Materials Letters 188 (2017) 156–158

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Synthesis and characterization of inorganic nonlinear optical material: MARK

Potassium sodium hydroxide borate hydrate (KSB) single crystal
⁎
C. Ramki, R. Ezhil Vizhi
Materials Research Laboratory, Department of Physics, VIT University, Vellore 632014, India

A R T I C L E I N F O A BS T RAC T

Keywords: Using the slow evaporation solution growth technique, a new compound of potassium sodium hydroxide borate
Solution growth hydrate (KSB) single crystal has been prepared. The title compound crystallized in a noncentrosymmetric
Slow evaporation hexagonal system with P62c space group was confirmed by single crystal X-ray diffraction. The functional group
Electrical bandgap was determined by using FTIR spectrum. The absorption spectrum shows an absorption edge at 265 nm with a
Dielectrics
band gap of 4.68 eV. The melting point of the material was found to be 105 °C using TG/DSC analysis. The
Nonlinear optics
frequency dependence of dielectric, ac conductivity and the relaxation of an ionically conducting crystal have
been studied for different temperatures. Nonlinear optical measurement of the grown crystal can displays a SHG
response which is almost equivalent to that of KDP.

1. Introduction
In the last few decades research interest has been more focussed on
the growth and characterization of inorganic materials for the devel-
opment of nonlinear optical (NLO) materials [1]. Borate crystals have
specially been used in various fields of research due to their potential
applications in ultraviolet (UV) nonlinear materials for frequency
conversion (SHG) and high laser damage threshold. In many borate
systems, including alkali metal, alkaline earth metal, rare-earth and
transition metals have been studied by several scientists. The bid to
design a new variety of borate based NLO crystal is still not possible
due to their complex reaction scheme arising from the richness of
crystal chemistry behind the borate related materials. The borate
crystals so far obtained were generally hydrated in nature at room
temperature and contain hydroxyl groups and exist in isolated struc-
ture [2–5]. In general, alkali-metal borates exhibit a framework
structure made up of BO4 tetrahedral and BO3 triangular [6]. In
several crystalline materials, an additional oxygen atom was attached
in a tetrahedral position surrounded by cations, leading to the existence
of a chemically different type of M-O bonds which shows an interesting
nonlinear effect. In borates, the B-O covalent bonds have no absorption
in the UV region due to their large covalent bond energy. They
generally have a high laser damage threshold, since they possess a
large band gap [7–9]. Based on these ideas, we expect that the
combination of borate group with alkali metal ion will generate a high
efficient NLO material for various applications. In the present work, a
new class of hydrated borate single crystals was grown. In this, the
structure of the crystal is built in the form of layers which are
perpendicular to the hexagonal axis and each layer contains borate
molecules in the material. Colourless, perfectly hexagonal shaped
crystals have been grown and these crystals are stable at room
temperature, which is the advantage of our crystal over the reported
one. The grown crystal was subjected to SXRD, FT-IR, UV, TG/DSC,
Dielectric and NLO studies.
2. Materials synthesis and method
Potassium sodium hydroxide borate hydrate was prepared using
potassium hydroxide, sodium hydroxide, malonic acid (Sigma Aldrich)
and boric acid (AR grade) in the equimolar ratio by slow evaporation
solution growth technique. The reaction between the complex mixture
was continued for 10 h, after which the homogeneous solution mixture
was filtered using high quality whatman filter paper CAT NO 1001 125.
Beautiful hexagonal shaped crystals were obtained in the span of 20
days at room temperature, which shows that the growth rate were
comparatively less and the crystal had a few concentration of point
defects arises from the crystal growth process.
C3H 4 O4
KOH+NaOH + B(OH)3 ⟹ KNaB4 O5 (OH)4 . 3H2 O

⁎
Corresponding author. Tel: +91 416 2202358, fax: +91 416 2243092.
E-mail addresses: rezhilvizhi@vit.ac.in, revizhi@gmail.com (R.E. Vizhi).

http://dx.doi.org/10.1016/j.matlet.2016.11.034
Received 6 October 2016; Received in revised form 6 November 2016; Accepted 9 November 2016
Available online 11 November 2016
0167-577X/ © 2016 Elsevier B.V. All rights reserved.
C. Ramki, R.E. Vizhi Materials Letters 188 (2017) 156–158

Table 1
100 16.04% 3
Unit cell parameters of KSB single crystal. (0.519 mg)
95 2

Heat flow (W/g)

Material a (Å) b (Å) c (Å) V (Å)3 System Space group

Weight (%)
14.55% 1
90
Reported[10] 11.278 11.278 15.806 1741.07 Hexagonal P62c (0.5364 mg) 0
Present work 11.35 11.35 15.90 1776.07 Hexagonal P62c 85
-1
80
-2
3. Results and discussion 75 -3
3.1. Single X-ray diffraction studies 70 -4
Residue: 69.42% (2.560 mg)
65 -5
The unit cell parameters were measured using a Bruker diffract- 100 200 300 400 500 600 700 800
ometer with Mokα (0.710 Å) radiation at room temperature. The single
crystal X-ray diffraction analysis was carried out using direct method Temperature (° C)
and the refinement by full matrix least square technique using SHELXL Fig. 2. TG-DSC curve of the KSB crystal.
program.
The calculated unit cell values of potassium sodium hydroxide 3.4. Thermal analysis
borate hydrate are given in Table 1.
TGA and DSC measurements were carried out in a powder
3.2. Fourier transform infrared spectroscopy analysis (3.687 mg) form of KSB using SDT Q600 V20.9 Build 20. From
Fig. 2, it is clear that the compound has two different weight losses
The presence of the functional groups existing in the grown crystal between 30–700 °C. The first weight loss of about 16.04% is due to the
was recorded between 400 and 4000 cm−1 using the Bruker 66 V FT-IR removal of one crystal water molecule and hydroxyl group in the
spectrometer. The peak at 3429.43 cm−1 represents the O–H stretching structure which leads to a broad endothermic peak at around 105 °C
vibration. The band at 1653 cm-1 is assigned to the H-O-H bending which represents the multiple compound decomposition process as
mode, which confirms the presence of water molecules in the com- shown in the DSC curve [14]. The second weight loss of about 14.5% is
pound. Normally, the trigonal BO3 group shows absorption between attributed to the liberation of one more water molecule from the
1200 and 1500 cm−1. In our results, the absorption is at 1253.73, compound. The total weight loss is 30.54%, which corresponds to the
1328.95 and 1431.18 cm−1, which clearly confirms that the trigonal loss of water molecules and hydroxyl groups in the compound. It is
BO3 groups exist in the material. The band at 935.48 cm−1 is inferred from the TGA curve that the grown crystal can retain its
symmetric stretching of B-O in BO3. The peak at 823.60 cm−1 is stability upto 80°C and the sharp endothermic peak at 105 °C designate
assigned to asymmetric stretching vibration of BO4 tetrahedral [11]. the melting point of the material.
The peaks in the 450–600 cm−1 range correspond to the tetrahedral B-
O bending vibrations. (Fig. 1).
3.5. Dielectric studies

3.3. UV–vis–NIR studies
The optical absorbance of KSB crystal was measured using Perkin-
Elmer spectrophotometer in the wavelength range 200–800 nm at
room temperature. The KSB crystal is found to be very transparent
from 265 to 800 nm, the absorption edge was found to be 265 nm [12].
The wide energy gap of about 4.68 eV is due to the bonding to
antibonding of 2p-B and 2p-O bonds. In addition, the p orbital in the
potassium are actively participate in forming bond with borate system
and therefore increase the angular flexibility of the chemical bonds,
which enhance the NLO properties of the material [13].
100
Transmittance (%)
Dielectric studies of KSB crystal was carried out at different
temperatures (313 K, 323 K, 333 K, 343 K and 353 K) using a
Numetric Q Impedance analyzer in the frequency range 100 Hz - 5
MHz. The effective dielectric response is somewhat similar in all types
of crystals studied. In our case, the variation of dielectric constant with
frequency represents that the material exhibit the electrode interface
polarization process occurs at low resistive grain boundaries in the
material [15]. From the Fig. 3(a) and 3(b), the unexpected fall in the
dielectric constant decreases continuously due to space charge, ionic
and orientation polarization die out at various frequency ranges. We
observe that the dielectric constant decreases with the increase in
temperature which is due to the loss of masses beyond a certain
temperature, which cause thermal fluctuation/change of modes of
bonding vibration, which allows them to orient in the direction of the

90 applied field at higher frequency and temperature [16]. From Fig. 3(c),
we observe two types of conductivity patterns. In a low frequency
1653.00

646.15 715.59

80 range, the conductivity gives a plateau region, which shows the

1253.73

(b) frequency-independent nature of the material. At a higher frequency,

3429.43

70 the plateau region starts increasing due to the dispersion known as

48 1130.29

As grown crystal
557.43
1431.18

hopping frequency. The activation energy (Ea) of the electrical process

1328.95

60 is calculated from the plot between ln σac and the inverse of

temperature using the relation [17]
935.48

50 823.60
9.

(a) σ = σac exp (−EA /kT) (1)

98

4000 3500 3000 2500 2000 1500 1000 500 where σac is the conductivity at temperature T, Ea the activation energy
and k is the Boltzmann constant. The plot of ln σac Vs 1000 T−1 is
Wavenumber (cm-1) shown in Fig. 3(d). The value of the activation energy comes out to be
Fig. 1. (a) Inset shows a photograph of as grown crystal, (b) FTIR spectrum of KSB 0.311, 0.173 and 0.082 eV at the various frequencies 500 kHz, 1 MHz
crystal. and 3 MHz respectively.

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C. Ramki, R.E. Vizhi Materials Letters 188 (2017) 156–158

Fig. 3. (a) log f with εr, (b) log f with tanδ, (c) log f with σac, (d) ln σac Vs 1000 T-1.

3.6. NLO test second harmonic generation (SHG) makes KSB crystal attractive for
continuing research and offers ample scope for the development of the
Considering the non-centrosymmetric nature of the crystal, it is inorganic material for NLO applications.
expected that the KSB crystal will show NLO properties. The Kurtz-
Perry technique was used to calculate the nonlinear optical efficiency of Acknowledgement
the grown crystal [18]. It is well known that the BO3 group in the
material are aligned in the crystallographic direction, which is respon- The authors are thankful to the management, VIT University,
sible for the large SHG effect. In this case, the addition of potassium to Vellore for their constant support and encouragement. Thanks to
the borate complexes increases the bond ionicity, which may be a DST-SERB (SR/FTP/PS-122/2012) Delhi, India for providing financial
consequence of additional polarization in the compound [19]. The support to carry out this work.
second harmonic generation (green light) signal of about 5.6 mV for
KSB and 6 mV for KDP was observed. Consequently, the overall SHG References
efficiency is almost equivalent to that of standard KDP.
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4. Conclusion
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14768.
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potassium and the efficiency was found to be equivalent to that
standard KDP. The characteristic of growing a perfect crystal with

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