J Mater Sci: Mater Electron
DOI 10.1007/s10854-017-8196-4
Bulk crystal growth, spectral, optical, thermal, electrical
and third-order NLO properties of benzylidene malononitrile
derivative single crystal: a promising material for nonlinear
optical device applications
A. Priyadharshini1 · S. Kalainathan1
Received: 16 August 2017 / Accepted: 3 November 2017
© Springer Science+Business Media, LLC, part of Springer Nature 2017
Abstract Bulk organic intramolecular charge transfer non-
linear optical single crystal of 2-(2,4-dimethoxybenzylidene)
malononitrile (DMM) with the sizes of 24 × 18 × 13 mm3
have been successfully grown by slow evaporation solution
growth technique at 35 °C using acetone as the solvent. The
lattice parameters of the grown DMM crystal was evalu-
ated by single crystal X-ray diffraction analysis. The opti-
cal transmittance (T) data was taken from the well-polished
crystal of DMM, and cut-off wavelength (λ = 483 nm) was
identified by UV–Vis spectral studies. Thermal stability and
melting point (145.78 °C) were studied with TGA–DSC
analysis. The low value of the dielectric constant (ε r) of
DMM suggests that the crystal can be used in the micro-
electronics industry. The laser-induced damage threshold
experiment shows that the grown DMM bulk crystal pos-
sess an excellent resistance to laser radiation with a high
threshold up to 1.75 GW/cm2, much larger than those of
several known organic and inorganic NLO materials. The
DMM crystal exhibits positive optical non-linearity and
reverse saturation absorption. It also exhibited a nonlinear
refractive index (­ n2) in the order of 1­ 0−11 m2/W, a nonlinear
absorption coefficient (β) in the order of 1­ 0−5 m/W, third
order non-linear susceptibility (χ(3)) in the order of ­10−5 esu
and a second-order molecular hyperpolarizability (γ) in the
order of 1­ 0−33 esu. All the above results indicate that DMM
has a potential application as a useful NLO candidate.
* S. Kalainathan
kalainathan@yahoo.com
1
Centre for Crystal Growth, VIT University, Vellore 632 014,
India
1 Introduction
Organic nonlinear optical (NLO) crystals with centrosym-
metric space group play a major role in a third-harmonic
generation (THG) and find a wide range of applications in
optical signal processing, optical power limiting for sensor
production, optical communication networks and integrated
optics, etc. To date, most of the organic molecules developed
for this purpose consist of extended π- conjugated system
end-capped with an electron donor (D) and electron accep-
tor (A) substituents which carrying vast application in the
field of chemistry. Organic materials exhibit large nonlinear
response when compared to inorganic materials because of
the presence of π-delocalized inter/intramolecular charge
transfer (ICT) configuration system. Moreover, such kind
of organic crystals are very promising candidate to enhance
the field induced NLO effect under the action of the applied
electric field [1]. Usually, to form a carbon–carbon (C=C)
bonds with π-conjugated chromophores of organic mate-
rials, many reactions have been reported, such as Knoev-
enagel condensation (hereafter cited in the text as KC),
Wittig–Horner–Emmons condensation (or Wittig reaction)
and Suzuki coupling reaction. Among these, KC reaction is
a favourable and easy method to form C=C double bonds
[2]. Uptaken of the benzylidene malononitrile derivatives
represent a group of disubstituted of the type D–π–A. How-
ever, the conjugated electron systems in a compound with
donor–acceptor benzylidene malononitrile derivatives dis-
play extremely large second-order optical susceptibility (γ)
[3]. Benzylidene malononitrile, the main products of the
KC of various substituted aldehydes with active methylene
compound malononitrile to form an extended conjugated
chain and the class of chromophore based on the ICT,
which play a significant role in the manifestation of non-
linearities. To investigate this possibility, we have chosen
13
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2-(2,4-dimethoxybenzylidene) malononitrile (DMM) com-
pound which is one of the best organic NLO crystal has been
synthesized by KC. Notably in this process based on the
elimination water molecule between the carbonyl aldehyde
group and active hydrogen compound in mild conditions
using a piperidine as the catalyst. In this respect, the for-
mation of the DMM consists of a benzene ring, in which a
donor of 2,4-dimethoxy group is substituted with one of the
ortho positions and para positions, while an acceptor nitrile
group is substituted directly across the ring in the other para
position and forms a centric crystal (centrosymmetric crys-
tal, space group P21/n) that is required for a manifestation
of the THG signal in the solid state [4]. Previously, Antipin
et al. [5] reported the crystal structure of DMM. A detailed
literature survey shows that no significant studies are avail-
able for this material. Based on these facts, in our previous
paper [6] we reported bulk crystal growth and third-order
NLO properties of the DMM crystal. Thereby at present, we
forward next step to investigate some other characterizations
of title crystal.
2 Experimental section
2.1 Raw materials, synthesis, solubility, crystal growth
Analytical grade 2,4-dimethoxybenzaldehyde and malo-
nonitrile were purchased from Sigma-Aldrich and were
used without any further purification. The acetone used as
a solvent was HPLC grade. The synthesis procedure for the
DMM compound has been described previously [6]. On the
commercial side, for all the practical device applications
requires the reasonable size of the good quality crystal.
For instance, solubility study is an essential parameter to
optimize the growth rate of crystal. The solubility of the
DMM was measured in acetone as a function of tempera-
ture between 25 and 45 °C in steps of 5 °C. From the graph
(Fig. 1) it was observed that solubility increases almost lin-
early with temperature (positive solubility gradient). There-
fore, slow evaporation solution growth (SESG) may be a
superior method to grow good quality crystals of the title
compound.
According to the solubility data, a saturated solution was
prepared using acetone as solvent. The solution was stirred
to get the homogenous mixture, and it was filtered and cov-
ered by an aluminium foil with few holes for controlled-
solvent evaporation using a constant temperature water bath
maintained at 35 °C in a dust free atmosphere. The crystal-
lization occurred within 22 days with average dimensions
of 24 × 18 × 13 mm3. The grown DMM crystal is shown in
Fig. 2a. The typical morphology of grown crystal along with
its corresponding faces is shown in Fig. 2b.
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J Mater Sci: Mater Electron
Fig. 1  The temperature dependence of solubility DMM
3 Results and discussions
3.1 Single crystal and powder XRD analysis
A Enraf–Nonius CAD-4 diffractometer with a graphite-
monochromated MoKα radiation (λ = 0.71073 Å) was used
to confirm the accurate cell parameters of the grown crys-
tal at 293(2) K. DMM crystallizes in a monoclinic system
with the space group of P21/n, and the unit cell parameters
are a = 8.394 (8) Å; b = 7.525 (2) Å; c = 17.152 (8) A˚ and
V = 1080.6 (2) Å3, which agreed well with the reported val-
ues [5]. It is worth noting that DMM is a two-dimensional
centrosymmetric crystal, whereupon second harmonic gen-
eration is prohibited, and it obeys the THG.
The crystalline nature and phase purity of the DMM was
analyzed by powder X-Ray diffraction analysis (PXRD).
For this analysis a defect-free single crystal was crushed
into a fine powder, and subjected to analysis by a BRUKER
X-ray diffractometer with CuKα (λ = 1.5406 Å) radiation
and a scan speed of 0.02°/s over a range of 10°–50° and
the obtained diffraction peaks (hkl) values are successfully
indexed by using Powder-X software package. The results
(Fig. 3) show that the XRD peak positions of the simulated
and experimental patterns are in good agreement with each
other.
3.2 CHN analysis
The carbon (C)–hydrogen (H)–nitrogen (N) analysis
was carried out with the powder sample derived from
recrystallized DMM material using a Bruker Biospin AG
CHN elemental analyzer by keeping Helium as a carrier
gas. The theoretically calculated values are found to be
approximately equal to the experimental values (Table 1).
J Mater Sci: Mater Electron

Fig. 2  a A photograph of DMM crystals grown by the slow evaporation method. b Predicted morphology of the grown crystal with plane which
is solved by WinX-morph software

Fig. 3  Simulated and experimental PXRD patterns

Fig. 4  Molecular structure of DMM crystal

Table 1  CHN analysis data
Elements Theoretical amount (%) Experimen-
3.3 Proton NMR (1H NMR) spectral analysis
tal amount
(%) Nuclear magnetic resonance (NMR) spectroscopy is a more
powerful tool than ultraviolet (UV) or infrared (IR) spec-
C 67.26 67.91
troscopy in terms of structural information derived from
H 4.71 4.86
the spectrum. The 1H NMR spectral analysis was made on
N 13.08 13.72
the finely crushed DMM crystal in chloroform-D ­(CDCl3)
with tetramethylsilane (δ = 0 ppm) as an internal standard
using a Bruker NMR spectrometer operating at 400 MHz.
The recorder 1H NMR spectrum provides information
Thus the molecular formula of the DMM compound is about the number of protons present in the DMM mol-
established as C
­ 12H10N2O2. Figure 4 shows the molecular ecule. 1H NMR spectrum of DMM shows six important
structure of DMM molecule. absorption peaks named A, B, C, D, E and F in Fig. 5. They

13

point to the different combination of protons (hydrogen
atoms) present in six different chemical environments in
the DMM molecule. The spectrum for DMM compound
display two singlet signals at 3.905 and 3.911 ppm, which
are assigned to protons of the –OCH3 groups. The sig-
nal at 6.452 ppm and doublet signal at 6.618 ppm were
assigned to aromatic ortho protons, while the doublet sig-
nal at 8.268 ppm belongs to aromatic meta protons and
the singlet signal at 8.171 ppm was assigned to –C=CH
group, which confirm the formation of DMM moiety. In
the NMR spectrum of DMM, the ratio of steps obtained
are A:B:C:D:E:F = 1:1:1:2:2:1. Thus the number of protons
associated with the signals are A—1H, B—3H, C—1H,
D—3H, E and F—1H. The absence of aldehyde is con-
firmed by the absence of a peak between 10 and 12 ppm
in 1H NMR spectrum of DMM, which clearly supports the
formation of a new compound.
3.4 Mass spectrum
The mass spectrum study is carried out for DMM in the mass
range 30–310 amu using a JEOL GCMATE II GC–MS dou-
ble focusing mass spectrometer, and it is shown in Fig. 6.
The crushed samples of DMM have been used for this anal-
ysis. The mass (m) to charge (z) ratio of the sample was
scanned, and the experimental molecular weight 214.17 amu
was found to be in good agreement with theoretical value
214.2 amu. There is no deviation from the proposed molec-
ular weight of the crystalline compound can be attributed
Fig. 5  1H NMR spectrum of
DMM
13
J Mater Sci: Mater Electron
to the absence of fractional impurities in the crystal. The
spectrum showed the molecular ion peak at m/z = 214.17
­(C12H10N2O2), and the other peaks may represent charged
fragments of this ion.
3.5 Optical transmittance study
The transmission spectrum is one of the important fac-
tors in order to identify a potential NLO material. The
UV–Vis–NIR transmission spectrum of DMM crystal with
thickness 1.3 mm was recorded in the wavelength range
from 400 to 1000 nm using a ELICO SL 218 double beam
UV–Vis–NIR spectrometer. From the recorded spectrum,
it is observed that DMM crystal has a high transmittance
of nearly 73–77% up to 1000 nm with lower cut-off wave-
length at 483 nm and is shown in Fig. 7a. Here it is worthy
to mention that, the minimum absorption in entire visible
and near IR region affirms high optical transparency and
wide transmittance range of the grown crystal imperative
for NLO applications.
The absorption co-efficient (α) was determined from the
transmittance (T) using the relation
2.3026 1
( )
𝛼= log (1)
t T
The optical band gap (Eg) was calculated by using the rela-
tion given as follows
(𝛼h𝜈)2 = A Eg − h𝜈 (2)
( )
J Mater Sci: Mater Electron

Fig. 6  Mass spectrum of DMM

where α is linear absorption co-efficient, A is a constant, in Fig. 7b. The optical band gap (Eg) of the crystal was
and hυ is incident photon energy. The Tauc’s graph [7, 8] evaluated by extrapolating the linear part of the graph to the
plotted between (αhν)2 and the photon energy (hν) is shown energy axis and is found to be 2.67 eV.

13

Fig. 7  a Optical transmission spectrum of DEBM single crystal. b
Plots of (αhυ)2 function against photon energy (hυ) with evaluation
of the band gap (Eg) of the material. The value of the Eg of grown
crystal was found to be 2.67 eV
Fig. 8  The PL spectrum of the DMM single crystal exhibits green
emission, and it suggests that it can be used as a new green emitting
material
3.6 Photoluminescence (PL) analysis
PL spectroscopy is one of the nondestructive tools to under-
stand the electronic energy band structure of material. The
PL signal is mainly depend on the density of photoexcited
electrons, the intensity of the incident beam and also change
with excitation position and wavelength. PL spectrum of
grown DMM crystal was recorded at room temperature by
exciting it at 485 nm as shown in Fig. 8. A sharp emis-
sion peak centred at 518 nm was observed in the spectrum
which indicates green emission. This broadening in emission
peak is attributed to the presence of strong intra-molecular
13
J Mater Sci: Mater Electron
molecular interaction present in the DMM crystal. The ICT
from donor to the acceptor gives rise to a large variation of
the dipole moment, which clearly explains the charge trans-
fer interaction between the methoxy (O–CH3) group and
nitrile (C≡N) group through the π-conjugated system. The
π–electron cloud moment from donor to acceptor can make
the molecule highly polarized through (–C=C–) path when it
changes from π–π* transition levels. Moreover, the absence
of any other visible emission peak in the measured region
confirms the good degree of crystallinity and structural per-
fection of grown DMM crystal. This result indicates that
DMM single crystal has a green emission and it suggests
that it can be used as a new green-light emitting material and
also potential candidate for NLO applications.
3.7 Etching analysis
Among various top-down techniques, chemical etching
analysis is one of the most promising methods to analysis
the quality of the grown crystal. Generally, for the fabrica-
tion of NLO devices, we need a good quality crystal. From
the practical viewpoint crystal with defects may destroy the
optical, electrical and mechanical properties, which affect
the usefulness of the crystals. In the present investigation,
the chemical etching was carried out at room temperature
using acetone as an etchant in the plane surface of DMM
crystal. Etching of the crystal surface was carried out by
dipping the crystal in acetone for a few seconds (15, 30,
and 45 s) at room temperature. Then the etched surface was
dried out by gently pressing them between tissue paper and
then their microstructures were immediately examined using
Carl Zeiss optical microscope (magnification of ×50) in the
reflection mode. Figure 9a shows the surface of the as-grown
DMM crystal. Figure 9b shows the pentagon shaped well
defined etch pits were observed on the surface of the crystal
after etching with acetone for 15 s. Figure 9c, d represents
the identical elongated pentagon shaped etch pits on the sur-
face of grown crystal after etched periods for 30 and 45 s,
respectively. It is noticed that the size of etch pits increased
with the increase in the etching times and to the closed look
the appeared pit pattern remains same. The calculated aver-
age dislocation etch pit density was about 1.146 × 103 cm−2,
and this was comparable with many crystals [9–11]. The
etching study suggests that the grown DMM crystal is of
better quality with less dislocation density.
3.8 Thermal studies
In the process of cutting, polishing and laser irradiation,
heat will be generated which may affect the device perfor-
mance of material. From the practical view, to understand
the thermal behaviour of the material is a necessary task.
Thermogravimetric and differential scanning calorimetry
J Mater Sci: Mater Electron
Fig. 9  Micrograph of the
surface of a as grown DMM
crystal; b after 15 s of etching;
c after 30 s of etching; d after
45 s of etching
Fig. 10  TG and DSC analysis of DMM crystal. DMM was stable up
to 139.73 °C, and there was no appreciable weight loss up to this tem-
perature
(TG–DSC) are quite useful tools since they provide reli-
able information’s like thermal stability, melting point and
decomposition of the grown crystal. Thermal studies such
as TG and DSC have been carried out on DMM using a
SDT Q600 V20.9 Build 20 instrument with a heating rate
of 20 °C/min starting from room temperature to 495 °C in a
nitrogen atmosphere. The TG and DSC curve of DMM are
presented in Fig. 10. From the TG analysis, it is clear that
the material is stable up to 139.73 °C and moisture free. A
weight loss was observed between 139.73 and 292.78 °C
(96.55%) in TG curve due to decomposition of the material.
The observed major weight loss is well matched with the
peak observed around 292.78 °C in DSC curve. The DSC
curve implies that first endothermic peak at 145.78 °C which
corresponds to the melting point of the DMM crystal. The
second sharp endothermic peak observed at 292.78 °C is
assigned as the decomposition point. The sharpness of the
endothermic peaks observed in DSC indicates a good degree
of crystallinity of the sample. Another important observation
is that there is no phase transition and decomposition till the
material melts and this aspect ensures the stability of the
material for NLO applications. The DMM crystal has better
thermal stability compared with some of NLO crystals like,
DMMC (94 °C) [12], TMEDA4NP (118.9 °C) [13], U2FA
(120 °C) [14], BHP (130 °C) [15].
3.9 Dielectric measurement
The electrical behaviour of the DMM crystal was stud-
ied over a wide range of frequencies (50 Hz–5 MHz) and
various temperatures (308–348 K) using a HIOKI 3532-50
LCR HITESTER meter. Dielectric constant (εr) is one of
the basic electrical properties of solid materials which pro-
vide information about the atoms, ions and their polariza-
tion (charge displacement) mechanism with in the crystal.
Well-polished crystal (thickness of 1.5 mm) with the clean
surface has been chosen for the present study. High-grade
silver paste was coated on the both the surface of the crys-
tal for ohmic contact, and that was mounted between a pair
13

of electrodes. The dielectric constant (εr) of the crystal is
calculated from the standard relation,
Ct
εr =
Aε0 (3)
where C, t, A, and εo are the capacitance, thickness, area
of the cross section and absolute permittivity in free space
(8.854 × 10−12 F/m) of the DMM crystal respectively. Fig-
ure 11 shows the frequency dependence of dielectric con-
stant (εr) at different temperatures. At lower frequencies,
the dielectric constant of the sample has a maximum value
which decreases with increasing frequency and attains
constant at higher frequencies. A Larger value of εr at low
frequencies may be attributed to space charge polarization
(SCP), which depends on the purity and perfection of the
material [16]. At lower frequencies, accumulation of dipoles
changing the applied electric field and therefore the SCP is
getting strong enough in certain frequency and which results
in a higher εr value. However, with increasing frequency,
dipoles cannot synchronize with the frequency of applied
electric field and undergo relaxation which reduces SCP
and hence εr is also reduced. Material with low εr at higher
frequencies is important for the fabrication of materials for
photonic and electro-optic device applications [17]. Fig-
ure 12 shows the plot of dielectric loss (tanδ) versus applied
frequency. The tan δ also shows similar behaviour as that
for εr. The low dielectric loss value, the crystal may have
enhanced optical quality with lesser defects [18], this param-
eter is of vital importance for NLO applications [19].
Fig. 11  Frequency dependence of dielectric constant (εr) of DMM
crystal at different temperatures
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J Mater Sci: Mater Electron
Fig. 12  Frequency dependence of dielectric loss (tanδ) of DMM
crystal at different temperatures
3.10 Laser‑induced optical damage study
Laser-induced damage is a common phenomenon observed
in the crystals when subjected to high intensities of laser
light. It is clear that the crystal usefulness not only depends
on the linear and NLO properties, but also greatly on its
ability to tolerance of high-intensity laser light [20, 21].
DMM crystal was investigated for multi-shot surface dam-
age (referred as “R on 1” method) [22] for 1064 nm laser
radiation using a frequency conversion of the Nd:YAG laser
of pulse width 10 ns and 10 Hz repetition rate operating in
­TEM00 mode. The fundamental laser light was focused using
a convex lens of focal length of 30 cm. The DMM single
crystal with the thickness of 2 mm is mounted on a crystal
holder and slightly kept away from the focal spot of the beam
in order to avoid any possible damage. The output intensity
of the source was controlled with a variable attenuator and
delivered to the test sample located at the near focusing of
the converging lens. The onset of damage can be confirmed
by visual damage and audible cracking. The energy density
(I) was calculated using the following expression [23],
I = E∕𝜏A GW/cm2 (4)
( )
where E is the input energy required to cause damage (mJ),
τ is the pulse width of the laser beam (ns), and A is the area
of the circular laser spot (mm). The multi-shot and mag-
nified damage profile of the DMM crystal is presented in
Fig. 13: this image reveals the nature of the damage and
its possible origin. The measured multi-shot laser damage
threshold (LDT) value for grown DMM crystal is 1.75 GW/
cm2. The laser damage property is nearly 8.75 times higher
than standard NLO material of potassium dihydrogen phos-
phate (KDP) about 0.20 GW/cm2. Hence the calculated
J Mater Sci: Mater Electron

Fig. 13  Micrograph of the laser-induced damage pattern of DMM

Fig. 14  Self-focusing CA Z-scan spectrum of DMM crystal. The
single crystal
valley to peak transmittance variation as a function of the linear
displacement of the sample along the z-axis shows its self-focusing
effect (SF) with positive nonlinearity (∆n > 0)
Table 2  The comparison of laser damage threshold of DMM crystal
with other NLO crystals

Crystals name Multi-shot LDT value References

(GW/cm2)

KDP 0.20 [24]

BBO 0.35 [20]
4MSTB 1.11 [25]
Urea 1.32 [20]
VMST 1.59 [26]
DMM 1.75 Present work

value is found to be in the higher range compared to a few

known organic and inorganic NLO materials (Table 2).
From the LDT studies, it is concluded that DMM crystal is
a potential material for electro-optic and other optical device
applications.
Fig. 15  OA (reverse saturable absorption) Z-scan spectrum of DMM
3.11 Third‑order NLO property crystal

The THG was tested for DMM crystal using Z-scan technique
2.537 × 10−5 m/W (from OA profile) and third order nonlinear
[27]. The Z-scan experiments were performed using a He–Ne
susceptibility χ(3) is 4.30 × 10−5 esu of DMM crystal [6]. Apart
laser beam of wavelength 632.8 nm which was focused by
from this, based on these data we paid significant attention to
a 30 cm focal length lens. Well-polished DMM crystal of
investigate the some of relative parameters like second-order
0.58 mm thickness is translated from − 15 to 15 mm with Z = 0
molecular hyperpolarizability (γ) and figure of merit (FOM)
at the focus of the lens in order to vary the incident intensity
of the DMM crystal.
falling on the crystal, and the corresponding output normal
The second-order molecular hyperpolarizability (γ) of
transmittance was measured using a detector fed to the digi-
DMM crystal was deduced from third order susceptibility
tal power meter. The closed aperture (CA) and open aperture
(χ(3)) by following equation [28],
(OA) Z-scan trace of DMM crystal is shown in Figs. 14 and 15.
In our previous paper we already reported the calculated value [ ]
[ ] Re χ(3)
positive nonlinear refractive index (­ n2) = 1.876 × 10−11 m2/W Re γ = (5)
(from CA profile), and non-linear absorption coefficient (β) Nf4

13
 J Mater Sci: Mater Electron

Table 3  Obtained NLO parameter from open and CA Z-scan meas- device application, optical limiting purpose, optical data
urement data for DMM crystal processing, optical logic gate, etc [30].
Laser beam wavelength (λ) 632.8 nm
Lens focal length (f) 30 mm
Aperture radius ­(ra) 2 mm 4 Conclusion
Sample thickness (L) 0.58 mm
Effective thickness of the sample (­ Leff) 0.5468 × 10−3 m An organic intramolecular charge transfer (ICT) compound
Nonlinear absorption co-efficient (β) 2.537 × 10−5 m/W of DMM, a bulk size NLO single crystal was successfully
Nonlinear refractive index (­ n2) 1.876 × 10−11 m2/W grown via SESG technique. The single crystal and PXRD
Third-order NLO susceptibility (χ(3)) 4.30 × 10−5 esu studies confirmed centrosymmetric space group (P21/n)
Second order molecular hyperpolarizability (γ) 1.116 × 10−33 esu and crystallinity of the title crystal. The molecular struc-
Number of molecules per unit volume 3.767 × 1027 m−3 ture and molecular weight were confirmed by proton NMR
and GC–mass spectral analysis. High transmittance spec-
trum (from UV), sharp emission spectrum (from PL) in
Table 4  The obtained value of third-order nonlinear susceptibility the visible region, and the low values of dielectric constant
(χ(3)) of DMM crystal compared with some of other NLO crystals and loss were principally authorized that the DMM crystal
acquires better optical prominence with lesser defects. The
Crystals name Third order NLO suscepti- References
bility (χ(3)) TG/DSC studies elucidated that DMM is thermally stable up
to 145.78 °C. The multi shot laser -induced surface damage
DMM 4.30 × 10−5 esu Present work threshold of grown crystal was found to be 1.75 GW/cm2,
EESI 4.22× 10−6 esu [31] which is fairly good compared with other reported crystals.
LAPA 5.24× 10−7 esu [32] The Z-scan measurement confirmed third order NLO activ-
DMAPHB 1.01 × 10−13 esu [33] ity of the desired material. Anyway the outcome of all these
KDP 4.0 × 10−14 esu [34] results substantiated that the ability to grow as bulk size
crystal of good crystalline quality coupled with a superior
THG activity and large optical transparency of DMM crystal
where N is a number of molecule per unit volume, and f make it a promising candidate material for all practical NLO
is the local-field correction factor according to the Lorentz device applications.
expression,
Acknowledgement The authors would like to express the acknowl-
edgement to VIT management for providing financial support and
( 2 )
no + 2
f= (6) excellent research facilities.
3
Ideally, two figure of merit W = n2I/αλ and, T = βλ/n2
have decisive influence to understand the suitability of References
the grown crystal for all-optical switching devices appli-
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I.V. Kityk, P. Bragiel, Field-induced non-linear optical features
W is 3.53 and T factor is 0.85, which staisfied the identi- of p-aminoazobenzene crystals. Eur. Phys. J. Appl. Phys. 42,
cal conditions W ≫ 1 and T ≪ 1. Therefore DMM mate- 263–267 (2008)
rial can be considered to be an excellent candidate to be 2. R. Vaid, M. Gupta, Silica-l-proline: an efficient and recyclable
applied in integrated optics field as all-optical switching heterogeneous catalyst for the Knoevenagel condensation between
aldehydes and malononitrile in liquid phase. Monatshefte fur Che-
devices [29]. The calculated third- order nonlinear param- mie-Chemical Monthly 146, 645–652 (2015)
eters of DMM crystal are given in Table 3. As expected, 3. A. Priyadharshini, S. Kalainathan, Bulk crystal growth, optical,
DMM show large third-order optical nonlinearity, due to electrical, thermal and third order NLO properties of 2-[4-(dieth-
donor–acceptor scheme. Here, nonlinearity is mainly due ylamino) benzylidene] malononitrile (DEBM) single crystal. J.
Phys. Chem. C 121(40), 22384–22395 (2017)
to the ICT from donor to acceptor unit, i.e., due to strong 4. R. Geetha Kumari, V. Ramakrishanan, M. Lydia Caroline, J.
delocalization of π–electrons system. The large value (χ(3)) Kumar, A. Sarua, M. Kuball, Raman spectral investigation of
DMM crystal is systematically compared with standard thiourea complexes. Spectrochim. Acta A 73, 263–267 (2009)
KDP crystal, and some of the other NLO materials tabu- 5. M.Y. Antipin, T.A. Barr, B.H. Cardelino, R.D. Clark, C.E. Moore,
T. Myers, T.V. Timofeeva, X-ray crystal structures, molecular
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