Optical Materials 122 (2021) 111730

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

Crystal structure, spectroscopic, crystalline perfection and optical studies of

a potential optical material: Bis-glycine hydrobromide
N. Sivakumar a, *, J. Venkatamuthukumar b, Magesh Murugesan c, Ali Alsalme d
a
Department of Physics, Sri Sairam Engineering College, Chennai, Tamil Nadu, 600 044, India
b
Department of Physics, School of Engineering, Saveetha University, Chennai, Tamil Nadu, 602 105, India
c
Institute of Materials Research, Washinton State University, Pullman, 99163, USA
d
Department of Chemistry, College of Science, King Saud University, Riyadh, Saudi Arabia

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

Keywords: Optically transparent single crystal of Bis-glycine hydrobromide (GHBr) is developed by cost effective slow
Crystal growth solvent evaporation method. The GHBr crystal is tested with X-ray diffraction study to understand the molecular
Optical materials structure. Present material crystallizes in the orthorhombic system with the space group of P212121. Spectro­
Crystal structure
scopic studies like FTIR and FT-Raman are carried out on the crystal to confirm the functional groups and to
Powder diffraction
FTIR and FT-Raman spectra
understand the presence of metal vibrations. Chemical construction of the material is further confirmed by 1H
Optical properties NMR and 13C NMR studies. The optical transmittance and optical band gap energy of the crystal are observed to
be 75% and 5.53 eV respectively. The third order optical nonlinearity analysis are carried out on the crystal using
Z-scan setup and the nonlinear optical susceptibility (χ3) and refractive index (n2) values are estimated to be
1.28 × 10− 6 esu and − 0.96 × 10− 8 cm2/W respectively. The grown crystal is subjected to single shot laser
damage threshold (LDT) study and its value is calculated to be 2.54 GW/cm2.

1. Introduction transparency and thermal stability [7,8]. The combined advantages of

The advanced optical technology requires the single crystals of well
developed morphology and less defect density for the development of
potential optical devices. There is a sustained requirement of single
crystals grown to a state of high purity with structural precision are
urgently needed for various optoelectronic and photonic applications
[1–3]. In particular, the development of nonlinear optical (NLO) single
crystal finds their efficient optical applications in optical parametric
oscillators and laser frequency conversion [4]. NLO efficiency of the
crystals depends on laser conditions, optical transmittance, phase
matching, damage threshold and thermal stability [5,6].
Materials researchers are working on various organic materials
owing to their considerable optical engineering applications like light
modulation, frequency conversion, signal processing and optical
switching. Even though the organic single crystals possess high advan­
tages like molecular flexibility and large polarizability, still they have
weak intrinsic physical properties such as poor mechanical strength,
small size and low optical transparency. Thus, in the recent years, the
developments of semi-organic and metal-organic single crystals have
been concentrated to get improved mechanical stability, optical
both organic and inorganic materials have been identified in the
semi-organic and metal-organic crystals which are attracted towards the
development of potential nonlinear optical effect [9].
The molecular arrangement of amino acids and their interaction with
the metal ions leads to the enhanced optical properties [10]. Amino acid
based single crystals such as L-histidine bromide, L-arginine chloride
monohydrate, L-arginine phosphate, bis-glycine sodium nitrate and
γ-glycine satisfies the basic requirements of NLO engineering such as
wide optical transparency high NLO efficiency and enhanced surface
laser damage threshold [11–15]. Among the amino acids, glycine has
interesting features such as optical, thermal, electrical properties and its
unique hydrogen bond structure which forms many crystal complexes
with various metals and inorganic salts. Because of its easy crystalliza­
tion, moderate optimization condition and polymorphic nature, it at­
tracts the researchers to develop glycine based single crystals and
characterize them to understand their various enhanced physical prop­
erties [16–19].
In the recent reports, it is found that the glycine doped semi-organic
crystal shows improved second harmonic generation efficiency, optical
transparency and mechanical stability [20,21]. The crystal structure,

* Corresponding author.
E-mail address: nsivakumar1986@gmail.com (N. Sivakumar).

https://doi.org/10.1016/j.optmat.2021.111730
Received 30 September 2021; Accepted 22 October 2021
Available online 6 November 2021
0925-3467/© 2021 Elsevier B.V. All rights reserved.
N. Sivakumar et al.
spectral, optical and thermal properties of bis-glycine hydrobromide are
already reported [22–25]. However, there are no systematic studies such
as crystalline perfection, laser light withstanding capacity and light
matter interaction observed on bis-glycine hydrobromide single crystals.
Therefore the present research work deals with the crystalline quality,
improved optical transparency, refractive index measurement and laser
damage threshold effect of the grown GHBr single crystal along with
FT-IR, FT-Raman, NMR and third order nonlinear optical studies.
2. Experimental
2.1. Synthesis and crystal growth
The calculated amounts of glycine (2 mol) and hydrogen bromide (1
mol) are taken in separate beakers. The combination of water and
acetone is identified as suitable solvent. Initially glycine is dissolved in a
mixed solvent and then hydrogen bromide is added gently. The entire
solution is allowed for stirring for about 8 h to get a clear, homogenous
mixture. A Whatmann filter paper with a fine pore size (8 μm, Grade 2) is
used to filter the resulting solution and transferred into a beaker. The
beaker is then covered with a plastic sheet containing microsized holes
for the slow evaporation of the solvent. After the 20 days of solvent
evaporation, the transparent single crystals of dimension 25x3x1 mm3 is
harvested and is used for further characterizations. Fig. 1 shows the
photograph of as-grown GHBr single crystal.
2.2. Characterization
The equipment ENRAF NONIUS CAD4 single crystal X-ray diffrac­
tometer (Mo-Kα, wavelength, λ = 0. 71,073 Å) is used for X-ray
diffraction study and the XRD data are collected. The crystallinity and
crystal system of the sample material is tested by Rich Seifert X-ray
powder diffractometer (Cu-Kα, wavelength λ = 1.5406 Å). Powdered
form of the sample is mixed well with KBr to make a pellet. It is then
subjected to vibrational studies to record the IR spectrum by utilizing
PerkinElmer Spectrum one FT-IR spectrometer in the range from 4000 to
450 cm− 1. The FT-Raman spectrum is also recorded for the sample in the
range between 4000 and 0 cm− 1 using Bruker IFS-88 spectrometer
equipped with Nd3+:YAG diode laser for the excitation. The present
investigation of GHBr grown crystal includes the 1H and 13C NMR study
to understand the chemical structure of the material using Bruker
Advance III 500 MHz spectrometer maintained at 22 ◦ C. DMSO is used as
a solvent in the NMR study. The HRXRD rocking curve of the grown
crystal is recorded in symmetrical Bragg geometry using an x-scan with
triple-axis geometry. A hybrid two-bounce Ge(220) monochromator is
employed to collect the incident X-ray beam on the sample. A triple-axis
three bounce Ge(220) analyzer with a scintillation detector setup is used
to detect the diffracted beam. The UV–Visible spectral study is per­
formed on the GHBr crystal of thickness 1.4 mm, using Varian Cary 5E
UV–Visible Spectrophotometer in the wavelength range of 190–1100
nm. Z-scan technique is employed on the cut polished GHBr single
crystal to understand the third order optical nonlinearity. In this
experiment, diode-pumped Nd;YAG (CW) laser (Coherent Compass™
Fig. 1. As-grown single crystal of GHBr.
2
Optical Materials 122 (2021) 111730
215M − 50) is used with a laser light of wavelength, 532 nm. In the
present research work, a single shot laser pulse is used to the study laser
effects on GHBr crystal. The testing setup containing Q-switched Nd:
YAG laser (λ = 1064 nm) with 10 ns pulse width, power meter and
converging lens are used to estimate the laser damage threshold (LDT)
value.
3. Results and discussion
3.1. Single crystal X-ray diffraction analysis
A GHBr crystal of suitable dimension (0.10 x 0.15 × 0.20 mm3) is
subjected to single crystal X-ray diffraction study to acquire the details
of lattice parameters and its crystal system. The obtained unit cell pa­
rameters values are, a = 8.1934(6) Å, b = 18.3528(13) Å, c = 5.3826(4)
Å and V = 809.39(10) Å3. The grown crystal belongs to orthorhombic
crystal system and shows non-centrosymmetric space group, P212121.
These results are in close agreement with the reported values [25]. The
ortep and packing diagram of GHBr crystal is shown in Fig. 2. The
chemical formula of the crystal is C4H11N2O4Br. The crystal structure
(Fig. 2a) explains that there are two glycine molecules in which one of
them receives additional H+ ion from HBr and thus forms the crystal
structure. The entire molecular system is stabilized through hydrogen
bonds and their connections with the neighboring molecules that are
shown in the packing diagram (Fig. 2b).
3.2. Powder X-ray diffraction study
The powder sample of GHBr is tested with powder X-ray diffraction
analysis and the data is recorded in the 2θ range from 10 to 60⁰. The
resulting powder XRD pattern of GHBr is presented in Fig. 3. All the
intensity peaks are indexed with their (hkl) values. The sharp diffraction
peaks at the various Bargg’s position confirms crystalline quality of the
sample. The XRDA 3.1 software program is employed to estimate the
unit cell parameters and are found to be, a = 8.2391 (4) Å, b = 18.2527
(7) Å, c = 5.2927(3) Å, V = 806.24(3) Å3 and these values are well
matched with the single crystal X-ray diffraction results. Also, this study
confirms that the sample material tends to orthorhombic crystal system
with the space group of P212121.
3.3. FT-IR and FT-Raman spectral analysis
The FT-IR and FT-Raman spectra of GHBr crystal are shown in Figs. 4
and 5 respectively. The observed bands in the recorded region of the
spectra arise from various internal vibrations of glycine, HBr, hydrogen
bonds and lattice vibration which confirms the formation of GHBr
complex.
The broad IR vibrations observed from 3100 to 2400 cm− 1 are
attributed to overlapping of O–H and NH3+ stretching. The IR bands at
3107 and 2886 cm− 1 may be due to N–H stretching and C–H stretching
band vibrations respectively. The peaks in the FT-Raman spectrum at
2995 and 2965 cm− 1 are belongs to CH2 asymmetric and CH2 symmetric
modes. IR bands at 2609, 2166 cm− 1 are due to NH stretching and
N. Sivakumar et al. Optical Materials 122 (2021) 111730

Fig. 2. (a) Crystal structure (ORTEP) and (b) Molecular packing of GHBr single crystal.

Fig. 3. Powder X-ray diffraction pattern of GHBr crystal.

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N. Sivakumar et al. Optical Materials 122 (2021) 111730

Fig. 4. FT-IR spectrum of GHBr single crystal.

Fig. 5. FT-Raman spectrum of GHBr single crystal.

NH⋯O stretching vibrations respectively. The IR bands observed at
1596, 1502, 1391 and 1336 cm− 1 represents COO− asymmetric, NH3+
symmetric bending, CH2 wagging and CH2 twisting vibrations respec­
tively. However, the FT-Raman vibrations appeared at 1668, 1581,
1502, 1440, 1409, 1329 and 1139cm− 1 are corresponding to NH3+
asymmetric bending, COO− asymmetric stretching, NH3+ symmetric
bending, CH2 wagging, COO− symmetric stretching, CH2 twisting and
NH3+ rocking vibrations respectively. The IR band of 1049 cm− 1 is due
to CCN asymmetric stretching and the respective FT-Raman band is
observed at 1046 cm− 1. The symmetric and asymmetric stretching vi­
brations of COO− show the existence of glycine in the zwitterionic na­
ture. Observation of IR bands at 922, 883, 689, 617, 562, 506 cm− 1 are
due to CH2 bending, CC stretching, COO− bending, COO− wagging,
NH3+ torsion and COO− twisting vibrations confirms, glycine in the
complex. The FT-Raman peaks at 893, 690, 506 cm− 1 are assigned to CC
stretching, COO− bending and COO− twisting respectively. The Raman
bands noticed at 155 and 94 cm− 1 are attributed to lattice vibrations in
the GHBr crystal. The assigned wavenumber and the mode of vibrations

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N. Sivakumar et al. Optical Materials 122 (2021) 111730

of both FT-IR and FT-Raman spectra are listed in Table 1.
3.4. NMR spectral analysis
The recorded 1H and 13C NMR spectra of GHBr are depicted in Figs. 6
and 7 respectively. This further supports the chemical structure of the
crystal. In 1H NMR of GHBr crystal, the proton of NH2 in glycine has its
chemical shift (δ) at 3.540 ppm and it is shifted to 3.407 ppm in the
complex. The chemical shift at 3.327 and 2.945 ppm are attributed to
amine (NH2) and methylene (CH2) protons of GHBr crystal. The multi­
plets in the range 2.527–2.501 ppm are due to the residual protons of
DMSO (Deutrated) [26].
The 13C NMR of methylene (CH2) carbon of α-glycine and γ-glycine is
observed at 42.6 and 41.38 ppm respectively [27,28]. But in the case of
GHBr crystal, the multiple peaks are observed in the range
40.610–40.011 ppm and corresponding to the methylene carbon of
synthesized material and the δ values in the multiplet 39.844–39.510
ppm is due to DMSO solvent. Thus the change in chemical shift clearly
affirms the formation of GHBr crystal.
3.5. High Resolution XRD analysis
The crystalline perfection is directly associated with the physical
properties of the materials like optical transparency, relative second
harmonic generation (SHG) efficiency, dielectric and fluorescence ef­
fect. Such kind of physical properties can be upgraded as the crystal
quality improves [29]. Fig. 8 represents a sharp rocking curve (RC) with
FWHM (full width at half maximum) of 243 arc sec. This value is
approximately close to the expected value for a perfect crystal [29].
The single peak of RC reveals that the absence of structural grain
boundaries in the grown crystal [30]. Also, the well defined rise and fall
of intensity on either side of the Bragg’s position shows the presence of
less defect density and agglomerations in the grown crystal [31]. On
close observation of RC accordance with the zero peak position, it is
interesting to note that the scattered intensity is little more in the +ve
side than that of –ve side. This is endorsed that the crystal contains
chiefly interstitial type of defects compared with vacancy defects. This
kind of defect leads to compressive stress in the grown crystal and de­
creases the interplanar spacing (d). The more scattering intensity of
Table 1
FT-IR and FT-Raman band assignments of GHBr crystal.
Wavenumber (cm− 1)
X-ray at slightly higher angles [32] shows that these defects are more or
less statistically distributed. Instead, the strain generated in the crystal
leads to cracks or structural grains that can be observed in the HRXRD
curve [32]. Parameters like growth process and thermodynamic condi­
tions are also result in the generation of point defects which cannot be
avoidable up to some extent [33]. However, the HRXRD curve of GHBr
does not show any additional peak which suggests that the absence of
clustering of point defects at bulk level and this can not affect the device
performance.
3.6. Optical studies
The recorded optical transmittance spectrum of plated GHBr crystal
without any antireflection coating/polishing is shown in Fig. 9a. It is
noted that the crystal posses large optical transparency (65%) in the
total visible region along with a lower cut-off wavelength of 238 nm.
3.6.1. Band gap energy calculation
Estimation of optical band gap energy and the linear refractive index,
characterizes the optical and electrical properties of the single crystals.
Similarly, the calculation of optical absorption co-efficient provides the
information about band structure and the type of electronic transitions
in the optical materials.
The optical absorption coefficient is estimated according to the
equation,
1
[ ]
1
α = log 10 (1)
t T
where T - Optical transmittance in % and t – thickness of crystal in mm.
The standard Tauc’s formula which relates the absorption coefficient
(α) and optical photon energy (hυ) is given by,
( )1/2
αhυ = β hυ − Eg (2)
Where α - absorption coefficient, hυ - the incident photon energy in eV,
Eg -optical band gap energy in eV and β - the materials constant.
Fig. 9b shows a plot of (αhυ)2 vs. photon energy (eV) of the as-grown
GHBr single crystal. The optical band gap energy is obtained by
extrapolating a straight line to the energy axis ((αhυ)2 = 0). From the
figure (Fig. 9b), the optical band gap energy is estimated to be Eg = 5.53
eV. Therefore, the single crystal of GHBr with large optical transparency
and wide band gap energy confirms its aptness for various opto-
electronic device performances [33,34].

FT-IR Raman Assignments 3.6.2. Refractive index estimation

3107 NH stretching The measurement of refractive index is an essential requirement for
2886 CH stretching any optical waveguide applications and optical device fabrication. The
2995 CH2 asymmetric stretching
light matter interaction play a major role in the calculation of refractive
2965 CH2 symmetric stretching
2609 NH stretching index of the optical material. Thus, the optical transmittance spectrum
2166 NH⋯O stretching of GHBr (Fig. 9a) is used for the calculation of optical refractive index.
1596 COO− asymmetric stretching The standard equation for the measurement of optical reflectance (R)
1668 NH3+ asymmetric bending and the refractive index (n) are given by,
1581 COO− asymmetric stretching
1502 1502 NH3+ symmetric bending
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
exp( − αt) ± exp( − αt)T − exp( − 3αt)T + exp( − 2αt)T 2
1391 1440 CH2 wagging R= (3)
1336 CH2 twisting exp( − αt) + exp( − 2αt)T
1409 COO− symmetric stretching √̅̅̅
1329 CH2 twisting − (R + 1) ± 2 R
1132 1139 NH3+ rocking n= (4)
(R − 1)
1049 1046 CCN asymmetric stretching
922 CH2 bending It is understood that the optical constants (R, n) are turn on ab­
883 893 CC stretching
sorption coefficient and transparency of the optical materials. The un­
689 690 COO− bending
617 COO− wagging derstanding of reflectance, transmittance, absorption and refractive
562 NH3+ torsion index are highly essential to enhance the internal quality of the mate­
506 506 COO− twisting rials. By regulating the optical band gap energy and the absorption co­
155 Lattice vibrations efficient, we can able to find a suitable material for efficient device
94 Lattice vibrations
performance.

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N. Sivakumar et al. Optical Materials 122 (2021) 111730

Fig. 6. 1H NMR spectrum of GHBr single crystal.

13
Fig. 7. C NMR spectrum of GHBr single crystal.

Fig. 10 shows the refractive index profile of GHBr single crystal. The
plot shows the dispersive nature of the refractive indices in the lower
wavelength region and is almost uniform in the higher wavelength re­
gion that designates the nonappearance of local absorption bands. Of
course, optical material with constant refractive index is a significant
condition in choosing the materials for the rudiments of high-
performance lenses, acousto-optic devices and coherent optics. Thus,
GHBr crystals with large optical transparency, potential refractive index
and low absorbance are suitable for antireflection coating in photovol­
taic and other optoelectronic devices [35].
3.7. Z-scan studies
Z-scan method is a simple experimental setup designed by Shiek
Bahae et al. to estimate the optical nonlinearity with greater accuracy
[36]. In the present setup all the optical factors such as nonlinear
refractive index (n2), nonlinear absorption co-efficient (β) and nonlinear
optical susceptibility χ(3) are measured with a laser pulse of power, 50
mW. A stepper motor attached with a Z-scan setup is used to change the
position of the sample along the axial direction (+Z to –Z). Therefore the
sample is allowed to experience various laser light intensities at different
positions. A digital power meter is connected to the photo detector
measures the transmitted laser light intensity. Fig. 11 represents the

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N. Sivakumar et al. Optical Materials 122 (2021) 111730

Fig. 8. HRXRD Curve of GHBr single crystal.

Fig. 9. (a) UV–Vis.-NIR transmittance spectrum and (b) Tauc’s plot for the estimation of optical band gap energy of GHBr single crystal.

experimental plots of closed aperture, open aperture and Z-scan ratio
modes of GHBr single crystal. The open and closed Z-scan modes are
used to estimate the nonlinear optical absorption co-efficient (β) and
nonlinear optical refractive index (n2) of the optical materials.
Z-scan closed aperture plot of GHBr is shown in Fig. 11a. The trend of
closed Z-scan curve (peak followed by valley) shows the negative optical
nonlinearity of the crystal that leads to the self defocusing effect. This is
attributed to the internal refractive index changes with respect to tem­
perature [37]. The localized absorption of laser beam develops spatial
distribution of temperature. This causes the spatial variation of refrac­
tive index of the material which in turn results in phase distortion of
laser beam that passes through the crystal. The negative nonlinear
refractive index of crystal is an essential requirement for optical sensors
as well as night vision devices [38].
The open Z-scan experiment is performed without using aperture to
collect the transmitted laser beam. The obtained data is not much sen­
sitive to nonlinear optical refraction and hence the plot is anticipated to
be symmetrical about the focus. A plot of open aperture Z-scan with
minimum (valley) and maximum (peak) transmittance value indicates
the multi-photon absorption and saturable absorption respectively [39].
In the present study, open Z-scan plot of GHBr crystal shows saturation
of absorption with most transmittance and is shown in Fig. 11b. The

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N. Sivakumar et al. Optical Materials 122 (2021) 111730

Fig. 10. Refractive index profile of GHBr single crystal.

value of effective nonlinear refractive index (n2) can be estimated using ( )

ε0 C2 n0 2 λβ (cm)
Z-scan ratio curve as shown in Fig. 11c. Imχ (3) (esu) = 10− 2
(11)
4π 2 W
The obtained Z-scan data is used to find out the measurable quantity
(ΔTp-v) as a function of on axis phase shift and is given by, where ε0 – vacuum permittivity (8.854 x 10–12C2 N-1 m-2), n0 - linear
ΔTp− v = 0.406(1 − S) 0.25
|Δφ| (5) refractive index (2.33) and c - velocity of light (3x108 ms-1). The third-
order nonlinear optical susceptibility of the crystal is calculated by
( ) √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
− 2ra 2
S = 1 − exp (6) χ (3) (esu) = (Re(χ (3) ))2 + (Im(χ (3) ))2 (12)
2ωa

where ΔΦ – on axis phase shift, S - aperture linear transmittance, ra - The third-order nonlinear susceptibility χ(3) of the GHBr crystal is found
radius of the aperture in mm and ωa - beam radius at the aperture in mm. to be 1.28 × 10− 6 esu and is attributed to the large number of delo­
The nonlinear refractive index (n2) and the effective thickness of the calized π-electron derived from the protonation of amino group in the
crystal (Leff) are estimated using the following equations [36,39], crystal structure [42]. Such kind of delocalization improves the molec­
ular polarizability which leads to greater third order NLO optical ac­
Δφ
n2 = (7) tivity [43]. The obtained results of Z-scan measurements are listed in
kI0 Leff Table 2 and some of the important results are compared with the re­
( ) ported values (Table 3) [44,45].
1 − exp( − αL)
Leff = (8)
α
3.8. Surface laser damage threshold (LDT) study
where k = 2λπ, I0 - intensity of the laser (at Z = 0), L - the thickness of the
sample in mm and α -the linear absorption coefficient. The study of laser withstanding capacity on the crystal surface plays
Open aperture Z-scan data is used for the calculation of nonlinear a vital role in fabrication of electro-optic modulators, NLO devices and
absorption coefficient according to the formula [40], optical waveguides [33,46]. The measurement of laser damage
√̅̅̅ threshold (LDT) study depends on various optical parameters such as
2 2ΔT laser irradiance, repetition rate, pulse duration, beam size and experi­
β= (9)
I0 Leff mental arrangements. The optical efficiency of the single crystals under
this study is limited for its use in many NLO activities [47]. Therefore, in
The + ve and –ve values of β represents the two photon absorption
the present research work, a single shot laser pulse is used to the study
and saturable absorption processes. In the present investigation, the
laser effects on GHBr single crystal. A size of laser beam on the crystal
estimated value of β is − 1.36 10− 4 cm/W which reveals the saturable
surface is measured to be 1mm and a repetition rate of 10 Hz is used for
absorption process of the crystal. This phenomenon further supports the
this analysis. The input laser energy density is recorded by a power
results of open Z-scan plot of GHBr crystal. The real and imaginary third-
meter and a controlled output laser light intensity is made to fall on the
order nonlinear optical susceptibility χ(3) can be calculated using the
crystal surface placed close to the converging lens. Thus, the laser power
experimentally determined values of β, n2 and no according to the
density is calculated according to the formula,
equations [41],
( )( ) E
ε0 C2 n0 2 n2 cm2 Pd = (13)
Reχ (3) (esu) = 10− 4 (10) τA
π W

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N. Sivakumar et al. Optical Materials 122 (2021) 111730

Fig. 11. (a) Z-scan closed aperture, (b) Z-scan open aperture and (c) Z-scan ratio plots of GHBr single crystal.

Table 2 Table 3
Results of Z-scan measurement on GHBr single crystal. Comparison of Z-scan results of GHBr with reported materials.
Parameters GHBr Z-scan GHBr [present] α-Glycine [44] γ-Glycine [45]
− 1 parameters
Linear absorption coefficient (α) ×m 244.666
Nonlinear optical refractive index (n2)×10− 8 cm2/W − 0.96 n2 − 0.96 × 10− 8 2.1445 × 10− 8 − 4.44 × 10− 6
Nonlinear optical absorption coefficient (β) ×10− 4 cm/W − 1.36 cm2/W cm2/W cm2/W
Linear refractive index (no) 2.33 β − 1.36 × 10− 4 cm/ 2.4763 × 10− 5 0.00527 cm2/W
Real part of the third-order susceptibility [Re(χ(3))]×10− 6 esu 0.97 W cm2/W
Imaginary part of the third-order susceptibility [Im(χ(3))]×10− 6
esu 0.84 χ(3) 1.28 × 10− 6 esu 8.018 × 10− 8 esu 2.863 × 10− 4
esu
Third-order nonlinear optical susceptibility (χ(3))×10− 6 esu 1.28

Where, E − laser energy in mJ, τ - pulse width in ns and A - area of the
circular spot size in mm2. A single shot pulse, surface laser damage
image of GHBr single crystal is presented in Fig. 12. The LDT value of
GHBr single crystal is estimated to be 2.54 GW/cm2. This is quite large
when compared to the standard NLO materials like KDP (0.2 GW/cm2)
and urea (1.5 GW/cm2) [48]. Therefore, the single crystals of GHBr can
find useful applications in the field of high-power lasers and other po­
tential optical devices.
4. Conclusion
Single crystal of Bis-glycine hydrobromide (GHB) is grown by solu­
tion growth technique. Single crystal X-ray diffraction study confirms

9
N. Sivakumar et al.
Fig. 12. Image of surface laser damage of GHBr single crystal (single shot pulse).
the orthorhombic crystal system with the space group of P212121.
Chemical structure of the crystal is confirmed by FTIR, FT-Raman and
1 [9] S. Dhanuskodi, J. Ramajothi, Cryst. Res. Technol. 39 (7) (2004) 592–597.
H NMR and 13C NMR studies. UV–Vis. NIR spectrum shows large op­
tical transparency of about 75%. The Z-scan experimental set up is used
to estimate the nonlinear optical susceptibility (χ3) and refractive index
(n2) values. Surface laser damage threshold test is employed on the
grown crystal is calculated to be 2.54 GW/cm2. Thus the large optical
transparency (75%), wide optical band gap energy (5.33 eV), better
refractive index (2.1), potential third order nonlinear optical suscepti­
bility (1.28 × 10− 6 esu) and excellent surface damage threshold value
(2.54 GW/cm2) of the grown single crystal of GHBr find its suitability in
various opto-electronic and photonic applications.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
One of the authors, Dr. N. Sivakumar, expresses his acknowledge­
ment to Researchers Supporting Project (RSP-2021/78), King Saud
University, Riyadh, Saudi Arabia.
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