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Journal of Minerals & Materials Characterization & Engineering, Vol. 11, No.6, pp.597-607, 2012
jmmce.org Printed in the USA. All rights reserved
Growth and Characterization of New Non Linear Optical Bis-Glycine
Hydro Bromide (BGHB) Single Crystal
S. Sampthkrishnana *, N. Balamuruganb, R. Kumuthac, Y. Vidyalakshmid, S. Muthua
a Department of Physics , Sri Venkateswara College of Engineering, Sriperumbudur, India.
b Department of Physics, PERI Institute of Technology, Chennai-600 048, India.
c Department of Physics, JAYA Engineering College, Chennai, India.
d Departments of Physics, MIT, Anna University, Chennai-48.
*Corresponding Author: Sambathk@svce.ac.in, firstname.lastname@example.org
A new non linear optical material, Bis-Glycine Hydro bromide (BGHB), has been synthesized.
Single crystals of BGHB have been grown successfully by slow evaporation method. The
solubility of the material was measured in various solvents such as ethanol, acetone and water.
It was found to have extremely low solubility in ethanol and acetone. The grown crystals were
characterized by recording the powder diffraction and identifying the diffracting planes. Using
single crystal diffractometer the morphology of BGHB crystal was identified. Fourier transform
infrared (FTIR) spectroscopic studies, optical behavior such as UV-visible-NIR absorption,
Thermogravimetic (TG) and differential scanning calorimetric (DSC) analyses have been
performed to show that BGHB is thermally stable up to 168.5oC and there is no phase transition
and decomposition till 168.5oC. Anisotropy in the hardness behavior has been observed while
measuring at different crystal planes by Vicker hardness test.
Key words: Solubility, Grown from solution, Crystal structure, FT-IRspectroscopy, Micro
In the technological society, development of new devices has been introduced through the
growth of single crystals. Crystals for practical and technological applications should have a well
developed morphology and contain low density of defects predicted by thermodynamic and
598 S. Sampthkrishnan, N. Balamurugan Vol.11, No.6
kinetic parameters which determine the growth mechanism and the growth kinetics and the
generation of defects respectively. This method is extremely popular in the production of many
technologically important crystals. Much organic and inorganic crystal can be grown using this
technique . Most of the organic NLO crystals usually have poor mechanical and thermal
properties and are susceptible for damage during processing even though they have large NLO
efficiency. Also, it is difficult to grow larger size optical-quality crystals of these materials for
device applications. Purely inorganic NLO materials have excellent mechanical and thermal
properties, but possess relatively moderate optical nonlinear property because of the lack of
extended π-electron delocalization [2, 3]. L-Cysteine hydrochloride , L-Histidine
hydrochloride , L-Histidine tetrafluroborate , L-Histinium bromide , L-Histidine
hydrofluride dehydrate  and L-Glutamic acid hydrocholoride (GHC)  are some examples of
semiorganic amino acid-related NLO materials reported recently. Presently, the single crystals of
a new semiorganic NLO material viz., Bis-Glycine hydrobromide (BGHB) have been grown by
slow evaporation method. In the present work, the solubility of BGHB was measured in different
solvents. The growth aspects, morphology, the results of the XRPD and FTIR analysis have been
discussed. The differential scanning calorimeter (DSC), DifferentialThermalAnalysis (TGA),
thermogravimetric (TGA) analysis and SHG efficiency of the powdered materials was measured
by using the Kurtz and Perry method . Measurements of microhardness are also reported.
2. EXPERIMENTAL PROCEDURE
2.1 Crystal Growth
High purity Glycine salt (E-merck) and hydrobromic acid (E-Merck) were taken in the molar
ratio 2:1 in deionized water to synthesis BiGlycine Hydrogen Bromide salt. The pH of the
solution was adjusted to be 2 and the growth experiment was maintained at 318K. The saturated
BGHB solution of pH 2 has been prepared using doubly recrystallised salt. The solution was
filtered using sintered glass filter 1µ porosity. The filtered solution was transferred into the petty
disc and allowed to evaporate slowly at room temperature. Transparent and flawless crystals
size: (22 x 6 x 8) mm3 were obtained after 10 days as shown in the Figure (1).
2.2 Solubility of BGHB
The solubility of BGHB was measured for different solvents (ethanol, methanol and acetone) by
gravimetrical analysis method. Water has been selected as a solvent, because the solubility of
BGHB is more in water compared with other solvents. The aqueous solution of recrystallised
BGHB was prepared and maintained at constant temperature with continuous stirring to ensure
homogeneous temperature and concentration over the entire volume of the solution. On reaching
saturation, the content of the solution was analyzed gravimetrically. The same procedure was
repeated for various temperatures such as 300C, 350C, 400C, 450C and 500C. The plotted
Vol.11, No6 Growth and Characterization of New Non Linear Optical 599
solubility curve is as shown in the figure (2). From the figure, it is evident that the solubility
increases with increase in temperature.
Fig.1: Photograph of BGHB crystal.
Fig.2. Solubility spectrum of BGHB single crystal
3.1 Structure Elucidation using Single Cry st a l X - r a y D i f f r a c ti o n
Single crystal powder X-ray diffraction pattern was recorded using a Siemens D500
diffractometer at room temperature (293K) with CuKa (X = 1.5418A) radiation for structural analysis
of Bi-Glycine Hydrogen Bromide and the lattice parameters were calculated.
To know the optical transparency of the grown crystal, the UV_Vis absorbance spectrum of
BHGB was recorded.using a carry 5E UV_Vis_NIR spectrophotometer. In the range between
200 and 2000nm
600 S. Sampthkrishnan, N. Balamurugan Vol.11, No.6
3.3 FT-IR Spectroscopic
The FTIR spectrum of BGHB crystals was recorded in the range near 2000 - 1800 cm-1by
employing a Brukker IFS66 V FTIR spectrometer by KBr pellet technique to study the presence
of glycine in the sample qualitatively.
3.4 Microhardness Studies
Microhardness measurements were carried out on BGHB crystal using a Leitz Weitzler hardness
tester fitted with a diamond pyramidal indentor. The well polished crystal moulted on the
platform of microhardness crystal and loads of different magnitudes (5, 10, 20, 30, 40, and 45)
were applied over a fixed interval of time. The indentation time was fixed as 5s.
3.5 Thermal Analysis
Thermal analysis was used to find out the weight loss (TGA) and energy change (DTA) in the
sample with respect to the temperature. The thermal analysis was carried out on the powder
specimen of BGHB by employing a MettlerToledoStar simultaneous DTA/TGA analyzer at
10oc/min heating rate in the nitrogen atmosphere by using an alumina crucible.
4. RESULTS AND DISCUSSION
4.1 Crystal Morpholo g y & S ingle Crystal X-ray Structure Analysis
Morphology measured using single crystal XRD reveals that there are well- developed faces
(102) and their freidels. The indices of the faces are shown in fig (3). In all grown crystals, the
most prominent face is (0 1 2). The width of the crystal is in the C direction. To identify the
morphology of the grown crystal, the Single crystal XRD was taken and the data were collected
using an ENRAF NONIUS CAD4 automatic X-ray diffractometer.
The physical crystal had the shape of parallelepiped. The line of intersection of the faces (012)
and (01-2) is length of the crystal. The line of intersection is (a*+ b*+ 2c*) x (0a* + b*-2c*) = -
4v*a. Hence it is inferred that the length of crystal is a -direction which is also the shortest unit
cell axis of the crystal. (010) and (001) planes are not morphologically developed.
The XRD pattern and diffraction indices of the crystal are shown in Fig. 4. The XRPD pattern
showed that the synthesized material and the as grown crystals are the single phase of BGHB.
The orthorhombic unit cell parameters calculated by TREOR program are a=5.39A0, b=8.18A0,
c=18.39A0, α=90.180, β=89.880, γ=89.990 and V=812.4A03, which are comparable with the
results determined by a R3m/E four circle X-ray diffractor .
Vol.11, No6 Growth and Characterization of New Non Linear Optical 601
Fig. 3: Morphology of the grown BGHB crystal
10 20 30 40 50 60 70 80 90
(4 0 5)
(3 2 5)
(0 4 5)
(1 4 3)
(2 0 7)
(0 0 9)
(1 2 6)
(0 0 8)
(1 3 2)
(2 0 3)
(1 2 3)
(1 2 2)(1 1 4)
(1 0 5)
(1 0 4)(0 2 2)
(0 2 1)
(0 0 4)
intensity (a r b. units)
Fig. 4: Powder XRD pattern of BGHB single crystal
4.2 UV-Vis –NIR Spectrum
The UV-Vis-NIR transmission spectrum (Fig. 5) of the crystal was reorded in the range: 200 –
2000nm using carry 5E UV-Vis_NIR spectrophotometer. It is seen that a strong absorption band
occurs at 750 nm and this absorption is due to the n->π* transition. The lower cutoff wavelength
occurs at 250 nm & 1600 nm is due to π->π* transition . After that, no absorption takes place
in the entire visible region.
2 -1 1
(0 1 -2)
(0 1 2
1 0 0
602 S. Sampthkrishnan, N. Balamurugan Vol.11, No.6
Fig.5: UV-vis-NIR spectrum of BGHB single crystal
4.3 FT-IR Studies
To identify the elements and the functional groups present in the grown crystal qualitatively, the
FTIR spectra were obtained using Brukker IFS66 V FTIR spectrometer by KBr pellet technique.
In the FTIR spectrum shown in Figure (6), there is a broad band between 2000 and 3500 cm-1.
The sharp peak at 3429, 3113 and 2897 cm-1 may be assigned to NH3+ stretching band. The
peaks at 2694 cm-1 and 2601 cm-1 are attributed to the C-H stretching mode vibration. The
overtone region contains a band near 2000 - 1800 cm-1 which is assigned to the combination of
the asymmetrical NH3+ bending and the torsional oscillation of the NH3+ groups. The intense
peaks at 1743, 1715 and 1125 cm-1 indicate the C= O stretching of the COO- group. The
asymmetric and symmetric stretching mode of COO- groups are reached by peaks at 1616,
1497, 1446, 1335 and 1254 cm-1. This observation confirms that one glycine is existing in
zwitterionic form the peak at 671 cm-1 is due to N-H out-of-plane bending vibration. The
torsional oscillation of NH3+ is revealed by the peak 540 cm-1. The strong carbonyl absorption at
1743 cm-1 characterizes α-amino acid hydro bromides.
4000 3000 2000 10000
W ave number (cm-1)
Fig .6.FTIR spectrum of BGHB single crystal
Vol.11, No6 Growth and Characterization of New Non Linear Optical 603
4.4 Micro Hardness Studies
Micro hardness measurements were carried out on BGHB crystals. Smooth surface of BGHB
was subjected to the Vickers static indentation test at room temperature (303k) using a Leitz
Wetzlar hardness tester fitted with a Vickers diamond pyramidal indenter. Loads of different
magnitudes (5, 10, 20, 30, 40 and 45g) were applied over a fixed interval of time. The
indentation time was kept as 5 s for all the loads. The Vicker micro hardness number was
evaluated from the relation
Hv = (1.6180 p)/ d2 kg / mm2 (θ = 1080)
(Where p is the applied load in kg and d is the diagonal length of the indentation impression in
Load P(gram )
Fig. 7: Micro hardness spectrum of BGHB single crystal
4.5 Second Harmonic Generation
The Kurtz powder SHG test confirms the NLO property of the grown BGHB crystals . The
relative conversion efficiency was calculated from the output power of BGHB crystals with
reference to BGHB and KDP crystals output power for various input powers. Table 1 shows the
relative conversion efficiency of BGHB crystals for output power. It is observed that the
conversion efficiency of BGHB is equal to that of KDP crystals.
604 S. Sampthkrishnan, N. Balamurugan Vol.11, No.6
Table 1: SHG Conversion of KDP, BGHB
Output power i n Watt Relative conversion
efficiency (SHG in %) of
0.6 0.75 125
0.8 0.99 123.5
1 1.16 116
1.2 1.49 125
1.3 1.76 135.4
5. THERMAL STUDIES
5.1 Thermal Gravimetric Analysis
In order to find the thermal properties of the grown BGHB crystal, Thermo gravimetric analysis
(TGA), and Differential thermal analysis were carried out for BGHB crystal. The TGA were
carried out between 25 0C and 1400C in nitrogen atmosphere at a heating rate of 100 C/min
using NETZSCH STA 409 C. The fig (8) shows the resulting traces of the grown crystal.
0200 400 600 800100012001400
Fig.8: TGA Spectrum of BGHB single crystal
Vol.11, No6 Growth and Characterization of New Non Linear Optical 605
5.2 Differential Thermal Analysis
In order to find the thermal properties of the grown BGHB crystal, Differential thermal analysis
(DTA) were carried out for BGHB crystal. The DTA were carried out between 25 0C and 1400C
in nitrogen atmosphere at a heating rate of 100 C/min using NETZSCH STA 409 C. The Fig (9)
shows the resulting traces of the grown crystal.
05001000 1500 2000 2500 3000
Temperature (degree celcius)
Fig.9: DTA Spectrum of BGHB single crystal
5.3 Differential scanning calorimetry (DSC)
In order to find the thermal properties of the grown BGHB crystal, Differential Scanning
Calorimetry (DSC) were carried out for BGHB crystal. Show the resulting traces of the grown
crystal. The differential scanning Calorimetry (DSC) of BGHB was also carried out between
200C and 2000C at a heating rate of 100C / min in nitrogen atmosphere using NETZSH DSC
Z04. It is shown in the Fig (10).
606 S. Sampthkrishnan, N. Balamurugan Vol.11, No.6
20406080100 120 140 160 180 200 220
Fig.10.DSC Spectrum of BGHB single crystal
Bulk single crystals of Bi-Glycine Hydrogen Bromide (BGHB) have been successfully grown by
the slow evaporation technique from the aqueous solution. The solubility curves for the BGHB
in de-ionised water, ethanol and methanol at various temperatures have been determined. From
the solubility curve, it is concluded that polar solvent like water is opt for growing a bulk size
crystal. It is observed from the morphology studies that the growth rate along c direction is faster
than other directions. Optical transmission studies confirm that the grown BGHB is transparent
in the entire visible region and the FTIR trace reveals the presence of amino groups and
functional groups. The NLO studies were carried out and compared with KDP. It is found that
the efficiency of BGHB is slightly higher than that of KDP. It is evident from the thermal studies
that the crystal is thermally stable up to 168.50C and there is no phase transition and
decomposition till 168.50C. Anisotropy in the hardness behavior has been observed while
measuring at different crystal planes by Vicker hardness test
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