT-IR techniques. The 4-STNBDHP
crystal shows the packing structure of hydrogen bond N–H  O,
of monodentate H  O  H and bidentate ligand O  Ni  O bond.
The structural arrangements of protons are confirmed by NMR
analysis. Photoluminescence study shows green light emission.
The grown 4-STNBDHP crystal has a high melting point and its
exhibits high thermal stability. Nonlinear optical (NLO) study
was performed by Kurtz powder technique and SHG efficiency is
1.3 times that of KDP. The mechanical strength of grown crystal
was analyzed by the Vickers microhardness tester. The elemental
analysis was done by EDAX. The dielectric response of these crys-
tals was studied in the frequency range 50 Hz to 5 MHz at various
temperatures and the results are discussed. To end with, it is con-
cluded that grown crystal is suitable for industrial applications
because it possesses good thermal stability, moderate SHG effi-
ciency, and better optical properties.
Conflict of interest
No conflict of interest.
Acknowledgements
The authors would like thank Professor Dr. R. Jayavel, Director,
Centre for Nanotechnology, Anna University, Chennai, and IIT-
Madras for constant support to the analysis of single crystal XRD
studies. Also express their gratitude to B. S. Abdur Rahman Univer-
sity, Vandalur, Chennai for providing the instrument facility for
characterization.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.mset.2019.01.002.
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