Materials Research Bulletin 68 (2015) 210–215

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Materials Research Bulletin

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

Influence of amaranth dye on the growth and properties of KDP single

crystal
Senthilkumar Chandran, Rajesh Paulraj * , P. Ramasamy
Centre for Crystal Growth, Department of Physics, SSN College of Engineering, Kalavakkam 603110, India

A R T I C L E I N F O A B S T R A C T

Article history: Amaranth dye doped KDP single crystals were grown by slow cooling seed rotation method with the
Received 30 October 2014 vision to improve the properties of the crystal. The grown crystals were of size up to 53
20
50 mm3.
Received in revised form 20 March 2015 The grown crystals were subjected to FTIR, UV–vis photoluminescence, microhardness and laser damage
Accepted 25 March 2015
threshold studies. The addition of dye improves the growth rate of the crystals. Photoluminescence (PL)
Available online 26 March 2015
emission spectra of amaranth doped KDP crystals are practically identical. Amaranth increases the
mechanical strength and laser damage threshold of the grown crystals compared to pure KDP crystals.
PACS:
ã 2015 Elsevier Ltd. All rights reserved.
77.22.Gm
78.20.-e
81.10.Dn

Keywords:
Crystal growth
Inorganic materials
Mechanical properties
Photoluminescence
Laser damage threshold

1. Introduction temperature reduction method to grow dye doped KDP crystal

Potassium dihydrogen phosphate (KDP) has been extensively
studied for many years (since 1930) due to its important
applications in science and technology. Extremely high optical
and structural perfection of KDP makes it possible to produce
elements for various non-linear optical and electro-optical
properties such as frequency multipliers, optical parametric
oscillators, electro-optical modulators, 3D optical data storage
and pockels cells for mega-joule laser systems of the new
generation [1–6]. The technology of large size KDP single crystal
growing on the point seed by the method of slow cooling is having
great practical importance because such crystals are widely used
in very high-energy Nd-glass lasers used for inertial confinement
fusion research. Large plates of nonlinear crystals are needed for
electro-optic switches and frequency converters. In the last three
decades, many research efforts have been made to promote the
high quality single crystal and increase the growth rate to meet
the requirements of inertial confinement fusion [3,7–10]. From
this point of view various rapid new growth techniques are
developed worldwide [6–8,10]. Zaitseva et al. used “point seed”
* Corresponding author. Tel.: +91 9445434893; fax: +91 4427475166.
E-mail address: rajeshp@ssn.edu.in (R. Paulraj).
with the growth rates from 0.5 to 25 mm/day in 1999 [8]. In 2008,
Pritula et al. grew urea doped KDP crystals by “point seed”
temperature reduction technique [10]. The amount of impurities
in the raw materials is an important factor for the rapid growth of
crystals. For pure KDP crystals, the degree of structural
imperfection is determined by the content of inorganic impurities
that are necessarily present in initial salt solutions. KDP crystals
can absorb different types of inorganic and organic molecules: the
high valence cationic ions Cu2+, Cr3+, Al3+, Bi3+ and Fe3+, organic
molecules such as phenols, fatty acids, amaranth, sunset yellow,
ethanol, 1-propanol and so on [3,5,10–13]. Some of the
parameters are generally affecting the growth habits of KDP
crystals, such as the super saturation of the solution, the
absorption of foreign particles, temperature and pH value
[3,10]. It is experimentally proved that the cationic ions are
easily absorbed on the prismatic faces and inhabit their growth
but the effects of anionic ions are rarely seen in these faces [12].
Different kinds of inorganic lattices can encapsulate organic dye
molecules and dyes inclusion in crystal promises spectroscopic,
optical and photonic applications [14]. The incorporation of the
dye molecules in KDP crystal is determined by the molecular
electrostatic potential (MESP) and the charge state of the growing
crystal face. The chemical bonds of KDP crystals are formed by
cations (K+), anions (H2PO4–) and the hydrogen bonds of the

http://dx.doi.org/10.1016/j.materresbull.2015.03.056
0025-5408/ ã 2015 Elsevier Ltd. All rights reserved.
 S. Chandran et al. / Materials Research Bulletin 68 (2015) 210–215
adjacent (H2PO4–) groups. The morphology of KDP crystals are
constituted by prism and pyramidal faces [15]. The prismatic
faces (1 0 0) of KDP crystals are framed of (H2PO4–) and K+
successively, whereas the pyramidal faces (1 0 1) end with K+ in
growth solution [16]. The surface of pyramidal face of KDP crystal
has a positive charge, while the electrostatic potential (ESP)
distribution of the anion impurity is totally negative. Therefore,
amaranth dye is easily occupying the lattices of the pyramidal
sector (1 0 1) [17]. Asakuma et al. reported that dyes can be
absorbed onto the different faces of KDP crystals. For example
sunset yellow, amaranth, sky blue are absorbed on the pyramidal
sector (1 0 1), methylene blue, crystal violet are absorbed onto the
prismatic sector (1 0 0) and brilliant blue, acid fuchsin are
captured onto both sectors [18]. In our investigation, anionic
amaranth dye is preferably absorbed onto the pyramidal
face (1 0 1) of KDP crystal. Concentration of impurity surface
assimilation is assigned to the alternating control of the cation
(K+) or anion (H2PO4) on various crystal facets in the case of KDP
crystal. The organic dye molecules tend to be absorbed by a
positively charged face of the pyramidal facet [19,20].
The present paper describes and discusses the experimental
results concerning the influence of amaranth organic dye on the
Fig. 1. (a) Pure KDP crystal, (b) 0.2 mol% amaranth doped KDP crystal, (c) 0.3 mol% amaranth doped KDP crystal and (d) 0.4 mol% amaranth doped KDP crystal.
211
crystal growth, FTIR, UV–vis photoluminescence, mechanical
stability and bulk laser damage resistance of the KDP single
crystals.
2. Experimental procedure
2.1. Crystal growth
The starting material was pure KDP, which was bought from
MERK-GR. Millipore ultrapure water with resistivity of 18.2 MV cm
was used as the solvent. Amaranth dye was used as additive in
different mole percentage 0.2, 0.3 and 0.4 respectively. Pure KDP
seed crystals were first obtained in the supersaturated KDP
solution by slow evaporation. The crystals were grown by the slow
cooling method on a point seed from an aqueous solution
containing 0.2, 0.3 and 0.4 mol% of the dye and pure KDP salt.
Seed crystals with perfect morphology and free from macro defects
were used for growth experiments. This experimental setup
consists of a seed rotation controller coupled with a stepper motor,
which is controlled using a microcontroller supported drive. This
controller rotates the seed holder in the crystallizer. The seed
crystal is mounted on the center of the platform made up of acrylic
212 S. Chandran et al. / Materials Research Bulletin 68 (2015) 210–215

material. The uniform rotation of the seed is necessary so that not

101
to produce undynamic regions or re-circulating flows, otherwise
100
inclusions in the crystals will be created due to inhomogeneous
99
super saturation in the solution. All experiments are carried out in
a standard glass 5000 ml crystallizer. The saturation solution is 98

prepared at 45  C temperature. The solution was filtered by 97

Transmittance(%)
Whatman filter paper of size 460 mm
570 mm. After the 96
filtration, the solution was overheated to 60  C for one day. Four 95
water baths are used for crystal growth process. The growth run 94 Pure KDP
was carried out in the temperature range between 45 and 30  C. 93 0.2 mol% Amaranth+KDP
The temperature of crystallizer is controlled using water bath, and 0.3 mol% Amaranth+KDP
92
the temperature fluctuations are less than 0.01  C. Then the 0.4 mol% Amaranth+KDP
91
temperature was increased to 2 (at 1  C/h) higher than saturation
90
point and again the temperature was decreased to saturation point
at 1  C/day. 10
10
3 mm3 size pure KDP crystal was fixed in the 89

centre of the crystallizer and it was kept inside a constant 88

temperature bath slowly. From the saturation point (45  C), the
temperature was decreased at the rate of 0.3  C/day. The reversible
rotation rate of the platform with the crystal was about 30 rpm.
After 3 days of growth the cooling rate was changed to 0.6  C/day.
The transparent good quality large size single crystals of pure KDP
and amaranth dye doped KDP were grown after 20 days. It is clearly
observed that the size of the crystals decreases with increasing
concentration level of dopant. The final sizes of pure and 0.2,
0.3 and 0.4 mol% amaranth doped KDP crystals were 36
29
54,
53
20
50, 43
40
40 and 40
38
49 mm3 respectively and
it is shown in Fig. 1. During the period of crystal growth, the dye
molecules were incorporated only into the pyramidal growth
sector, whereas the prismatic sector remained colorless. This
may be due to the electrostatic potential (ESP) distribution of the
dye in the prepared KDP solution. Protonation reaction is the
significant mechanism for the dye coloring characteristics [18].
2.2. Characterization methods
As grown dye doped KDP and pure KDP crystals have been
subjected to various characterization studies to analyze the
structural, optical and mechanical properties. The functional
groups were identified using BRUKER IFS66V FT-IR spectrometer
in the range of 500–4000 cm1 with single reflection ATR
accessory. The optical behavior of the crystals was examined at
room temperature using PERKIN-ELMER LAMBDA-35 UV–vis–NIR
spectrophotometer with slit width of 2 nm and spectral range
between 190 and 1100 nm. Photoluminescence measurements
were carried out on a spectrophotometer of the Shimadzu
spectrofluorophotometer R.F-5031 PC Series with the slit width
of 3 nm. To study the mechanical property, the grown crystals were
subjected to Vickers microhardness tester Mututoyo Model
MH112. The laser damage threshold was determined using YAG:
Nd laser operating at 7 ns pulse width. The samples used in our
investigations were prepared from the pyramidal face of the pure
and different concentration of amaranth added KDP crystal.
Optically clear and low dislocation density samples were polished
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )
Fig. 2. FTIR spectra of pure and amaranth doped KDP crystals.
using alumina powder to study the optical, mechanical and
laser damage threshold. For these measurements 2 mm samples
were used. The fine powder samples were used for FTIR and
photoluminescence response studies.
3. Results and discussion
3.1. FTIR spectra measurements
Fig. 2 shows mid-infrared transmission spectra of pure and dye
doped KDP crystals. There is no any considerable change in the
position and nature of peaks. However, the doping of amaranth in
KDP crystal normally gives rise to a moderate shift in some of the
characteristic vibrational frequencies and variation in peak
intensities. The wave number assignments of pure and dye doped
KDP crystals are given in Table 1. The deviation in the peaks may
be due the interaction of dye with OH group of KDP crystal. The
peak position in pure KDP crystal at 3468 cm1 is shifted to
3461 cm1, 3375 cm1 and 3358 cm1 for doped crystals. The
O¼POH peak at 1661 cm1 is shifted to 1673 cm1 for 0.3,
0.4 mol% doped crystals. The POH band at 858 cm1 is shifted to
857 cm1, 866 cm1 and 864 cm1 for doped crystals. The
HO P OH band at 537 cm1 is shifted to 532 cm1, 530 cm1
for 0.3, 0.4 mol% doped KDP crystals [21]. However, there is no
other appreciable deviation which supports that addition of small
concentration of dye does not affect the functional groups of the
KDP crystals [22].
3.2. Optical analysis
Single crystals are generally used in optical applications, the
optical transmission range has been examined for pure and dye

Table 1
FTIR vibrational assignments of pure and dye doped KDP crystals.

Observed FTIR Frequency (cm1)

Pure KDP 0.2 mol% 0.3 mol% 0.4 mol% Vibrational assignments
amaranth + KDP amaranth + KDP amaranth + KDP
3468 3461 3375 3358 OH stretching vibration
2399 2429 2399 2401 POH stretching
1661 1661 1673 1673 O¼POH stretching
1289 1287 1291 1290 P¼O stretching
1082 1081 1082 1084 P¼O stretching
858 857 866 864 POH stretching
537 537 532 530 HOPOH bending vibration
 S. Chandran et al. / Materials Research Bulletin 68 (2015) 210–215 213

doped KDP crystals. High transparency in the visible region is a and it is noted that as the dislocation density increases in crystal,
desirable property for NLO applications. The transmission spectra normally scattering centers also increase [24]. Fig. 3b shows the
of pure and dye doped KDP single crystal are shown in Fig. 3a. From absorbance spectra of amaranth doped crystals. The absorption
the figure, it is clear that pure KDP is highly transparent in UV, range of amaranth doped KDP crystals lies within the wavelength
Visible and near IR region. It is evident that, pure KDP crystal has from 400 to 630 nm. The broad predominant absorption peaks are
high degree of purity and optical quality. The pure KDP crystals observed around 500 nm for 0.3 and 0.4 mol% doped KDP crystals
have higher transmission efficiency than the dye doped KDP single but in the case of 0.2 mol% doped KDP crystal modest absorption
crystals. The transmittance also decreases with increasing the peak is observed in the same wavelength. More absorption on the
amount of dye concentration in KDP, because organic dye 0.3 mol%, 0.4 mol% doped KDP crystals may be due to the high
molecules tend to be absorbed by a positively charged face of incorporation of amaranth in the crystal lattice.
the pyramidal lattice site of KDP crystal [23]. From Fig. 1 it is
observed that, 0.4 mol% amaranth doped KDP has high coloration 3.3. Photoluminescence study
on the pyramidal faces compared to 0.2 mol% and 0.3 mol% doped
KDP. The high concentration of the dye predominantly disturbs The determination and control of point defects in crystals is an
regular sites of lattice and this leads to segregation onto growth essential issue from the application point of view. Dye doped
sectors. Further, it is attributed to more dislocations in 0.4 mol% of crystals show a variety of photochemical and photophysical
amaranth doped KDP crystal. This may be reason for the reduction properties [14]. Photoluminescence spectroscopic analysis is a
in the transmittance. Also, the scattering centers are the reason for sensitive technique to investigate the electronic structure of
the loss of transmittance in 0.4 mol% amaranth doped KDP crystal substances. The intensity and spectral content of the emitted
photoluminescence is a direct measure of various important
material properties, such as recombination mechanisms, impurity
levels and defect detection. The quantity of PL emitted from a
a material is directly related to the relative amount of radiative
110 pure KDP
and non-radiative recombination rates. Non-radiative rates are
0.2 mol% Amaranth+KDP
100 typically associated with impurities and thus, this technique can
0.3 mol% Amaranth+KDP
90 0.4 mol% Amaranth+KDP qualitatively monitor the changes in material quality as a function
of growth and processing conditions. The PL spectrum recorded for
80 the excitation wavelength 454 nm is shown in Fig. 4a. The recorded
Transmittance ( % )

70 PL emission spectrum of amaranth doped KDP crystal in the range

from 510 to 750 nm is given in Fig. 4b. It should be pointed out that
60
for the pure KDP crystals luminescence at room temperature is
50 absent. Luminescence appears only after the dye incorporation
into the KDP crystal. The interaction between KDP and amaranth
40
molecule reveals that the anionic part of the amaranth molecule
30 interacts with the cationic part of the KDP molecule. From Fig. 4b
20
the emission spectra of all amaranth doped KDP crystals are
identical. The prominent emission peaks observed at 683 nm are in
10 close agreement with reported results. The results show that dye
0 doped KDP crystals exhibit red fluorescence emission [25]. It might
be due to proton donor organic dye functional SO3 group and the
200 400 600 800 1000 proton acceptor KDP (K+) group in the host crystal matrix.
Wavelength (nm)
3.4. Vickers microhardness measurement
b 5
The microhardness analysis is the simplest characterization
0.2 mol% Amaranth+KDP technique that can be applied to study the mechanical hardness of
0.3 mol% Amaranth+KDP crystals which is intimately related to their structures such as
4 0.4 mol% Amaranth+KDP
bond strength and crystallographic orientation. The hardness
of the material depends on several parameters such as Debye
temperature, lattice energy, heat of formation and inter-atomic
0.34

0.2 mol% Amaranth+KDP

Absorbance (a.u)

501

3 0.32
spacing [26–28]. For load dependence of Vickers microhardness
Absorbance (a.u)

measurement, the indentation time was constant at 5 s. The

0.30
diagonal lengths of the indented impression were measured for
0.28
different loads varying from 5 to 200 g. The consecutive
2 450 500 550
indentations were made at various sites of the sample surface.
Wavelength (nm)

The whole experiment was repeated several times and the

averages of the values were taken for the calculation. For
1 each load, the microhardness value was calculated using the
expression
P
Hv ¼ 1:8544 2 ½kg mm2 
0 d
200 400 600 800 1000 1200
where Hv is the Vickers hardness number, P is the applied load (kg),
Wavelength (nm) d is the average diagonal length of indentation (mm). The plot of
Fig. 3. (a) UV–vis transmittance spectra of pure and amaranth doped KDP crystals. Vickers hardness (Hv) versus load (P) for the pure KDP and various
(b) UV–vis absorbance spectra of pure and amaranth doped KDP crystals. concentrations of amaranth dye doped KDP crystals is shown in
214 S. Chandran et al. / Materials Research Bulletin 68 (2015) 210–215
Fig. 4. (a) Excitation spectra of pure and amaranth doped KDP crystals. (b) Emission
spectra of pure and amaranth doped KDP crystals.
Fig. 5. It is observed that, compared to pure KDP, hardness value
increases with the increase in the concentration of dye molecules.
The value of hardness predominantly varies at essential changes in
the concentration of amaranth. The calculated microhardness
number of pure KDP and 0.2, 0.3, 0.4 mol% amaranth doped KDP are
94.9 and 129.3, 139.2, 109.5 kg/mm2 respectively. It is observed
from the figure that, while loading with low weights there was not
much difference in the hardness number for the pure and doped
KDP crystals, but when loading with weights above 60 g there was
drastic change in the behaviour of the crystals. In pure KDP above
60 g crack is developed, whereas in the case of amaranth doped
KDP there is a gradual increase of the hardness and no damages has
been observed up to 200 g [10]. It is clear that, the addition of
amaranth in KDP enhances the hardness of the crystals. Hence,
larger hardness value for amaranth doped KDP crystals indicates
greater stress required to form dislocation of the crystals [29]. In
addition, it is observed from Fig. 5, the hardness value of 0.4 mol%
amaranth doped KDP crystal deviates compared with other
amaranth doped samples. This may be due to high incorporation
150
140 pure KDP
0.2 mol% Amaranth+KDP
130 0.3 mol% Amaranth+KDP
0.4 mol% Amaranth+KDP
120
110
Hv (Kg/mm )
2
100
90
80
70
60
50
40
-20 0 20 40 60 80 100 120 140 160 180 200 220
Load P (g)
Fig. 5. Vickers microhardness of pure and amaranth doped KDP crystals.
of amaranth dye entering into crystal lattice and due to this more
dislocations are formed in the 0.4 mol% doped crystal. The crystal
hardness depends on the type of chemical bond involving in the
crystal system. Number of slip systems is involved in the
deformation process during indentation of the crystal surface.
The considerable increase of the hardness is observed in
0.2 mol%, 0.3 mol% doped KDP crystals, whereas exceeding the
dye concentration above 0.3 mol% is not accompanied by the
corresponding rise of the hardness value. The reason for hardness
increase in 0.2 mol%, 0.3 mol% doped KDP crystals are squeezing
of dislocation mobility by dye molecules [30]. These results show
that the limited concentration of dye molecules in the crystal
matrix enhances the properties by occupying the vacancy sites of
the crystals and above certain concentration it produces more
defects in the crystal.
3.5. Laser damage threshold (LDT)
Laser induced breakdown is a common physical process
observed in the crystals when exposed to high intensities of laser
light. So, it is important to know the threshold intensities of the
crystal can withstand without getting damaged [27]. High laser
damage threshold is a significant parameter for NLO crystal. The
LDT of nonlinear optical components depends on physical and
chemical imperfections, especially on growth imperfection and
impurities concentration and segregation [28]. Laser damage
threshold studies are normally carried out by pulsed irradiation.
For this measurement 1.2 mm of the beam was focused on the
crystal with 10 cm focal length lens and 10 Hz of repetition rate was
used. The beam was passed along the plane (1 0 1) surface of KDP
crystals. Experiments were executed by maintaining the directions
of the lens and crystal surface as fixed and increasing the laser
pulse energy until a whitish visible spot was seen at the surface of
the crystal. The laser damage threshold for bulk materials depends
on numerous factors like pulse width, imperfections in the
material, focal spot geometry, growth technique used to crystallize
the sample, wavelength, energy, transverse and longitudinal mode
and so on [31]. Initially 10 mJ was applied on the surface of the pure
and amaranth doped KDP crystals and no damage is seen up to 30 s
and the energy increased to 20 mJ and similar behavior is observed.
Again, in 30 mJ, a small dot like damage is seen in the volume of the
pure and 0.3, 0.4 mol% doped KDP crystals in 20 s. Then, the energy
is slowly increased to 35 mJ, 45 mJ and 55 mJ respectively. When
 S. Chandran et al. / Materials Research Bulletin 68 (2015) 210–215 215

Table 2
Laser damage values of pure and dye doped KDP crystals.

SI no. Energy (mJ) Time (s) Laser damage threshold

Pure KDP 0.3 mol% 0.4 mol%

amaranth + KDP amaranth + KDP
1 10 30 No change No change No change
2 20 30 No change No change No change
3 30 20 Small dota Small dota Small dota
4 35 20 cracked Big dotb Big dotb
5 45 20 – Big dotb Big dotb
6 55 20 – Cracked Cracked

Spot size: a = 0.9 mm, b = 1.05 mm.

the energy reached 35 mJ a clear visible damage is observed and
this energy is noted as threshold energy for pure KDP crystal. In the
case of 0.3, 0.4 mol% doped KDP crystals laser damage was
observed when the energy reached 55 mJ. The experiment was
repeated for 10, 20, 35 and upto 55 mJ no changes were observed in
the crystal upto 20 s. The spot size of the damaged samples was
measured using optical microscope. The measurement errors are
calculated to be 3–5%. The details of observed laser damage
threshold for all prepared samples are given in Table 2. It evidently
shows that the laser damage threshold of the doped samples is
higher than that of the pure KDP sample.
4. Conclusions
The large size single crystals of pure and amaranth dye doped
KDP were grown by slow cooling seed rotation method. For KDP
crystals, luminescence appears only after the dye incorporation
into the KDP lattice sites. It was found that the dye doped samples
acquire a more mechanical hardness as compared with pure KDP
crystals. The higher laser damage threshold value shows that
amaranth doped KDP crystals have high laser damage resistance.
Acknowledgements
The authors would like to thank R. Gopalakrishanan, Anna
University, Chennai, for providing the Vickers microhardness
facility and also thank Dr. K. Venu Gopal Rao, ACRHEM, University
of Hyderabad, for extending the laser damage threshold facilities.
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