Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

journal homepage: www.elsevier.com/locate/matpr

Synthesis, crystal growth and characterizations of 4-fluorobenzyl

ammonium dihydrogen phosphate of NLO single crystal [PFBADP]
V. Manivannan a, N. Bhadhusha a, T. Gunasekaren a, C. Inmozhi b, M. Subash c, R. Uthrakumar c,⇑
a
Department of Chemistry, Govt. Arts College (A), Salem 636 007, Tamil Nadu, India
b
Department of Physics, Govt. Arts College for Women, Salem 636 008, Tamil Nadu, India
c
Department of Physics, Govt. Arts College (A), Salem 636 007, Tamil Nadu, India

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

Article history: Good quality single crystal of p-fluorobenzyl ammonium dihydrogen phosphate [PFBADP], a compound
Received 21 July 2020 has been successfully grown from aqueous solution by slow evaporation solution growth method. The
Received in revised form 16 August 2020 crystal system and lattice parameters are confirmed by the single crystal X-Ray diffraction analysis. An
Accepted 19 August 2020
optical absorption study on the sample shows that the material is well suitable for optical applications.
Available online xxxx
The functional groups of the compound are confirmed qualitatively by FT-IR spectral analysis. The pho-
toluminescence studies indicate that the grown crystals have a green fluorescence emission. Dielectric
Keywords:
studies have been carried out for the grown crystal and the results were discussed in detail.
Characterization
Crystal Growth
Ó 2020 Elsevier Ltd. All rights reserved.
FTIR Analysis Selection and peer-review under responsibility of the scientific committee of the National Conference on
UV–Visible Analysis Material Science.
XRD
Optical properties and Dielectric constant

1. Introduction tions organic and inorganic components are incorporated together

In recent years, research of inorganic and inorganic materials
have attracted many researchers due to its high nonlinear, ultrafast
response in electro optic effect, large optical susceptibilities, large
second order molecular polarizability, and higher resistance to
optical damage and they have wide applications in optical commu-
nications, frequency mixing, optical parameter oscillation, infor-
mation storage [1–3]. These crystals with aromatic ring have
been the foci of infinite scientific interest attracting much attention
because of their high non linearity, fast response and tailor made
flexibility [4–8]. A new type of hybrid NLO material has been
explored from organic and inorganic complexes named semi
organic [9]. Organic nonlinear materials are often formed by weak
vander Waals and hydrogen bond and hence possess high degree of
delocalization. Organic materials are molecular materials those
after unique opportunities for fundamental research as well as
for technological application [10]. Organic crystals with large order
nonlinear optical susceptibilities appeal great interest because of
their potential application in SHG [11]. In the present investiga-
⇑ Corresponding author.
E-mail address: uthraloyola@yahoo.com (R. Uthrakumar).
through strong chemical covalent or iono-covalent bonds. In par-
ticular hybrid system derivatives from orthophosphoric acid are
often associated with functionalized organic molecules to produce
organic–inorganic materials with potentially forceful hydrogen-
bonding interactions between donor and acceptor components.
The grown crystal was subjected to single crystal characterization
such as single crystal X-ray diffraction studies, UV–Visible, FTIR
and Photoluminescence spectroscopy analysis to confirm enhance-
ment of optical property and to identify the improvement in diver-
sified properties of the crystals.
2. Experimental
The title compound was obtained by slow evaporation method
from a saturated aqueous solution containing 4-flourobenzyl
amine and phosphoric acid in the 1:1 M ratio. Repeated recrystal-
lization process was employed so as to improve the purity of the
solution and prepared seed crystals were just immersed into the
purified solution. Good quality crystals with the size of
12
5
2 mm3 are obtained with in a period of 15 days, the
grown single crystal is as shown in the Fig. 1.

https://doi.org/10.1016/j.matpr.2020.08.697
2214-7853/Ó 2020 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the National Conference on Material Science.

Please cite this article as: V. Manivannan, N. Bhadhusha, T. Gunasekaren et al., Synthesis, crystal growth and characterizations of 4-fluorobenzyl ammo-
nium dihydrogen phosphate of NLO single crystal [PFBADP], Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.08.697
V. Manivannan, N. Bhadhusha, T. Gunasekaren et al.
Fig. 1. Photograph of the grown PFBADP single crystal.
3. Results and discussion
3.1. Single crystal XRD studies
The grown single crystal of PFBADP subjected to single crystal
X-ray diffraction analysis for the grown crystals have been carried
out to confirm the crystalline and also to identify the lattice param-
eters using an Bruker Kappa APEX-2 diffractometer with MoKa
(k = 0.71073 Å) radiation X-ray diffract meter. From this analysis,
it was confirmed that the grown crystals belongs to orthorhombic
system with space group Pbcn. The cell parameters are
a = 7.1627 Å, b = 9.1310 Å, c = 29.694 Å, a = b = c = 90°. The XRD
data of the grown crystal are well matched with reported literature
[12].
3.2. UV–Vis NIR spectral studies
To determine the transmission range and hence to know the
suitability of PFBADP single crystals for optical applications, UV–
Vis-NIR analysis was made in the wavelength range from 200 to
800 nm using Shimadzu model UV-1061 UV–Vis spectrometer.
The plot of absorption against wavelength is shown in Fig. 2. For
optical fabrications, the crystal should be highly transparent in
the considerable region of wavelength [10]. The UV absorption
edge for the grown crystal was observed to be around 430 nm
and is an essential parameter for frequency doubling process using
diode and solid-state lasers [13] and the less absorption in the
entire visible region shows the crystalline nature of the product.
Fig. 2. UV–Visible spectrum of title material.
2
Materials Today: Proceedings xxx (xxxx) xxx
3.3. FT-IR spectral analysis
Infrared spectroscopy is used to identify the functional groups
and modes of vibration of the synthesized compound (Fig. 3).
The absorption of IR radiation causes the various bonds in a mole-
cule to stretch and bend with respect to one another. The most
important range (3500 – 500 cm1) is of prime importance of
organic and inorganic compound by spectral analysis [14]. The
medium peak is due to asymmetric bending of NH+3 (1590 cm1)
and also strong peak is symmetrical bending of NH+3 [15]. The peak
observed at 3077 cm1, 2875 cm1 and 2638 cm1 corresponding
to aromatic C–H stretching and N–H stretching. C–H, N–H and
bending vibration modes shows absorption peaks at 2339 cm1,
2109 cm1 1993 cm1 and 1713 cm1 are respectively. C = C ,N–
H,C-N and C-Fl stretching vibration modes shows absorption peaks
at 1623 cm1 to 515 cm1 are respectively.
3.4. Photoluminescence (PL) spectroscopy
The PL emission spectrum provides information concerning the
point defect nature of the crystal. Observation of near-bandedge
emission provides approximate determination of the band gap
energy (Eg) and thus the composition. The photoluminescence
spectrum was recorded using JOBIN YVON FLUROLOG-3–11 Spec-
tro flurometer at room temperature. Photoluminescence in solids
is the phenomenon in which electronic states of solids are excited
by light of particular energy and the excitation energy is released
as light Photons produced as a result of the various recombinations
of electrons and holes are emitted from the sample surface and it is
the resulting photon emission spectrum that is studied in photolu-
minescence (PL). From the luminescence spectrum (Fig. 4) of
PFBADP, the emission of green band at 340 nm and 400 nm is
assigned to an extremely rapid excited-state intramolecular proton
transfer (ESIPT) with hydrogen bonding [16].
3.5. Dielectric studies
Hence, the grown crystal PFBADP of (2
0.6
0.5) mm3 dimen-
sion was subjected to dielectric studies using HIOKI 3532–50 LCR
HITESTER. The experiment was carried out at constant tempera-
ture (35 °C) for frequencies from 100 Hz to 5 MHz. The dielectric
constant (e) is calculated using the relation,
Cd
e¼ ð1Þ
Ae0
e0 ¼ etand ð2Þ
Fig. 3. FTIR spectrum of grown crystal.
V. Manivannan, N. Bhadhusha, T. Gunasekaren et al. Materials Today: Proceedings xxx (xxxx) xxx

the space charge polarization. The dielectric loss is also studied as

a function of frequency at constant temperature is shown in
Fig. 6. These curves suggest that the dielectric loss strongly depends
on the frequency of the applied field, similar to that of dielectric
constant, which is common in the ionic system. A good insight into
the electric field distribution within crystalline materials can be
gained by an investigation of their dielectric property. The permit-
tivity of the material can greatly vary in magnitude with variation
in their structural properties. Through the study of dielectric con-
stant (e) as a function of frequency (f), d.c bias and temperature
etc, the different polarization mechanisms in solid such as atomic,
ionic, electric, space-charge, and orientation polarization can be
understood easily. The very high value of dielectric constant (e) at
low frequencies is attributed to space charge polarization. The
low values of dielectric constant (e) at higher frequencies are
important for the fabrication of material towards ferroelectric, pho-
tonic and electro-optic devices [17–20]. The characteristic of low
dielectric loss with higher frequency of the sample suggests that
Fig. 4. PL Spectrum of grown PFBADP single crystal.
the crystal growth process enhances optical quality with fewer
defects.

4. Conclusions

Single crystals of PFBADP were successfully grown from aque-

ous solution by slow evaporation technique at room temperature.
X-ray diffraction analysis showed that the crystal belongs to the
orthorhombic crystal system with space group Pbcn. Optical
absorption studies shows that p-fluorobenzyl ammonium dihydro-
gen phosphate is optically transparent in the entire visible region
with a lower cut-off below 300 nm. FTIR analysis confirmed the
functional groups present in the title compound. The PL emission
is also more advantageous due to cross relaxation energy transfer
phenomenon”. The characteristic of low dielectric loss with higher
frequency of the sample suggests that the crystal growth process
enhances optical quality with fewer defects. From the above con-
clusions, the synthesised material could be a potential candidate
for NLO applications.
Fig. 5. Dielectric constante versus log frequency (f).
CRediT authorship contribution statement

where, ‘C’ is the capacitance, ‘d’ is the thickness and ‘A’ is the area of
V. Manivannan: Writing - original draft, Writing - review &
cross section of the grown crystal. The plot of dielectric constant (e)
editing. N. Bhadhusha: Validation, Visualization, Writing - review
versus frequency (f) at constant temperature is shown in Fig. 5. The
& editing. T. Gunasekaren: Data curation, Writing - review & edit-
dielectric constant has higher value 380 in the lower frequency
ing. C. Inmozhi: Writing - review & editing, Visualization. M. Sub-
region and then it decreases to 90 with higher frequency. The
ash: Data curation, Writing - review & editing. R. Uthrakumar:
increase in dielectric constant at low frequency is attributed to
Writing - original draft, Investigation, Methodology, Supervision,
Data curation.

Declaration of Competing Interest

The authors declare that they have no known competing finan-

cial interests or personal relationships that could have appeared
to influence the work reported in this paper.

References

[1] Cong Zhang, Zhen Li, Hengjiang Cong, Jiyang Wang, Huaijin Zhang, R.I.
Boughton, J. Alloys Compd. 507 (2010) 335-340.
[2] M.J. Rosker, P. Cunningham, M.D. Ewbank, H.O. Marcy, F.R. Vachss, L.F. Warren,
R. Gappinger, R. Borwick, P. Appl, Opt. 5 (1996) 667.
[3] K. Selvaraju, R. Valluvan, K. Kirubavathi, S. Kumararaman, Opt. Commun. 269
(2007) 230.
[4] S. Gao, W. Chen, G. Wang, J. Chen, J. Cryst. Growth 297 (2006) 361.
[5] A. Pricilla Jeyakumari, J. Ramajothi, S. Dhanuskodi, J. Cryst. Growth 269 (2004)
558.
[6] H.Q. Sun, D.R. Yuan, X.Q. Wang, X.F. Cheng, C.R. Gong, M. Zhou, H.Y. Xu, X.C.
Fig. 6. Dielectric loss versus log frequency (f). Wei, C.N. Luan, D.Y. Pan, Z.F. Li, X.Z. Shi, Cryst. Res. Technol. 40 (2005) 882.

3
V. Manivannan, N. Bhadhusha, T. Gunasekaren et al. Materials Today: Proceedings xxx (xxxx) xxx

[7] P.M. Ushasree, R. Muralidharan, R. Jayavel, P. Ramasamy, J. Cryst. Growth 218
(2000) 365.
[8] C. Justin Raj, S. Krishnan, S. Dinakaran, R. Uthrakumar, S. Jerome Das, Cryst. Res.
Technol. 43 (2008) 245–247.
[9] R. Uthrakumar, C. Vesta, C. Justin Raj, S. Dinakaran, R.C. Dhas, S. Jerome Das,
Cryst. Res. Technol. 43 (2008) 428.
[10] A. Jonie Varjula, C. Vesta, C. Justin Raj, S. Dinakaran, A. Ramanand, S. Jerome
Das, Materials Letters 61 (2007) 5053–5055.
[11] T. Suzuki, Y. Arai, Y. Ohishi, J. Lumin. 128 (2008) 603.
[12] Ali Rayes, Ahlem Dadi, Najla Mahbouli Rhouma, Francesco Mezzadric and
Gianluca Calestani, Acta Cryst. E72 (2016) 1812-1815.
[13] S. Sahaya Jude Dhas, S. Jerome Das, Arab. J. Chem. 10 (2017) 854–858.
[14] J. Tauc, Grigorovici, A. Vancu, Phys. Status Solidi (b) 15 (1966) 627.
[15] C. Justin Raj, S. Dinakaran, S. Krishnan, B. Milton Boaz, R. Robert, S. Jerome Das,
Opt. Com. 281 (2008) 2285.
[16] V. Venkataramanan, S. Maheswaran, J.N. Sherwood, H.L. Bhat, J. Cryst. Growth
179 (1997) 605.
[17] R. Uthrakumar, C. Vesta, M. Jose, K. Sugandhi, S. Krishnan, S. Jerome Das,
Physica B 405 (2010) 3371–3375.
[18] R. Uthrakumar, C. Vesta, R. Robert, G. Mangalam, S. Jerome Das, Physica B 405
(2010) 4274–4278.
[19] R. Uthrakumar, C. Vesta, C. Justin Raj, S. Krishnan, S. Jerome Das, Curr. Appl.
Phys. 10 (2010) 548.
[20] C. Justin Raj, S. Krishnan, M. Navis Priya, R. Uthrakumar, S. Jerome Das, Cryst.
Growth Des. 8 (2008) 2729.