Optical Materials 35 (2013) 1151–1156

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Growth and characterization of ammonium acid phthalate single crystals

A. Arunkumar, P. Ramasamy ⇑
Centre for Crystal Growth, SSN College of Engineering, Kalavakkam 603 110, India

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

Article history: Ammonium acid phthalate (AAP) has been synthesized and single crystals were grown by slow evaporation
Received 21 June 2012 solution growth technique. The unit cell parameters were confirmed by single crystal X-ray diffraction
Received in revised form 24 December 2012 analysis and it belongs to orthorhombic system with the space group of Pcab. The high resolution X-ray
Accepted 2 January 2013
diffraction studies revealed the crystalline perfection of the grown crystal. The various functional groups
Available online 16 February 2013
of AAP were identified by FT-IR and Raman spectral analyses. Thermal stability of the grown crystals
was studied by TGA/DTA. The optical properties of the grown crystals were analyzed by UV–Vis-NIR and
Keywords:
photoluminescence spectral studies. The mechanical property of the grown crystal was studied by Vickers
A. Organic compounds
B. Crystal growth
microhardness measurement. The growth features of AAP were analyzed by chemical etching.
C. Thermo gravimetric analysis Ó 2013 Elsevier B.V. All rights reserved.
C. X-ray diffraction
D. Optical properties

1. Introduction 2. Experimental

In recent years, there has been considerable interest on organic
materials due to their potential applications such as frequency
conversion, optical signal processing, light modulation, optical
switching and logic gates. Organic crystals are especially interesting
because they can offer a highly aligned and stable orientation of
NLO chromophores in the crystal lattice [1–5]. Generally, organic
materials contain donor and acceptor groups positioned at either
end of a suitable conjugation path. Extension of benzene derivatives
has permitted an increase in the number of p electrons as well as their
delocalization length, so as to lead to remarkable enhancement in
hyperpolarizability. Organic molecules have delocalized electrons
which exhibit various photo responses such as photoluminescence,
photoconductive, photovoltaic and photocatalytic behavior [6]. It
has been reported that phthalate based crystals possess high
piezoelectric coefficients with acousto-optical interaction [7,8]. This
feature allows one to use them for data processing and intra laser
modulation in various acousto-optical devices. The organic hydrogen
phthalate crystals are widely known for their application in the long-
wave X-ray spectrometers and their optical, piezoelectric, NLO, and
elastic properties are investigated in detail [9–12]. The phthalate
crystals are often used as diffracting crystals because they are rela-
tively inexpensive, easily cleaved, and sufficiently bendable for a
compact spectrograph. The structure of ammonium acid phthalate
crystal has been reported recently [13]. In the present investigation,
we are reporting the bulk growth, optical, thermal and mechanical
properties of ammonium acid phthalate crystal for the first time.
⇑ Corresponding author. Tel.: +91 9283105760; fax: +91 44 27475166.
E-mail address: ramasamyp@ssn.edu.in (P. Ramasamy).
2.1. Synthesis and crystal growth
The analytical grade of ammonia and phthalic acid were taken
in equimolar ratio and the calculated amount of material was dis-
solved in deionized water with the resistivity of 18.2 MX cm at
room temperature. The reaction mechanism is depicted in Fig. 1.
The recrystallized salt of AAP was taken as the raw material and
the saturated solutions of AAP were prepared at room temperature
using water. The solubility of AAP was measured as a function of
temperature in the range from 25 to 50 °C. From the solubility curve
(Fig. 2), it is observed that AAP has a positive solubility gradient in
water. In accordance with the solubility data, the growth solution
was prepared and filtered off using Whatmann filter paper. The
solution was taken in a beaker and closed with perforated polythene
cover and kept in a dust-free atmosphere. After 25 days of growth, a
good quality and well faceted single crystals were harvested from
the mother solution with the dimension of 12  10  5 mm3. The
grown AAP crystals were harvested when they attained an optimal
size and shape. The grown crystals are optically transparent and
non-hygroscopic. The grown crystal is shown in Fig. 3.
3. Results and discussion
3.1. Single crystal X-ray diffraction studies
The grown crystal was subjected to single crystal X-ray diffrac-
tion study using Bruker Kappa APEXII diffractometer with Mo Ka
radiation with the wavelength of 0.71073 Å. The calculated cell
parameters are a = 6.30 Å, b = 10.07 Å and c = 25.73 Å and it be-

0925-3467/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.optmat.2013.01.001
1152 A. Arunkumar, P. Ramasamy / Optical Materials 35 (2013) 1151–1156

O O

OH OH
NH3
O O

-O
OH
NH4+

Phthalic Acid Ammonia Ammonium Acid Phthalate

Fig. 1. Reaction scheme of AAP.

Fig. 4. The morphology diagram of AAP single crystal.

speed of 1 °/min over a range of 10–70°. The obtained diffraction

Fig. 2. Solubility diagram of AAP. peaks were indexed using ‘TWO THETA’ software package. The in-
dexed powder X-ray diffraction pattern is depicted in Fig. 5.

3.3. HRXRD studies

The crystalline perfection of the grown single crystals was

characterized by HRXRD by employing a multicrystal X-ray
diffractometer developed at NPL [14]. The well-collimated and
monochromated Mo Ka1 beam obtained from the three monochro-
mator Si crystals set in dispersive (+, , ) configuration has been
used as the exploring X-ray beam. The specimen crystal is aligned
in the (+, , , +) configuration. Due to dispersive configuration,

1200
(114)

1000
(131)

Fig. 3. As grown single crystals of ammonium acid phthalate (AAP).

Intensity (counts)

800
longs to orthorhombic system with space group of Pcab. The unit
cell parameters and space group are in good agreement with the 600
reported values [13]. Fig. 4 shows the morphology of AAP crystal
and it was indexed using Enraf Nonius CAD4 diffractometer
400
equipped in the graphite monochromated Mo Ka radiation
(211)
(012)

(113)
(004)

(120)
(021)

k = 0.71073 Å.
(008)

(206)
(043)

200
(110)

3.2. Powder X-ray diffraction

0
10 20 30 40 50
The purity and crystallinity of AAP crystals have been confirmed 2θ (degree)
by recording powder X-ray diffraction pattern using a0 REICH SEIF-
ERT X-ray diffractometer employing Cu Ka (1.54058 Å A) with a scan Fig. 5. Indexed powder X-ray diffraction spectrum of AAP.

though the lattice constant of the monochromator crystal(s) and
the specimen are different, the unwanted dispersion broadening
in the diffraction curve (DC) of the specimen crystal is insignificant.
The specimen can be rotated about the vertical axis, which is per-
pendicular to the plane of diffraction, with minimum angular inter-
val of 0.4 arc s. The rocking or diffraction curves were recorded by
changing the glancing angle (angle between the incident X-ray
beam and the surface of the specimen) around the Bragg diffraction
peak position hB (taken as zero for the sake of convenience) starting
from a suitable arbitrary glancing angle and ending at a glancing
angle after the peak so that all the meaningful scattered intensities
on both sides of the peak are included in the diffraction curve. The
DC was recorded by the so-called x scan wherein the detector was
kept at the same angular position 2hB with wide opening for its slit.
This arrangement is very appropriate to record the short range or-
der scattering caused by the defects or by the scattering from local
Bragg diffractions from agglomerated point defects or due to low
angle and very low angle structural grain boundaries [15]. Before
recording the diffraction curve to remove the non-crystallized sol-
ute atoms which remained on the surface of the crystal and the
possible layers which may sometimes form on the surfaces on
crystals grown by solution methods [16] and also to ensure the
surface planarity, the specimen was first lapped and chemically
etched in a non-preferential etchant of water and acetone mixture
in 1:2 volume ratio. Fig. 6 shows the high-resolution diffraction
curve (DC) recorded for a typical AAP crystal grown by SEST meth-
od using (1 1 4) diffracting planes in symmetrical Bragg geometry
by employing the multicrystal X-ray diffractometer with Mo Ka1
radiation. As seen in the figure, the DC contains a single peak and
indicates that the specimen is free from structural grain bound-
aries. The FWHM (full width at half maximum) of the curve is
15 arc s which is somewhat more than that expected from the
plane wave theory of dynamical X-ray diffraction [17], for an ide-
ally perfect crystal but close to that expected for nearly perfect real
life crystals. This much of broadness with good scattered intensity
along both the wings of the DC indicates that the crystal contains
interstitial type of defects [18]. More details may be obtained from
the study of high-resolution diffuse X-ray scattering measure-
ments [14], which is not the main focus of the present
investigation.
3.4. FTIR and laser Raman studies
Fig. 7 shows the FTIR spectrum of AAP recorded employing a
Perkin–Elmer lambda 32 using KBr pellet technique in the range
of 4000–400 cm1. The broadening of peaks in higher wavenumber
AAP(114) Plane
4500
MoKα1 (+,−,−,+)
Diffracted X-ray intensity [c/sec]
3000
1500
0
-100 -50
Glancing angle [arc sec]
Fig. 6. High resolution X-ray diffraction curve of AAP.
A. Arunkumar, P. Ramasamy / Optical Materials 35 (2013) 1151–1156 1153
region is due to the combination of COOH, NH and OH stretching
vibrations. The peaks at 2900 and 1609 cm1 are due to aromatic
CAH and COO stretching vibrations. The NAH deformation mode
occurs at 1406 cm1, CAO stretching in 1386 cm1 and NH2 torsion
in 1115 cm1 are clearly observed. The absorption band at
895 cm1 is assigned to the aromatic CAH bending vibration. The
Raman spectra were measured using a WiTec GmbH confocal
microRaman using the excitation wavelength of 532 nm as shown
in Fig. 8. The band at 3078 cm1 is due to NAH summation band.
The peaks at 1723 cm1 and 1603 cm1 are due to C@O and COO
stretching vibrations respectively. The peak at 1603 cm1 confirms
the origin of COO stretching both from IR and Raman. The peak at
1505 cm1 indicates the aromatic stretching. The torsional oscilla-
tion of NH occurs at 1050 cm1. It clearly shows the aromatic out
of plane bending at 811 cm1.
3.5. UV–Vis-NIR spectral studies
The optical transmittance range and transparency cut-off wave-
length are the main requirements for device applications [19]. The
transparent behavior of AAP crystal was measured using the Per-
kin–Elmer lambda 35 spectrophotometer and the entire UV–Vis-
NIR spectrum is shown in Fig. 9. A crystal with the thickness of
2 mm without polishing and antireflection coating is used for the
measurement. The lower cut off wavelength of AAP is around
300 nm and it has sufficient transmittance in the entire visible
and NIR regions. It may be noted that the ammonium contained
phthalate (AAP) crystal may possess the substantial contribution
of the phonon subsystem [20]. The absence of absorption in the re-
gion between 300 and 1100 nm shows that the crystal can be used
for optical window applications.
The dependence of optical absorption coefficient with the pho-
ton energy helps to study the band structure and the type of tran-
sition of the electron. The absorption coefficient (a) and the optical
parameters such as refractive index (n), reflectance (R) and extinc-
tion coefficient (K) have been determined from the transmission
(T) spectrum based on the following relations:
2:3026
a¼ logð1=TÞ ð1Þ
t
where T is the transmittance and ‘t’ is the thickness of the crystal.
The absorption coefficient ‘a’ is related to the extinction coeffi-
cient K by:
15"
0 50 100
Fig. 7. FT-IR spectrum of AAP.
1154 A. Arunkumar, P. Ramasamy / Optical Materials 35 (2013) 1151–1156

Fig. 8. Raman spectrum of AAP crystal.

ak Fig. 11. TG/DTA curve of AAP crystal.

K¼ ð2Þ
4p
The reflectance (R) in terms of the absorption coefficient and
refractive index (n) can be derived from the relations: 120

qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
expðatÞ  ðatÞT  expð3atÞT þ expð2atÞT 2 Hardness Number Hv (Kg/mm2) 100
R¼ ð3Þ
expðatÞ þ expð2atÞT

pffiffiffi 80
ðR þ 1Þ  2 R
n¼ ð4Þ
ðR  1Þ
60
In the high photon energy region, the energy dependence of
absorption coefficient suggests the occurrence of direct band gap
of the crystal obeying the following equation for high photon ener- 40
gies (hm).

20
ðahmÞ2 ¼ AðEg  hmÞ ð5Þ

where Eg is the optical band gap of the crystal and A is a constant. 0

The variation of (ahm)1/2 with hm in the fundamental absorption re- 0 10 20 30 40 50
gion is plotted in Fig. 9b. The band gap of the crystal was evaluated Load P (gm)
by extrapolation of the linear part of the graph and found to be
Fig. 12. Load (P) vs. hardness number (Hv) of AAP single crystal.
4.1 eV. The wide band gap of the AAP crystals confirms the large
transmittance in the visible region. Fig. 9c and d represents the var-
iation of reflectance and extinction coefficient with respect to pho-
ton energy (n = 1.538 at 1100 nm) respectively. Fig. 9e represents 2.2
the variation of refractive index with wavelength.
From the optical constants, the electric susceptibility vc can be
2.0
calculated according to the relation [21]:

e0 þ 4pvc 1.8
er ¼ ¼ n2  K 2 ð6Þ
4p
Log D

1.6
ðn2  K 2  e0 Þ
vc ¼ ð7Þ
4p
1.4
where e0 is the dielectric constant in the absence of any contribu-
tion from free carriers. The value of electric susceptibility vc is 1.2
0.188 at 1100 nm.
The real and imaginary dielectric constants er and ei can be cal-
culated from the following relations [22]: 1.0

er ¼ n2  K 2 and ei ¼ 2nK ð8Þ 0.0 0.5 1.0 1.5 2.0

Log P
The value of real er and imaginary ei dielectric constants at
1100 nm are 2.36 and 5.4  103 respectively. Fig. 13. Plot of log P vs. log d.
 A. Arunkumar, P. Ramasamy / Optical Materials 35 (2013) 1151–1156
3.6. Photoluminescence (PL) studies
Photoluminescence (PL) measurement is a prominent tool for
determining the crystalline quality of a system as well as its exci-
ton fine structure [23]. The photoluminescence spectra were mea-
sured with a Nanolog HORIBA JOBINYVON spectrofluorometer
with a 100 W xenon lamp as the excitation source at a scan speed
of 240 nm/s. The band-pass for both excitation and emission
monochromators was kept at 5 nm. The sample is excited at wave-
length of 350 nm. The recorded PL spectrum is shown in Fig. 10.
The strong and sharp emission peak with kmax = 635 nm corre-
sponds to red emission centered at 1.95 eV. This red emission is
due to the presence of interstitial type of defects in the crystal.
Thus the crystals can be used in laser diode applications [24].
3.7. Thermal studies
The thermal stability of AAP was studied by thermogravimetric
(TG) and differential thermal analyses (DTA) using NETZSCH STA
409/CD TG/DTA instrument. A powder sample weighing 14.20 mg
was used and an alumina crucible was used for heating the sample.
This study was carried out in a nitrogen atmosphere at a heating
rate of 10 °C/min over the temperature range of 27–1000 °C. From
the TG curve, it is evident that the material is stable up to 185 °C.
The TG curve shows two stage weight loss patterns. The first major
weight loss occurred between the temperatures 186 and 222 °C
with 40%, this weight loss may be due to loss of ammonia and car-
bon monoxide. The second stage weight loss noticed between the
temperatures 222 and 265 °C experiences a weight loss of about
60% with complete decomposition of phthalic acid. From the ther-
mal study Fig. 11, it is concluded that the crystal is thermally stable
up to 185 °C and it could be exploited for any suitable applications
up to this temperature.
3.8. Microhardness
The good quality single crystals are very much needed for de-
vice fabrication with good mechanical strength. In order to study
(a) 1sec
(c) 6 sec
Fig. 14. Etching time of AAP single crystal on (0 0 1) face with water as an etchant (a) 1 s, (b) 3 s, (c) 6 s and (d) 9 s.
1155
the mechanical property, the Vickers microhardness measurement
was carried out on the grown crystals. Microhardness studies were
carried out at room temperature on (0 0 1) plane using MATSUZA-
WA model MMT-X series microhardness tester fitted with a Vick-
ers diamond pyramidal indenter with a dwell time of 5 s. The
diagonal length of the indentation impression was measured using
a microscope. The indentation marks were made on the surfaces by
varying the load from 1 to 50 g. The microhardness value was cal-
culated by using formula:
2
Hm ¼ 1:8544 P=d kg=mm2 ;
where Hv is the Vickers hardness number, P is the applied load and d
is the diagonal length of the indentation. Fig. 12 shows the variation
of hardness number (Hv) as a function of applied load ranging from
1 to 50 g for AAP crystal. It is very clear from the figure that hard-
ness number (Hv) increases with the increase of load and the cracks
have been observed beyond 25 g for AAP. It may be due to the inter-
nal stress released. In order to calculate the value of work hardening
coefficient n, a graph is plotted of log P vs. log d and is shown in
Fig. 13. The slope of this line gives the value of ‘n’. The work hard-
ening coefficient (n) for AAP is found to be 1.9. According to Onitsch
[25], n should lie between 1 and 1.6 for harder materials and above
1.6 for softer materials. Hence, AAP crystal belongs to softer mate-
rial category.
3.9. Etching studies
Etching is the selective dissolution of the crystal which reveals
the crystal symmetry and lattice defects [26]. The patterns ob-
served on surface like spirals, hillocks and step pattern, yield con-
siderable information on the growth process and growth
mechanism of the crystal. When a surface is etched, well defined
etch patterns are produced at the dislocation sites. The shape
and orientation of the pits can be related to crystal symmetry.
The etching experiment was carried out on (0 0 1) plane using
water as an etchant at room temperature for 1 to 10 s. The dis-
torted rectangular type of etch pits were observed for 1 s.
Fig. 14a–d illustrates the successive stages of the development of
(b) 3 sec
(d) 9 sec
1156 A. Arunkumar, P. Ramasamy / Optical Materials 35 (2013) 1151–1156
etch pits of AAP crystal and the etch patterns were observed using
optical microscope (Olympus U-TV0.5XC-3, Japan) in the reflection
mode. The resulting etch patterns are the characteristic distribu-
tion of defects in the sample. It has been observed that AAP crystal
has two dimensional growth mechanisms with the increasing size
of the pattern with increase in etching time. Further, the patterns
obtained were quite stable and did not degrade for several days.
4. Conclusion
Good optical quality single crystals of organic ammonium acid
phthalate (AAP) were grown by slow solvent evaporation tech-
nique. The unit cell parameters of the grown sample were con-
firmed by single crystal X-ray diffraction analysis. The crystalline
perfection of the crystal was confirmed by high resolution X-ray
diffraction and found to be reasonably good. Functional groups
present in the grown crystal were confirmed by FTIR and Raman
spectral studies. The optical behavior has been evaluated by UV–
Vis-NIR and photoluminescence analysis and it substantiates the
suitability for opto-electronic applications. Thermal studies re-
vealed that AAP is thermally stable up to 185 °C. Microhardness
measurements showed that the AAP comes under the soft materi-
als category. The distorted rectangular etch patterns are observed
in etching studies.
Acknowledgments
The authors are thankful to Dr. G. Bhagavannarayana, National
Physical Laboratory, New Delhi for HRXRD studies, Dr. R. Gopala-
krishnan, Anna University, Chennai for providing microhardness
studies, SAIF, IIT Madras for providing single crystal X-ray diffrac-
tion studies and TG/DTA studies.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.optmat.2013.01.001.
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