Arabian Journal of Chemistry (2017) xxx, xxx–xxx

King Saud University

Arabian Journal of Chemistry

[Link]
[Link]

ORIGINAL ARTICLE

Optical, piezoelectric and mechanical properties of

xylenol orange doped ADP single crystals for NLO
applications
Sahil Goel a, Nidhi Sinha b, Harsh Yadav a, Abhilash J. Joseph a, Abid Hussain a,
Binay Kumar a,*

a
Crystal Lab, Department of Physics & Astrophysics, University of Delhi, Delhi 110007, India
b
Department of Electronics, SGTB Khalsa College, University of Delhi, Delhi 110007, India

Received 14 December 2016; accepted 12 March 2017

KEYWORDS Abstract Single crystals of pure and xylenol orange (XO; C31H32N2O13S) dye doped (0.01, 0.05
Nonlinear optical materials; and 0.1 mol%) ammonium dihydrogen phosphate (ADP; NH4H2PO4) were grown by slow evapo-
Dye-doped crystals; ration method with the vision to improve the properties of pure ammonium dihydrogen phosphate
Optical properties; crystal. The theoretical morphology of the grown crystals was drawn using Bravais–Friedel–Don
Piezoelectricity; nay–Harker (BFDH) law. The selective nature of xylenol orange dye to selectively stain the partic-
Mechanical properties ular growth sectors of ADP crystal was studied. The structural analysis of as grown crystals was
carried out using powder XRD study. The identification of the functional groups present in the
ADP material was done using Fourier transform infrared (FTIR) spectroscopy. The linear optical
study on pure and dye doped crystals was carried out using UV–vis–NIR spectroscopy. The optical
band gap, extinction coefficient, refractive index and optical conductivity were calculated using the
transmittance spectra for all the samples. In photoluminescence studies, the blue emission intensity
got quenched and an orange emission at 597 nm was seen as a result of XO doping. The thermal
stability and decomposition temperature of ADP crystal were found to decrease as an effect of
dye doping. The piezoelectric charge coefficient, SHG conversion efficiency, mechanical strength
and wettability were also enhanced as a result of XO dye doping.
Ó 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license ([Link]

1. Introduction

* Corresponding author.
In recent years, the need for fast data retrieving, amplifying, modulat-
E-mail address: b3kumar69@[Link] (B. Kumar). ing, transforming and transmitting a signal by optical techniques has
Peer review under responsibility of King Saud University. inspired many researchers to grow new nonlinear optical (NLO) mate-
rials with exceptionally high optical transparency in the ultraviolet to
near IR spectral range (Nie, 1993; Nitti et al., 1993). The NLO active
materials extend the applications of the lasers, which include second
Production and hosting by Elsevier harmonic generation (SHG), mode-locking and Q-switching (Nie,

[Link]
1878-5352 Ó 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license ([Link]
Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
2 S. Goel et al.

1993; Nitti et al., 1993; Garmire, 2013). The crystals have been coworkers have grown large size distyrylbenzene crystals doped with
observed to exhibit optical nonlinearities at a wavelength from infrared tetracene and pentacene for light emitting diodes, transistors and
to UV and also used to generate THz radiation (Garmire, 2013). The electrically pumped laser applications (Wang et al., 2009).
ammonium dihydrogen phosphate (NH4H2PO4; ADP) and potassium The electrostatic potential, degree of protonation, crystal surface
dihydrogen phosphate (KH2PO4; KDP) crystals find their application conditions, and steric exclusion of the dye molecules play an important
in optical storage devices, in modern optoelectronics and as monochro- role for the inclusions of dyes in the crystal planes (Kahr and
mators for X-ray fluorescence analysis (Ren et al., 2008; Xu and Xue, Shtukenberg, 2016). The striking pattern of the dye molecules on the
2006). Such excellent applications of ADP and KDP crystals encour- crystal plane is because of the anisotropic effect of the crystal faces
age the researchers to grow large plates of these crystals for the fabri- (Lovell et al., 1999). Pritula et al. have observed that the xylenol
cation of electro-optic switches and frequency convertors. Many orange dye inclusion takes place in prismatic {1 0 0} growth sectors
reasonable studies have been reported by researchers on pure KDP of KDP crystals (Pritula et al., 2009). The physical and optical proper-
and ADP crystals (Xu and Xue, 2006; Yokotani et al., 1986; Takubo ties of the CV-doped KDP crystals got enhanced along with higher
and Makita, 1989; Reintjes and Eckardt, 1977). The unremitting inter- crystalline perfection in comparison with pure KDP (Rajesh et al.,
est shown by researchers to ADP and KDP crystals is due to their 2014). The SHG efficiency of KDP single crystal got enhanced by
unique low temperature antiferroelectric, piezoelectric, NLO and dye doping such as methyl orange, Rhodamine B, amaranth, and xyle-
electro-optic properties. nol orange (Pritula et al., 2009; Kumaresan et al., 2008). High trans-
The orientational dependences of piezoelectric charge coefficients mittance, more efficient luminescence, large dielectric constant and
and SHG conversion efficiency depend on the anisotropy of the crystal good laser stability were demonstrated for CV dye doped potassium
(Aleshin and Raevski, 2013; Sapaev et al., 2003). The mechanical hard- acid phthalate crystal (Rao et al., 2016). In our previous paper (Goel
ness of ADP crystal is anisotropic in nature (Anbukumar et al., 1987). et al., 2016), increase in optical transmittance, mechanical strength
In order to search new NLO materials, it becomes necessary to tailor and piezoelectric coefficient was reported as a result of crystal violet
the physical properties of the crystals by addition of suitable dopants dye doping in ADP crystal. In the literature, there is no report avail-
and by introduction of intrinsic defects to optimize their applicability able on xylenol orange (XO) dye doped ADP single crystals. The
for the future aspects. In past, many scientists have carried out an organic crystalline materials have higher optical nonlinearity than
extensive research on the growth and characterizations of large size inorganic materials (Monaco et al., 1987). The inorganic materials pos-
ADP and KDP crystals doped with some inorganic and organic sess high mechanical strength, high thermal stability and poor nonlin-
dopants (Dhanaraj et al., 2008; Hasmuddin et al., 2014; Hudson earity. Keeping this in view, our main aim in the present report was to
et al., 2014; Rajesh et al., 2010, 2013; DuVarney and Kohin, 1968; combine thermal stability and mechanical strength of inorganic ADP
Pritula et al., 2001; Shaikh et al., 2015; Meena and Mahadevan, matrix with high second order nonlinear optical susceptibility and
2008; Bhagavannarayana et al., 2006). chemical flexibility of organic (xylenol orange) dye so that it can be
Xylenol orange (XO; 3,30 -bis[N,N-di(carboxymethyl)aminome successfully employed as a working media for SSDL.
thyl]-o-cresolsulfonephthalein; C31H32N2O13S) is a water-soluble In this work, we have reported the effect of XO dye doping on the
organic dye, which belongs to triphenylmethane (TPM) group. XO structural (powder XRD), spectral (FTIR), optical (UV–vis–NIR, PL),
dye is widely used in analytical chemistry for the spectrophotometric thermal (TG/DTA), piezoelectric, mechanical (Vickers micro-
determination of various metallic ions in aqueous solution, as XO hardness) and nonlinear optical (SHG) properties of the grown ADP
dye forms stable complexes with numerous transition metals crystals. The morphological studies of the pure and XO dye doped
(Gupta, 1974; Vandersteen et al., 2004). Dyeing process is a conve- ADP crystals were examined using BFDH law. The influence of differ-
nient way to introduce the NLO active chromophores in the lattice ent dye concentrations in the solution on the color of doped ADP crys-
of single crystal, which promotes the solid state photonic device tals was investigated and the obtained coloring pattern has been
applications (Pan et al., 1996). As a result of intrinsic polarization, discussed in detail.
high thermal conductivity, anisotropy and less scattering centers pre-
sent in the single crystals, crystal becomes an attractive host matrix 2. Experimental procedure
for dye molecules (Rifani et al., 1995). Dyes lased in liquid phase
(dyes in organic solvent) serve as a perfect solution to avoid dye
destruction. However, liquid dye lasers suffer from major drawbacks
2.1. Crystal growth and solubility
such as inconveniency in disposal of large organic liquid solutions,
technical complexities in handling, cleaning and maintaining bulky The commercially available (Merck; AR grade) xylenol orange
cells (Costela et al., 2013). These problems can be taken care of by (XO) dye and ammonium dihydrogen phosphate (ADP) salt
designing compact and easy to handle solid matrices based dye laser were used for crystal growth. A clean beaker was filled with
devices. Over the past years, great enhancements in the efficiency of
50 ml of double distilled water (18.2 MX cm resistivity) and
SSDL have been achieved as a result of organic dye inclusion in var-
measured quantity of the ADP and XO dye (0.0 mol%,
ious solid matrixes (Mauri and Moret, 2000; Yariv et al., 2001;
Ashwell et al., 1995). Organic dye incorporated into the host matrix 0.01 mol%, 0.05 mol% and 0.1 mol%) was added till super-
of alumina gels, xerogels, silica gels and organic polymers was being saturation for different temperatures. The solubility curves of
used as laser gain media for solid state dye laser (SSDL) devices pure and XO dye doped ADP in the temperature range 35–
(Hermes et al., 1993; Amat-Guerri et al., 1993; Reisfeld et al., 70 °C in steps of 5 °C are illustrated in Fig. 1. The solubility
1997; Yariv and Reisfeld, 1999). However, the dye inclusion into of XO doped ADP got slightly increased in comparison with
the polymer host leads to thermal degradation of dye (Costela pure ADP. Similar results were observed by Rajesh et al. for
et al., 2013). Thus, the inorganic crystals doped with organic dye CV doped KDP (Rajesh et al., 2014).
can serve as a promising alternative material for laser working media The homogenous solution of pure ADP was prepared by
because of their reduced scattering, intrinsic polarization and high
dissolving 25 g of ammonium dihydrogen phosphate in 50 ml
thermal stability (Benedict et al., 2003). Dye molecules in doped
of double distilled water at 35 °C. The above prepared solution
crystal provide an alluring option for solid state laser gain media
(Kahr and Shtukenberg, 2016). Electrically pumped laser devices was stirred continuously for 1 day using a magnetic stirrer to
based on dye doped organic crystals were found to be more efficient obtain a homogenous and transparent solution. The homoge-
due to tunably high luminescence and high mobility characteristics of nous solution was filtered using micro pore filter paper and
dye doped crystals (Kuehne and Gather, 2016). H. Wang and his was kept for evaporation in a clean beaker. Now a perforated

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
Xylenol orange doped ADP single crystal 3

et al., 2016a,b). Fig. 2 displays the photograph of as grown

pure and XO dye doped ADP crystals.

2.2. Morphological studies and distribution of dye in different

crystallographic planes

The theoretical modeling of the crystal morphology is impor-

tant for efficient device applications. In the case of pharmaceu-
tical products, powder density, optimum packing, etc., the
advanced prediction of the crystal morphology is needed.
The accurate prediction of the crystal morphology saves time
and helps to avoid technical troubleshooting of the crystalliza-
tion systems (Yadav et al., 2016a). Due to the anisotropic
response of the crystal planes, the various physical and chem-
ical properties of the crystal vary along different directions
(Liu et al., 1995; Rohl, 2003; Mou et al., 2012). As a result
of different growth rates associated with different crystal
planes, the crystals are found to be developed with a particular
Fig. 1 Solubility curve of pure ADP, 0.01 mol% XO dye doped morphology. On the basis of geometrical interpretation, Bra
ADP (XADP-1), 0.05 mol% XO dye doped ADP (XADP-2) and vais–Friedel–Donnay–Harker (BFDH) law is used to predict
0.1 mol% XO dye doped ADP (XADP-3). the crystal morphology. BFDH law states that the growth rate
of a particular (h k l) plane is inversely proportional to the
interplanar spacing (dhkl) (Docherty et al., 1991). The growth
aluminum foil paper was used to cover the beaker and the cov- rate (Rhkl) of the (h k l) plane is defined as the growth distance
ered beaker was kept in a constant temperature oil bath for in a unit time interval in a direction normal to the plane. Fig. 3
controlled evaporation at 35 °C (±0.1 °C). Transparent color- displays the simulated indexed morphology of as grown ADP
less pure ADP crystals were collected after a time span of crystal using WinXMorph program (Kaminsky, 2005). Table 1
15 days. For the growth of XO dye doped single crystals, summarizes the growth rate and morphological importance of
0.01, 0.05 and 0.1 mol% of XO dye were added as dopant to different planes of pure ADP crystal. The value of the morpho-
the solution containing 25 g of ADP salt in 50 ml of double logical importance (MI) of {0 1 0} plane is larger than that of
distilled water. The same growth parameters as described {1 0 1} plane, which is in proximity with the experimentally
above were followed to obtain 0.01 mol% (XADP-1), observed morphology.
0.05 mol% (XADP-2) and 0.1 mol% (XADP-3) XO doped The morphology of pure and XO dye doped ADP crystals
ADP crystals. Large size XO doped ADP crystals with good showed no change except the inclusion of dye in various
transparency were obtained from the aqueous solution in a les- growth sectors in the XO-doped ADP crystal. Due to the ani-
ser time of about 12 days. A similar growth enhancing effect sotropy of ADP crystal, the crystal faces of ADP that are not
was also identified due to dye doping in several other single related to one another by symmetry must show different affini-
crystals (Goel et al., 2016; Bhandari et al., 2014; Yadav ties to the XO dye molecules in the solution (Kahr and

Fig. 2 Photograph of as grown pure and XO dye doped ADP single crystals by slow evaporation technique.

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
4 S. Goel et al.

dyeing pattern was observed for CV-doped ADP crystal

(Goel et al., 2016).

2.3. Characterization techniques

Powder X-ray diffraction (XRD) analysis of the pure and XO-

doped ADP crystals was characterized using Bruker D8
Advanced X-ray diffractometer (Cu Ka X-ray source of wave-
length 1.5408 Å). The powdered specimen of pure and XO dye
doped ADP samples was examined for FTIR analysis using
Perkin Elmer FTIR RXI spectrophotometer in the wavelength
range 400–4000 cm1. The optical transmittance spectra of the
pure and dye doped specimens were recorded in the UV–vis–
NIR range of 200–1100 nm using Perkin-Elmer Lambda-35
UV–vis spectrometer. The PL emission spectra of pure and
XO dye doped ADP crystals were characterized using a Varian
Fig. 3 Indexed morphology of as grown ADP crystal. Cary Eclipse fluorescence spectrophotometer. Thermo gravi-
metric analysis was performed using Perkin–Elmer diamond
TG/DTA analyzer in the nitrogen atmosphere at a heating rate
Table 1 Morphological importance of the crystal faces of of 1 °C/min in the temperature range from 30 °C to 330 °C.
ADP crystal from BFDH law. The RT longitudinal piezoelectric charge coefficient (d33) of
Faces (hkl) dhkl Calculated Morphological the grown crystals was measured along [0 1 0] using PM-300
(Å) relative importance Piezometer system by applying a force of 0.25 N with a tap-
growth (M.I.) by ping frequency of 110 Hz. SHG conversion efficiency of the
rates from BFDH law crystal was measured using Kurtz powder technique employ-
BFDH law ing a Nd:YAG laser (k = 1054 nm). The Vickers micro-
(1 0 0), ð
1 0 0Þ 7.484 1.000 1.000 hardness MVH-I tester was used to measure the variation of
(0 1 0), ð0 
1 0Þ 7.484 1.000 1.000 hardness with respect to the applied indenter load for pure
(1 0 1), ð1 0 
1Þ, ð
10 1Þ, ð1 0 1Þ 5.311 1.409 0.709 and XO dye doped ADP crystals.
(0 1 1), ð0 1 1Þ, ð0 1 1Þ, ð0 1 1Þ
  5.311 1.409 0.709
3. Result and discussion

3.1. Powder XRD analysis

Gurney, 2001). Fig. 4(a) depicts the photograph of as grown Grown crystals of pure and doped ADP were crushed and sub-
XO dye doped ADP crystal. From Fig. 4(a) it is clear that jected to powder X-ray diffraction (XRD) analysis in the 2h
the XO dye selectively stains the different growth sectors of range of 20–80° (at R.T.) with Cu Ka radiation of wavelength
ADP single crystal. The incorporation of XO dye into various 1.5405 Å. Fig. 5 depicts the XRD patterns of the pure and dye
crystallographic planes was examined by drawing the mor- doped samples with reflection peaks being well indexed. The
phology of XO-doped ADP crystal using the WinXMorph sharp peaks observed in the XRD data confirm that the grown
program. The morphology and distribution of dye in ADP crystals are of good crystallinity. The least-squares refinement
crystal are shown in Fig. 4(b). It was found that only the of lattice parameters of pure and XO dye doped ADP samples
{1 0 0} growth sectors of ADP crystal were selectively stained to indexed reflections and to determine the best possible space
by the XO dye molecules. Fig. 4(c) shows the fluorescence group was performed using checkcell software (Katrusiak and
from the XO-doped crystal, which confirms the inclusion of McMillan, 2004). The unit cell parameters of ADP crystal
XO dye in the {1 0 0} growth sectors of ADP crystal. Similar match well with standard JCPDS card No. 01-078-2414.

Fig. 4 (a) Photograph of xylenol orange in {1 0 0} growth sectors of ADP. (b) Morphological representation of the dye distribution into
{1 0 0} sectors of ADP. (c) Fluorescence from the same XO-doped ADP crystal.

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
Xylenol orange doped ADP single crystal 5

ADP crystals in the mid infrared range (400–4000 cm1) are

illustrated in Fig. 6.
The observed FTIR spectrum matches well with the earlier
works reported in the literature (Dhanaraj et al., 2008; Shaikh
et al., 2015), which confirms the presence of different func-
tional groups in ADP sample. The FTIR vibrational band
assignments of pure ADP and XO doped ADP crystals are
represented in Table 3. As such, no noticeable differences in
the FTIR spectra of pure and XO doped samples were
observed, which can be attributed to the small concentration
of XO dopant in ADP. In addition, only minor changes in
the peak positions were observed in the spectra of XO doped
samples, but no secondary vibrational bands were observed
suggesting the presence of XO additive in ADP lattice.

3.3. UV–Vis–NIR spectral analysis

The key optical properties of any sample are determined by its

Fig. 5 X-ray powder diffraction patterns of as grown pure and extinction coefficient (k), refractive index (n) and absorption
XO doped ADP single crystals. coefficient (a). These optical constants play an important role
in analysis of laser frequency conversion, designing of opto-
Table 2 shows the values of refined lattice parameters of the electronic devices and new NLO media. For desired optical
pure and XO dye doped crystals. Doping with XO dye results
in the variation of peak intensity but no shift is observed in the
position of XRD peaks. The incorporation of heavy XO dye
molecules induces strain in the ADP lattice, which results in
a slight change in the cell parameter values (Table 2). The pure
and XO dye doped ADP crystals belong to the tetragonal crys-
tal system with space group I-42d with a small variation in cell
parameter values. Thus, XRD analysis confirms the inclusion
of dye molecules in ADP crystal lattice.

3.2. Functional group analysis using FTIR spectroscopy

In the process of FTIR spectroscopy, an infrared light signal is

passed through the material and the resultant infrared spec-
trum for the material is recorded. Only those frequencies from
the complete incident spectrum (400–4000 cm1) are absorbed,
which are equal to characteristic vibrational frequency of the
bond. FTIR spectra reveal details about the normal mode of
motion, bond strength, bond type and molecular structure of
the material. Also the study of intensity, position and shape
of the absorption bands in FTIR spectra provides information Fig. 6 FTIR Spectra of as grown pure and XO dye doped ADP
about several functional groups present in the sample. Using indicating the formation of most of the expected functional groups
KBr pellet technique, four different pellets of pure and XO in crystals; a slight change in the intensity and position of
dye doped ADP (0.01, 0.05 and 0.1 mol%) mixed with KBr absorption bands confirms the incorporation of XO dye in ADP
were prepared. The FTIR spectra for pure and XO dye doped crystals.

Table 2 Refined cell parameters of pure and XO dye doped ADP crystals.
Parameters Pure ADP XADP-1 XADP-2 XADP-3
Crystal system Tetragonal Tetragonal Tetragonal Tetragonal
Space group I-42d I-42d I-42d I-42d
Cell length, a (Å) 7.4844 7.4871 7.4996 7.5008
Cell length, b (Å) 7.4844 7.4871 7.4996 7.5008
Cell length, c (Å) 7.5386 7.5442 7.5449 7.5515
Cell angle, a (°) 90 90 90 90
Cell angle, b (°) 90 90 90 90
Cell angle, c (°) 90 90 90 90
Volume, (Å3) 422.29 422.90 424.36 424.86

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
6 S. Goel et al.

Table 3 Assignment of various functional groups to the characteristic absorption frequencies observed in the FTIR spectra of Pure
and XO dye doped ADP crystals.
Frequency in wave number (cm1) Assignments of Functional groups
Pure ADP XADP-1 XADP-2 XADP-3
3245 3233 3240 3233 Asymmetric stretching mode of NH3+, OAH stretching of hydrogen bonded carboxyl group
3127 3126 3125 3124 PAOAH Stretching, NAH Vibration of Ammonium, OAH Stretching
2877 2875 2873 2878 (O‚)POAH stretching
2371 2362 2361 2361 PAH stretching
1707 1720 1727 1670 P‚O stretching
1447 1446 1447 1456 Bending vibration of Ammonium (NH4)
1404 1403 1403 1402 Bending vibration of Ammonium (NH4)
1296 1292 1291 1295 Combination of Asymmetric bending vibration of PO4 with lattice
1105 1100 1097 1093 P‚O bending vibration
916 917 917 922 PAOAH bending vibration
545 548 549 543 PO4 bending vibration
460 466 459 451 PO4 bending vibration

applications in industry, the crystal needs to possess high

transmittance and lower cutoff wavelength in the range 200–
300 nm (Levanyuk et al., 1979). The transparency cutoff wave-
length and optical transmittance window provides information
about the various types of optical transitions in any material.
The electrons in the r and p orbital are promoted from ground
state to the excited states due to absorption of UV and visible
light, which provides structural information of the crystal.
Fig. 7(a) displays the UV–vis–NIR transmittance spectra of
pure and XO dye doped ADP sample in the wavelength range
200–1100 nm at room temperature. The cutoff wavelength for
pure ADP is found to be 202 nm. With dye inclusion, the cut-
off wavelength increased to 209 nm, 215 nm and 217 nm for
XADP-1, XADP-2 and XADP-3, respectively. The optical
transparency decreased from 88% (pure) to 85% (XO doped)
due to dye doping. The UV–vis–NIR transmittance spectra of
XO doped ADP crystals depict three characteristic absorption
peaks observed at 270, 440 and 590 nm. These three absorp-
tion peaks confirm the presence of XO dye in doped ADP crys-
tals (Pritula et al., 2009). The intensity of the three absorption
peaks is the weakest for XADP-1, which increased for XADP-
2 and is largest for XADP-3. This pattern of the intensity of
absorption peaks for dye doped crystals agrees well with the
concentration of XO dye doping in ADP lattice. More absorp-
tion on the XADP-3 crystal is due to the high incorporation of
XO dye in the ADP crystal lattice.
Fig. 7(b) depicts the UV–vis–NIR transmittance spectra of
XO dye in neutral water solution. In the case of XO dye in
aqueous solution, four characteristic absorption peaks were
observed at 280 nm, 372 nm, 453 nm and 565 nm. The small
absorption peak in the case of XO doped ADP was observed
at 590 nm and is red shifted in comparison with that of XO
dye in aqueous solution at 565 nm. The two absorption bands
of XO doped ADP at 270 nm and 440 nm are blue shifted rel-
ative to the absorption peak observed in the case of XO dye in
neutral water solution at 280 nm and 453 nm. These red and Fig. 7 (a) UV–vis–NIR spectrum of pure and XO doped ADP.
blue shifts in the absorption bands can be attributed to the (b) The transmittance spectrum of XO dye in aqueous solution.
dye incorporation into the growth sectors of the doped crystal.
The absorption spectrum of the isolated molecules differs
from the spectrum of the aggregates. According to the molec- the absorption bands of XO dye in crystal and in neural water
ular exciton coupling theory, XO dye inclusion into the host solution are mainly due to the change in environmental condi-
ADP crystal can produce splitting of the excited states of the tions. The Hamiltonian operator of the isolated chromophore
aggregate (Subramony et al., 1997). The changes observed in is perturbed by the interactions with the neighboring mole-

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
Xylenol orange doped ADP single crystal 7

Fig. 8 Schematic representation of the inline and parallel transition dipoles depicting the spectral shift (red and blue shifts) based on the
molecular exciton coupling theory (Yadav et al., 2016b).

cules. This perturbation leads to exciton splitting of the excited

states of the aggregates. The exciton coupling between the
neighboring chromophores leads to a shift of the absorption
bands either toward lower energies (red shift) or toward higher
energies (blue shift), depending on their orientation of mole-
cules next to each other (Marek, 2013). The corresponding
aggregates to blue shifts and red shifts are referred to as H-
aggregates and J-aggregates, respectively (Yadav et al.,
2016b). The sign of the difference in dipole moment of dye
molecule in the ground and excited state decides the nature
of shift. In aggregate molecules, inline transition dipoles refer
to the red shift and parallel transition dipoles correspond to
the blue shift in the exciton energy level spectrum (Fig. 8).
The value of optical band gap (Eg) for pure and XO dye
doped ADP single crystal was calculated from the transmit-
tance spectra using the Tauc’s relation: ðahmÞn ¼ Aðhm  Eg Þ,
where h is Planck’s constant, A is a constant and m denotes
the incident frequency. The value of n is 1/2 for indirectly
allowed transition and n is 2 for directly allowed transition
Fig. 9 Tauc’s plot of (ahm)2 vs. hm and evaluation of direct
(Tauc and Menth, 1972). In Tauc’s relation, a denotes the
optical band gap for pure ADP and XO doped ADP crystals; red
absorption coefficient (cm1) and is calculated from the for-
logð 1 Þ
shift in the cutoff wavelength and decrease in optical band gap due
mula a ¼ 2:3026 t T , where t is thickness of the crystal and to XO dye doping.
T is the transmittance of the grown sample. From the Tauc’s
relation analysis, it was found that n = 2 was best fitted for
the pure and dye doped crystals, which suggests that the grown Table 4 The optical transmittance percentages, cutoff
crystals have direct band gap transitions. The Tauc’s plot was wavelengths, direct energy band gap of pure ADP and XO
drawn with (ahm)2 on the y-axis and hm along the x-axis for the dye doped ADP crystals.
grown samples (Fig. 9). The linear portion of the absorption
Crystals Optical Cutoff Direct energy
edge was extrapolated and the x-intercept of the extrapolated
transmission wavelengths band gap (eV)
straight line depicted the value of direct band gap (Eg) of the percentages (%) (nm)
as grown crystals. The value of direct band gap was found
to be 6.13 eV, 5.93 eV, 5.77 eV and 5.72 eV for pure ADP, Pure ADP 88.0 203 6.13
XADP-1 85.3 209 5.93
XADP-1, XADP-2 and XADP-3, respectively. Table 4 reports
XADP-2 85.0 215 5.77
the values of optical transmittance, cutoff wavelengths, optical XADP-3 84.2 217 5.72
band gap of pure and XO doped ADP crystals. The transmit-
tance decreases, cutoff wavelength increases and band gap
decreases with increase in the amount of XO dye concentration
in ADP crystal. The inclusion of XO dye in the ADP crystal
causes an increase in the scattering centers and dislocation den-
The reflectance (R) and the absorption coefficient (a) are
sity, which may be the reason behind the decreased transmit- pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1expðatÞþexpðatÞ
tance in dye doped crystals (Chandran et al., 2015). related by the following relation: R ¼ 1  1þexpðatÞ

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
8 S. Goel et al.

(Dalal et al., 2014). From the reflectance data, the two optical of crystal structure. The PL emission spectra were recorded
parameters, refractive indices (n) and extinction coefficients on the solid samples of as grown pure and XO dye doped crys-
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
tals. The reason for choosing solid samples was that the fluo-
(K) were calculated using n ¼ ðRþ1Þ2ðR1Þ
3R2 þ10R3 ak
and K ¼ 4p ,
rescing dye molecules interact with solvent molecules and
respectively, where k is the wavelength (Dalal et al., 2014). hence give low emission in fluid solvents. PL emission spectra
Fig. 10(b) and (c), shows the plot of refractive indices (n) for all the samples were recorded at RT in the wavelength
and extinction coefficients (K) against photon energy (hm). range 370–670 nm with an excitation wavelength of 350 nm
The refractive index was found to decrease as a result of XO and are demonstrated in Fig. 11. In the PL analysis of pure
dye doping in ADP matrix. The optical conductivity (r) for ADP, a broad blue emission band consisting of three peaks
the as grown pure and dye doped crystals was evaluated from at 396 nm, 419 nm and 437 nm was observed. For the XO
refractive index (n) and absorption coefficient (a) as follows: doped ADP samples, the intensity of this broad blue emission
r ¼ acn
4p
(Yadav et al., 2016a), where c represents the speed of band centered at 420–430 nm decreased with increase in dye
light. Fig. 10(d) depicts the variation of optical conductivity concentration. In addition to the characteristic blue emission
with respect to hm. From Fig. 10(a), (b) and (d), it can be con- band (420–430 nm) observed for pure ADP, an orange emis-
cluded that the reflectance, extinction coefficient and optical sion band centered at 597 nm (2.08 eV) was also observed
conductivity are enhanced for XO dye doped ADP crystals for the XO dye doped samples. This orange emission confirms
in the high photon region. the XO dye inclusion in ADP lattice. Also, the intensity of
orange emission increased further with an increase in dye con-
3.4. Photoluminescence properties centration. The orange emission intensity is the largest for
XADP-3 crystal, suggesting the largest incorporation of XO
The photoluminescence (PL) emission from any material is dye in the ADP crystal lattice. Quenching of the blue emission
very sensitive to the presence of defects in single crystal and intensity can be attributed to the collision between fluorophore
helps to investigate the change in local atomic configuration (ADP) and quencher (XO dye) molecules (Lakowicz, 1999).

Fig. 10 (a) Variation of reflectance (R) as a function of photon energy (hm). (b) Plot of refractive index (n) with photon energy (hm) on x-
axis. (c) Plot of extinction coefficient (K) against photon energy (hm). (d) Variation of optical conductivity (r) as a function of photon
energy (hm).

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
Xylenol orange doped ADP single crystal 9

3.5. Thermal analysis

Thermo gravimetric (TG) and differential thermal analysis

(DTA) are the useful tools to get information regarding
decomposition temperature and phase transition of the crystal
system. Fig. 12 shows the TG/DTA spectra of pure and XO
dye doped ADP crystals. The curve clearly shows that there
is no weight loss up to 168 °C indicating that the pure ADP
crystal is thermally stable in the temperature range of RT to
168 °C. Above 168–325 °C, 30% of pure ADP gets decom-
posed. In case of XO dye doped ADP crystals, no weight loss
was observed up to 166.4 °C, 165.7 °C and 163 °C for XAP-1,
XADP-2 and XADP-3, respectively. There occurs an
endothermic peak (decomposition temperature) at 216.9 °C,
216 °C, 215.5 °C and 213.9 °C for the pure ADP, XADP-1,
XADP-2 and XADP-3, respectively, in the DTA curves. When
compared to pure ADP, the decomposition temperature is
Fig. 11 Photoluminescence spectra of pure ADP and XO dye decreased as a result of dye doping. The difference in decom-
doped ADP single crystals at room temperature with an excitation position temperature observed for the pure and dye doped
wavelength 350 nm; emission of orange fluorescence confirmed crystals indicates the incorporation of XO dye molecules into
xylenol orange dye incorporation into the ADP lattice. the ADP crystal lattice. The xylenol orange dye molecule has

Fig. 12 TG/DTA curves of (a) pure ADP single crystal, (b) 0.01 mol% XO doped ADP (XADP-1) single crystal, (c) 0.05 mol% XO
doped ADP (XADP-2) single crystal and (d) 0.1 mol% XO doped ADP (XADP-3) single crystal.

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
10 S. Goel et al.

grown pure and XO dye doped ADP crystals were poled at

1 kV/mm for 2 h. The value of d33 for pure ADP, XADP-1,
XADP-2, and XADP-3 was found to be 1.80, 2.54, 2.80 and
2.92 pC/N, respectively, along [0 1 0]. The charge asymmetry
developed as a result of dye doping leads to large dipoles on
application of mechanical stress, thus explaining the increase
in value of d33 for XO doped ADP crystals.

3.7. Nonlinear optical studies

In NLO active crystals, the induced polarization is nonlinearly

related to the applied electric field produced by high power
laser system. In particular, doubling of the input frequency is
known as SHG. The SHG conversion efficiency of the pure
and dye doped crystals was tested using the powder technique
developed by Kurtz and Perry (Kurtz, 1968). For SHG testing
of the materials, uniform crystalline powder of 63 lm size was
packed in a micro-capillary (1.5 mm diameter) tube. A high
Fig. 13 The variation of Vickers micro-hardness number on the power Q switched Nd:YAG laser system operated at the repe-
(0 1 0) plane with applied load for pure and XO dye doped ADP tition rate of 10 Hz with a fundamental beam of wavelength
crystals; XO dye doping increased the mechanical strength of ADP 1054 nm was used for SHG measurement. The input energy
crystals. of 0.68 J/pulse was allowed to strike normally on the powder
sample. The green emission with a wavelength of 532 nm
low decomposition temperature (210 °C; Science Material was procured from the samples, which confirmed the SHG.
Safety Data Sheet) compared with ADP and hence the decom- The output energy was measured to be 4.83, 4.89, 5.59 and
position temperature of XO doped ADP single crystals got 5.84 mJ/pulse for pure ADP, XADP-1, XADP-2 and XADP-
reduced. The same results have been reported in the past for 3, respectively. Therefore, the XO doped ADP crystals have
glycine doped ADP crystal (Rajesh and Ramasamy, 2015) shown enhanced SHG efficiency. XO dye molecules exhibit
and CV dye doped KAP crystal (Rao et al., 2014). low symmetry representing a polar charge distribution pro-
moting the NLO activity of host (ADP) crystal (Aboulfadl
3.6. Piezoelectric response et al., 2012). Moreover, the aligned growth of the XO dye
molecules at ADP crystal plane features the nonlinear optical
The lack of center of symmetry is essential for the existence of properties (Aboulfadl et al., 2012). Peramaiyan et al. have
many useful properties in a single crystal including piezoelec- reported an enhancement in SHG efficiency of L-arginine
tricity (Wojtaś et al., 2014a). Piezoelectric materials are those phosphate crystal by doping with XO dye molecules
which produce electric charge (field) when a mechanical force (Peramaiyan et al., 2013).
is applied on them or conversely develop strain under the
application of electric field (Wojtaś et al., 2014b). In either 3.8. Vickers micro-hardness testing
way, there is a linear coupling between stress and the applied
field. This makes a piezoelectric crystal useful for various The material hardness is defined as the measure of the resis-
devices such as sensors, actuators and transducers. The as tance offered by the material to local deformation under

Fig. 14 The photograph of honey droplet on (1 0 0) crystal face of pure ADP, XADP-1, XADP-2 and XADP-3 crystals; XO dye doping
increased the wettability of ADP crystals.

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
Xylenol orange doped ADP single crystal 11

indentation or scratching (Goel et al., 2016). Vickers micro-

Table 5 Average contact angles of the honey
hardness technique was used to test the mechanical strength
droplets on pure and XO doped ADP crystals.
of as grown pure and dye doped crystals. A diamond indenter
with pyramid tip was employed to make indents on the (0 1 0) Crystal Contact angle (o)
plane of all the samples. The varying indenter load of values Pure ADP 81.8 ± 0.9
5 g, 10 g, 20 g, 30 g, 40 g, 50 g, 100 g and 200 g was applied XADP-1 80.2 ± 0.7
for a constant dwell time of 5 s on (0 1 0) plane of pure and XADP-2 77.4 ± 0.8
XO doped ADP samples. The value of Vickers micro- XADP-3 61.9 ± 1.7
hardness number (Hv; MPa) was evaluated using the formula
(Goel et al., 2013): Hv = 1.8544 P/d2, where P represents the
applied indenter load in kg and d is the average diagonal length
of the indent in mm. Fig. 13 illustrates the plot of harness num- that XO dye doped ADP crystal wets too much in comparison
ber (Hv) versus applied load (P) on the (0 1 0) face of pure and with pure ADP crystal. The XO dye molecules selectively stain
doped ADP samples. It can be observed from the figure that the {1 0 0} growth sectors of ADP crystal, due to which (1 0 0)
the XO doping increases the micro-hardness value of ADP plane of doped ADP is more dense than that of pure. The high
crystal and thus doped ADP crystals show high resistance to density leads to more attractive force and large surface tension
motion of dislocation in comparison with pure ADP crystal. of solids, thus, explaining the decrease in contact angle with
The high micro-hardness value for XO dye doped ADP crys- increase in dye concentration.
tals makes them a more suitable candidate than pure ADP
from a mechanical point of view for device fabrication. That 4. Conclusions
the micro-hardness value increases with rising applied load
up to 20 g load and then decreases with further increase in In summary, pure and XO dye doped ADP single crystals of good
indenter load up to 40 g is clearly reflected by the Vickers transparency were grown by slow evaporation method at RT. BFDH
micro-hardness curve depicted in Fig. 13. After 40 g, the har- law was successfully employed to understand the crystal morphology
ness value shows no remarkable change and attained a con- of grown crystals. As a result of XO dye doping, the morphology of
ADP crystal was not altered and inclusion of XO dye in {1 0 0} growth
stant value. This type of nonlinear variation in hardness with
sectors of ADP crystal was observed. The presence of XO dye in the
indenter load can be justified on the basis of penetration of
lattice of ADP was confirmed by the powder XRD, FTIR spec-
the diamond indenter. At lower values of applied indenter troscopy, UV–vis–NIR and photoluminescence spectral studies. Pow-
load, only the top surface layers of the crystal are penetrated der XRD analysis confirmed that the grown pure and dye doped
resulting in an increase in hardness with applied loads, which crystals belong to tetragonal structure with non-centrosymmetric space
shows the reverse indentation size effect (RISE) (Sahin et al., group (I-42d). As a result of low concentration of the dye molecules,
2007). However, at higher value of indenter load the indenta- no extra absorption bands were observed in the FTIR spectra of dye
tion depth is large due to which the effect of inner layers is doped sample. Moreover, only a slight variation in the peak intensity
inevitable. The internal stress generated at large load indenta- and peak positions in the FTIR spectra was observed as a result of XO
tion gets released in the form of cracks resulting in a drastic dye dopant. From UV–vis–NIR analysis, it can be concluded that
transparency decreased (by 3%) and direct energy band gap decreased
decrease of hardness with applied loads, which shows the nor-
as a result of dye doping. The value of optical band gap was evaluated
mal indentation size effect (ISE) (Sahin et al., 2007). After
to be 6.13, 5.93, 5.77 and 5.72 eV for pure ADP, XADP-1, XADP-2
40 g, the value of hardness number remains almost constant and XADP-3, respectively. Three absorption peaks were found at
which is due to the piling-up of the crystal surface. Similar 270, 440 and 590 nm in the transmittance spectra of XO dye doped
results showing increase in mechanical strength as a result of samples, which suggests the presence of XO dye in ADP crystal. In
dye doping had been reported in the literature for various the PL spectra, the blue emission centered at 420–430 nm was
dye doped crystals (Goel et al., 2016; Chandran et al., 2015; quenched and the intensity of orange emission centered at 597 nm
Raju et al., 2011). was enhanced with an increase in XO dye doping. Increasing XO
dye concentration gradually decreased the decomposition temperature
3.9. Measurement of the contact angle of ADP crystal. The piezoelectric charge coefficient value increased
with increasing XO dye concentration. The SHG conversion efficiency
of the XO doped crystals was larger than that of pure ADP sample and
To investigate the effect of XO dye doping on the wettability it further increased with an increase in dye concentration. The mechan-
of the (1 0 0) plane of ADP crystal, we chose honey as a probe ical hardness of ADP crystal was found to increase as a result of XO
liquid. Honey was dropped on the ADP crystal using a micro- dye doping. Increasing XO dye concentration gradually decreased
pipet. The honey droplet was pictured using digital camera the contact angle of honey with (1 0 0) crystal plane of ADP.
(Canon SX510HS) featuring a 30 optical zoom. Drop shape
analysis for contact angle measurement was done using snake Acknowledgment
based approach in ImageJ software (Stalder et al., 2006). It
was observed that the pure and dye doped ADP crystals exhib- We are thankful for the financial support received through the
ited hydrophilic properties in air with honey (Fig. 14). The DRDO Project (ARMREB/MAA/2015/163) and R & D
shape of the droplet we used in this experiment was uninflu- Grant (Sanction No. RC/2015/9677). Dr. Nidhi Sinha
enced by gravity. In order to determine more accurate value expresses her gratitude to the Principal, SGTB Khalsa College,
of contact angle for each crystal, 30 honey droplets were made for encouragement and support for research work. Sahil Goel,
and the mean value of contact angle was taken. The effect of Abhilash J. Joseph and Abid Hussain would like to thank
XO dye doping on contact angle of honey on (1 0 0) crystal CSIR for their Junior Research Fellowship. Harsh Yadav is
plane of ADP is summarized in Table 5. It can be concluded thankful to UGC for Merit Scholarship.

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
12 S. Goel et al.

References Goel, S., Sinha, N., Yadav, H., Hussain, A., Kumar, B., 2016. Effect
of crystal violet dye on the structural, optical, mechanical and
Aboulfadl, H., Burgener, M., Benedict, J., Kahr, B., Hulliger, J., 2012. piezoelectric properties of ADP single crystal. Mater. Res. Bull. 83,
Polar alignment of dye molecules in sectors of host lattices revealed 77–87. [Link]
by phase sensitive second harmonic generation and scanning Gupta, B.L., 1974. Absorption characteristics of xylenol orange.
pyroelectric microscopy. CrystEngComm 14, 4391. [Link] Talanta 21, 683–684. [Link]
org/10.1039/c2ce25152c. 80215-8.
Aleshin, V.I., Raevski, I.P., 2013. Piezoelectric anisotropy of Hasmuddin, M., Singh, P., Shkir, M., Abdullah, M.M., Vijayan, N.,
orthorhombic ferroelectric single crystals. J. Appl. Phys. 113. Ganesh, V., Wahab, M.A., 2014. Study of pure and l-tartaric acid
[Link] doped ammonium dihydrogen phosphate single crystals: a novel
Amat-Guerri, F., Costela, A., Figuera, J.M., Florido, F., Sastre, R., nonlinear optical non-centrosymmetric crystal. Mater. Chem. Phys.
1993. Laser action from rhodamine 6G-doped poly (2-hydroxyethyl 144, 293–300. [Link]
methacrylate) matrices with different crosslinking degrees. Chem. 12.033.
Phys. Lett. 209, 352–356. [Link] Hermes, R.E., Allik, T.H., Chandra, S., Hutchinson, J.A., 1993. High-
80029-O. efficiency pyrromethene doped solid-state dye lasers. Appl. Phys.
Anbukumar, S., Vasudevan, S., Ramasamy, P., 1987. The hardness Lett. 63, 877. [Link]
anisotropy of ADP crystals. Mater. Chem. Phys. 16, 125–132. Hudson, J.A., Mahadevan, C.K., Padma, C.M., 2014. Int. J. Eng. Res.
[Link] Appl. 4, 257.
Ashwell, G.J., Jefferies, G., Hamilton, D.G., Lynch, D.E., Roberts, M. Kahr, B., Gurney, R.W., 2001. Dyeing crystals. Chem. Rev. 101, 893–
S.P., Bahra, G.S., Brown, C.R., 1995. Strong second-harmonic 952. [Link]
generation from centrosymmetric dyes. Nature 375, 385–388. Kahr, B., Shtukenberg, A.G., 2016. Dyeing crystals since 2000.
[Link] CrystEngComm 18, 8988–8998. [Link]
Benedict, J.B., Wallace, P.M., Reid, P.J., Jang, S.-H., Kahr, B., 2003. C6CE02185A.
Up-conversion luminescence in dye-doped crystals of potassium Kaminsky, W., 2005. WinXMorph : a computer program to draw
hydrogen phthalate. Adv. Mater. 15, 1068–1070. [Link] crystal morphology, growth sectors and cross sections with export
10.1002/adma.200303715. files in VRML V2.0 utf8-virtual reality format. J. Appl. Crystal-
Bhagavannarayana, G., Parthiban, S., Meenakshisundaram, S., 2006. logr. 38, 566–567. [Link]
Enhancement of crystalline perfection by organic dopants in ZTS, Katrusiak, A., McMillan, P.F., 2004. High-Pressure Crystallography.
ADP and KHP crystals as investigated by high-resolution XRD Springer Science+Business Media, New York.
and SEM. J. Appl. Crystallogr. 39, 784–790. [Link] Kuehne, A.J.C., Gather, M.C., 2016. Organic lasers: recent develop-
10.1107/S0021889806033139. ments on materials, device geometries, and fabrication techniques.
Bhandari, S., Sinha, N., Ray, G., Kumar, B., 2014. Enhanced optical, Chem. Rev. 116, 12823–12864. [Link]
dielectric and piezoelectric behavior in dye doped zinc tris-thiourea chemrev.6b00172.
sulphate (ZTS) single crystals. Chem. Phys. Lett. 591, 10–15. http:// Kumaresan, P., Babu, S.M., Anbarasan, P.M., 2008. Growth and
[Link]/10.1016/[Link].2013.11.007. characterization of metal ions and dyes doped KDP single crystals
Chandran, S., Paulraj, R., Ramasamy, P., 2015. Influence of amaranth for laser applications. Mater. Res. Bull. 43, 1716–1723. [Link]
dye on the growth and properties of KDP single crystal. Mater. [Link]/10.1016/[Link].2007.07.018.
Res. Bull. 68, 210–215. [Link] Kurtz, S.K., 1968. A powder technique for the evaluation of nonlinear
2015.03.056. optical materials. J. Appl. Phys. 39, 3798. [Link]
Costela, A., Cerdán, L., Garcı́a-Moreno, I., 2013. Solid state dye lasers 10.1063/1.1656857.
with scattering feedback. Prog. Quantum Electron. 37, 348–382. Lakowicz, J.R., 1999. Principles of Fluorescence Spectroscopy.
[Link] Springer, Baltimore, Maryland.
Dalal, J., Sinha, N., Kumar, B., 2014. Structural, optical and dielectric Levanyuk, A.P., Osipov, V.V., Sigov, A.S., Sobyanin, A.A., 1979.
studies of novel non-linear Bisglycine Lithium Nitrate piezoelectric Change of defect structure and the resultant anomalies in the
single crystal. Opt. Mater. (Amst) 37, 457–463. [Link] properties of substances near phase-transition points. Soviet J. Exp.
10.1016/[Link].2014.07.006. Theor. Phys. 49, 176–188.
Dhanaraj, P.V., Bhagavannarayana, G., Rajesh, N.P., 2008. Effect of Liu, X.Y., Boek, E.S., Briels, W.J., Bennema, P., 1995. Prediction of
amino acid additives on crystal growth parameters and properties crystal growth morphology based on structural analysis of the
of ammonium dihydrogen orthophosphate crystals. Mater. Chem. solid–fluid interface. Nature 374, 342–345. [Link]
Phys. 112, 490–495. [Link] 10.1038/374342a0.
2008.06.003. Lovell, S., Subramony, P., Kahr, B., 1999. Poppy acid: synthesis and
Docherty, R., Clydesdale, G., Roberts, K.J., Bennema, P., 1991. crystal chemistry. J. Am. Chem. Soc. 121, 7020–7025. [Link]
Application of Bravais-Friedel-Donnay-Harker, attachment energy org/10.1021/ja990402a.
and Ising models to predicting and understanding the morphology Marek, P.L., 2013. Biomimetic Dye Aggregate Solar Cells Springer
of molecular crystals. J. Phys. D. Appl. Phys. 24, 89–99. [Link] Theses. Springer International Publishing, Cham. [Link]
[Link]/10.1088/0022-3727/24/2/001. org/10.1007/978-3-319-00636-9.
DuVarney, R.C., Kohin, R.P., 1968. Domain switching in irradiated Mauri, A., Moret, M., 2000. Growth of potassium sulfate crystals in
ferroelectric KH2PO4 observed by electron spin resonance. Phys. the presence of organic dyes: in situ characterization by atomic
Rev. Lett. 20, 259–262. [Link] force microscopy. J. Cryst. Growth 208, 599–614. [Link]
20.259. 10.1016/S0022-0248(99)00401-7.
Garmire, E., 2013. Nonlinear optics in daily life. Opt. Express 21, Meena, M., Mahadevan, C.K., 2008. Growth and electrical charac-
30532. [Link] terization of L-arginine added KDP and ADP single crystals.
Goel, N., Sinha, N., Kumar, B., 2013. Growth and properties of Cryst. Res. Technol. 43, 166–172. [Link]
sodium tetraborate decahydrate single crystals. Mater. Res. Bull. 10.1002/crat.200711064.
48, 1632–1636. [Link] Monaco, S.B., Davis, L.E., Velsko, S.P., Wang, F.T., Eimerl, D.,
01.007. Zalkin, A., 1987. Synthesis and characterization of chemical

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
Xylenol orange doped ADP single crystal 13

analogs of L-arginine phosphate. J. Cryst. Growth 85, 252–255. Reintjes, J., Eckardt, R.C., 1977. Efficient harmonic generation from
[Link] 532 to 266 nm in ADP and KD*P. Appl. Phys. Lett. 30, 91. http://
Mou, X., Wei, X., Li, Y., Shen, W., 2012. Tuning crystal-phase and [Link]/10.1063/1.89300.
shape of Fe2O3 nanoparticles for catalytic applications. CrystEng- Reisfeld, R., Yariv, E., Minti, H., 1997. New developments in solid
Comm 14, 5107. [Link] state lasers. Opt. Mater. (Amst) 8, 31–36. [Link]
Nie, W., 1993. Optical nonlinearity: phenomena, applications, and 10.1016/S0925-3467(97)00036-0.
materials. Adv. Mater. 5, 520–545. [Link] Ren, X., Xu, D., Xue, D., 2008. Crystal growth of KDP, ADP, and
adma.19930050704. KADP. J. Cryst. Growth 310, 2005–2009. [Link]
Nitti, S., Tan, H.M., Banfi, G., Degiorgio, V., Bailey, R.T., Cruick- 10.1016/[Link].2007.11.008.
shank, F., Pugh, D., Shepherd, E.A., Sherwood, J.N., Simpson, G. Rifani, M., Yin, Y., Elliott, D.S., Jay, M.J., Jang, S., Kelley, M.P.,
S., 1993. Nonlinear susceptibility and damage thresholds of organic Bastin, L., Kahr, B., 1995. Solid state dye lasers from stereospecific
MBA-NP crystals. J. Phys. D. Appl. Phys. 26, B225–B229. http:// host-guest interactions. J. Am. Chem. Soc. 117, 7572–7573. http://
[Link]/10.1088/0022-3727/26/8B/038. [Link]/10.1021/ja00133a042.
Pan, F., Shing Wong, M., Bosshard, C., Günter, P., Gramlich, V., Rohl, A.L., 2003. Computer prediction of crystal morphology. Curr.
1996. Strong hydrogen bonds as a design element for developing Opin. Solid State Mater. Sci. 7, 21–26. [Link]
new non-linear optical crystals: co-crystals of merocyanine dyes S1359-0286(03)00019-6.
and phenol derivatives. Adv. Mater. Opt. Electron. 6, 261–266. Sahin, O., Uzun, O., Kolemen, U., Ucar, N., 2007. Vickers microin-
[Link] dentation hardness studies of b-Sn single crystals. Mater. Charact.
AID-AMO279>[Link];2-K. 58, 197–204. [Link]
Peramaiyan, G., Pandi, P., Vijayan, N., Bhagavannarayana, G., Sapaev, U.K., Kulagin, I.A., Usmanov, T., 2003. Theory of second-
Kumar, R.M., 2013. Studies on growth, structural, optical and harmonic generation for limited laser beams in nonlinear crystals.
mechanical properties of xylenol orange dye admixtured l-arginine J. Opt. B Quantum Semiclassical Opt. 5, 355–356. [Link]
phosphate single crystal. Opt. - Int. J. Light Electron Opt. 124, org/10.1088/1464-4266/5/4/305.
4058–4063. [Link] Shaikh, R.N., Anis, M., Shirsat, M.D., Hussaini, S.S., 2015. Study on
Pritula, I., Gayvoronsky, V., Gromov, Y., Kopylovsky, M., Koly- optical properties of l-valine doped ADP crystal. Spectrochim.
baeva, M., Puzikov, V., Kosinova, A., Savvin, Y., Velikhov, Y., Acta Part A Mol. Biomol. Spectrosc. 136, 1243–1248. [Link]
Levchenko, A., 2009. Linear and nonlinear optical properties of org/10.1016/[Link].2014.10.009.
dye-doped KDP crystals: effect of thermal treatment. Opt. Com- Stalder, A.F., Kulik, G., Sage, D., Barbieri, L., Hoffmann, P., 2006. A
mun. 282, 1141–1147. [Link] snake-based approach to accurate determination of both contact
optcom.2008.11.043. points and contact angles. Colloids Surfaces A Physicochem. Eng.
Pritula, I.M., Salo, V.I., Kolybaeva, M.I., 2001. Laser damage Asp. 286, 92–103. [Link]
threshold and UV absorption of doped potassium dihydrogen Subramony, J.A., Jang, S., Kahr, B., 1997. Dyeing KDP. Ferroelectrics
phosphate crystals. Inorg. Mater. 37, 184–185. [Link] 191, 293–300. [Link]
10.1023/A:1004126114703. Takubo, H., Makita, H., 1989. Refractometric studies of NH4H2PO4
Rajesh, P., Ramasamy, P., 2015. Growth and characterization of large and KH2PO4 solution growth; experimental setup and refractive
size ADP single crystals and the effect of glycine on their growth index data. J. Cryst. Growth 94, 469–474. [Link]
and properties. Opt. Mater. (Amst) 42, 87–93. [Link] 10.1016/0022-0248(89)90023-7.
10.1016/[Link].2014.12.024. Tauc, J., Menth, A., 1972. States in the gap. J. Non. Cryst. Solids 8–10,
Rajesh, P., Ramasamy, P., Bhagavannarayana, G., 2013. Growth of 569–585. [Link]
ADP–KDP mixed crystal and its optical, mechanical, dielectric, Vandersteen, O.S., Vrublevska, T., Lang, H., 2004. Acta Chim. Slov.
piezoelectric and laser damage threshold studies. J. Cryst. Growth 51, 127.
362, 338–342. [Link] Wang, H., Li, F., Gao, B., Xie, Z., Liu, S., Wang, C., Hu, D., Shen, F.,
Rajesh, P., Ramasamy, P., Kumar, B., Bhagavannarayana, G., 2010. Xu, Y., Shang, H., Chen, Q., Yuguang, M., Sun, H., 2009. Doped
Effect of cobalt and dl-malic acid on the growth rate, crystalline organic crystals with high efficiency, color-tunable emission toward
perfection, optical, mechanical, dielectric, piezoelectric properties laser application. Cryst. Growth Des. 9, 4945–4950. [Link]
and SHG efficiency of ADP single crystals. Phys. B Condens. org/10.1021/cg9007125.
Matter 405, 2401–2406. [Link] Wojtaś, M., Czupiński, O., Tylczyński, Z., Isakov, D., Belsley, M.,
02.054. Jakubas, R., 2014a. Optical nonlinearity and piezoelectricity in
Rajesh, P., Silambarasan, A., Ramasamy, P., 2014. Effect of crystal 2,4,6-trimethylpyridinium perchlorate. Chem. Phys. 441, 59–65.
violet dye on the optical, dielectric, thermal and mechanical [Link]
properties of <001> directed KDP single crystal. Mater. Res. Wojtaś, M., Gaz gor, A., Kholkin, A., 2014b. Piezoelectricity and
Bull. 49, 640–644. [Link] crystal structure of H-b-(2 Pyridyl)-Ala-OH amino acid microcrys-
10.007. tals. J. Mol. Struct., 213–219 [Link]
Raju, B., Saritha, A., Bhagavannarayana, G., Hussain, K., 2011. A [Link].2014.06.084.
comparative study on growth, structural, optical, thermal and Xu, D., Xue, D., 2006. Chemical bond analysis of the crystal growth of
mechanical properties of undoped and dye doped bis glycine KDP and ADP. J. Cryst. Growth 286, 108–113. [Link]
cadmium chloride single crystals. J. Cryst. Growth 324, 184–189. 10.1016/[Link].2005.09.040.
[Link] Yadav, H., Sinha, N., Kumar, B., 2016a. New geometrical modeling to
Rao, G.B., Rajesh, P., Ramasamy, P., 2016. Investigations on the study crystal morphology. Cryst. Growth Des. 16, 4559–4566.
growth, optical, thermal, dielectric, and laser damage threshold [Link]
properties of crystal violet dye-doped potassium acid phthalate Yadav, H., Sinha, N., Kumar, B., 2016b. Modified low temperature
single crystal. Appl. Phys. A 122, 175. [Link] Czochralski growth of xylenol orange doped benzopheone single
s00339-016-9693-7. crystal for fabricating dual band patch antenna. J. Cryst. Growth
Rao, G.B., Rajesh, P., Ramasamy, P., 2014. A study on the growth, 450, 74–80. [Link]
optical, thermal, mechanical, dielectric and piezoelectric properties Yariv, E., Reisfeld, R., 1999. Laser properties of pyrromethene dyes in
of dye doped KAP single crystals. Mater. Res. Bull. 60, 709–713. sol–gel glasses. Opt. Mater. (Amst) 13, 49–54. [Link]
[Link] 10.1016/S0925-3467(99)00010-5.

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]
14 S. Goel et al.

Yariv, E., Schultheiss, S., Saraidarov, T., Reisfeld, R., 2001. Efficiency Yokotani, A., Sasaki, T., Yoshida, K., Yamanaka, T., Yamanaka, C.,
and photostability of dye-doped solid-state lasers in different hosts. 1986. Improvement of the bulk laser damage threshold of potas-
Opt. Mater. (Amst) 16, 29–38. [Link] sium dihydrogen phosphate crystals by ultraviolet irradiation.
3467(00)00056-2. Appl. Phys. Lett. 48, 1030. [Link]

Please cite this article in press as: Goel, S. et al., Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications.
Arabian Journal of Chemistry (2017), [Link]