This article appeared in a journal published by Elsevier.

The attached
copy is furnished to the author for internal non-commercial research
and education use, including for instruction at the authors institution
and sharing with colleagues.
Other uses, including reproduction and distribution, or selling or
licensing copies, or posting to personal, institutional or third party
websites are prohibited.
In most cases authors are permitted to post their version of the
article (e.g. in Word or Tex form) to their personal website or
institutional repository. Authors requiring further information
regarding Elseviers archiving and manuscript policies are
encouraged to visit:
http://www.elsevier.com/copyright
Author's personal copy
Crystalline perfection, optical and dielectric studies on L-histidine nitrate:
A nonlinear optical material
B. Riscob
a
, S.K. Kushwaha
a
, Mohd. Shakir
a
, K. Nagarajan
b
, K.K. Maurya
a
, D. Haranath
c
, S.D.D. Roy
c
,
G. Bhagavannarayana
a,n
a
National Physical Laboratory (CSIR),Dr. K.S. Krishnan Road, New Delhi 110012, India
b
Deptartment of Physics, PSG College of Arts and Science, Coimbatore 641015, Tamil Nadu, India
c
Department of Physics, Nesamony Memorial Christian College, Marthandam 629165, India
a r t i c l e i n f o
Article history:
Received 14 December 2010
Received in revised form
29 August 2011
Accepted 1 September 2011
Available online 7 September 2011
Keywords:
Crystal growth
Optical materials
Photoluminescence spectroscopy
Optical properties
Raman spectroscopy and scattering
Dielectric properties.
a b s t r a c t
Single crystals of L-histidine nitrate (LHN), a recently investigated nonlinear optical material, were
grown by conventional solution technique. Crystal structure and vibrational modes of the grown
crystals were conrmed by powder X-ray diffractometry and FT-Raman spectrometry, respectively.
Crystalline perfection of the grown crystals was evaluated by employing an in-house developed high-
resolution X-ray diffractometer (HRXRD) and it was found that the grown crystals were free from
structural grain boundaries and the perfection was reasonably good. However, HRXRD could reveal the
fact that the crystals contain predominantly the interstitial point defects. The birefringence was
measured over a range of wavelength between 5480 and 5630

A and it was found that its value is
nearly constant and 10 times higher than that of KDP. The optical band gap was found to be 3.73 eV.
The photoluminescence excitation and emission spectra for single crystals were recorded. The SHG
efciencies of LHN samples of different particle sizes were measured by the Kurtz and Perry technique
and they removed the ambiguity in the values reported differently in the literature. Dielectric
properties were studied as a function of temperature over a wide range of frequency. The optical
and dielectric studies along with the crystalline perfection reveal that the LHN crystal could be a good
candidate for nonlinear optical devices.
& 2011 Elsevier B.V. All rights reserved.
1. Introduction
Due to unique properties the nonlinear optical (NLO) single
crystals have promising applications in the area of photonics such
as high-speed information processing, frequency conversion, opti-
cal communication, high optical disk data storage, etc. [14].
Birefringent crystals are key materials for optical isolators, circu-
lators and beam displacers needed for devices for optical commu-
nication [5]. Up to now several hundreds of donors and acceptors
substituted delocalized P electron systems have been reported,
which show NLO properties. In this respect, amino acids are also
found to be interesting materials for NLO applications. The
importance of amino acids for NLO application lies in the fact that
almost all amino acids contain an asymmetric carbon atom and
crystallize in non-centrosymmetric space groups. Therefore in the
recent years many amino acid materials such as L-arginine maleate
dihydrate (LAMD), L-histidine hydrochloride monohydrate, L-argi-
nine formomaleate (LAFM), L-valinium fumarate (LVF), etc. [69]
with good NLO efciency have been synthesized and their single
crystals have been grown and characterized. To date, the birefrin-
gent crystals widely used are the natural calcite and YVO
4
.
However, calcite crystal has serious problems of optical inhomo-
geneity, small size and difculty to process precisely due to its
cleavability, while YVO
4
crystals with large size and high quality
are difcult to obtain [10,11]. It is therefore necessary to search for
a new birefringent crystal having high quality, large size, good
chemical stability and mechanical workability.
The present material LHN is a known NLO material, crystallizes
in orthorhombic crystal structure with space group P2
1
2
1
2
1
and
on this material few other studies were also reported like FT-IR,
FT-Raman, mechanical, thermal and room temperature dielectric
behavior [1214]. However, to the best of our knowledge, there
are no report(s) on crystalline perfection, birefringence and
optical studies like band gap, photoluminescence, nonlinearity
with different particle sizes and dielectric behavior with tem-
perature on this crystal, which are also very important para-
meters to know their use for device applications.
In the present investigation, single crystals of LHN were grown
by the slow evaporation solution technique (SEST). The structural
and vibrational studies were carried out for the grown crystals
Contents lists available at SciVerse ScienceDirect
journal homepage: www.elsevier.com/locate/physb
Physica B
0921-4526/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2011.09.004
n
Corresponding author. Tel.: 91 11 45608261; fax: 91 11 45609310.
E-mail address: bhagavan@mail.nplindia.ernet.in (G. Bhagavannarayana).
Physica B 406 (2011) 44404446
Author's personal copy
powder XRD and FT-Raman analysis. The crystalline perfection of
the grown crystals was assessed using high resolution X-ray
diffractometry (HRXRD). The birefringence measurement was
carried out. The optical band gap was also calculated using
UVvis. study. The photoluminescence emission and absorption
studies were carried out by using a photoluminescence (PL)
spectrophotometer. SHG efciency of the material with different
particle sizes was also measured by the Kurtz and Perry techni-
que. The dielectric studies over a wide range of frequency for the
grown crystal along [0 0 1] were performed at and above the
room temperature.
2. Experimental details
2.1. Synthesis and crystal growth
The title material was synthesized from L-histidine and nitric
acid in 1:1 molar ratio [12]. The product was puried by a
repeated recrystallization process and used for the growth of
single crystals using double distilled water as the solvent. The
saturated solution of recrystallized LHN was prepared at 308 K
with continuous stirring for 24 h. The ltered solution in a beaker
covered with perforated lid was housed in a Eurotherm controlled
constant temperature bath with good stability (70.01 1C) at
308 K. In a time span of 20 days well faceted transparent single
crystals were harvested and the photograph of such a typical
grown crystal is shown in Fig. 1. The observed morphology of
grown crystals was found to be the same as that reported [12].
2.2. Analysis techniques
For conrmation of the crystal system and space group as well
as determining lattice parameters, a homogeneous powdered
specimen of LHN crystals was subjected to PW1830 Philips
Analytical Powder X-ray diffractometry with nickel ltered CuK
a
radiation (35 kV, 30 mA). The data was recorded by operating the
diffractometer in the angular range of 10601 of 2 y at the scan
rate of 0.011/s. The single crystal specimens with natural faceted
surfaces were subjected to Perkin Elmer GX 2000 FT-Raman
spectrometry to carry out the vibrational studies in the wave
number range 1003500 cm
1
at 293 K.
Crystalline perfection of LHN crystals was evaluated using a
multicrystal X-ray diffractometer designed and developed at
National Physical Laboratory [NPL] [15]. The well-collimated
and monochromated MoKa
1
beam (0.709261

A) obtained from
the three monochromator Si crystals set in dispersive (, , )
conguration has been used as the exploring X-ray beam. The
specimen crystal is aligned in the (, , , ) conguration.
Because of the dispersive conguration, though the lattice con-
stants of the monochromator crystal(s) and the specimen are
different, the unwanted dispersion broadening in the diffraction
curve (DC) of the specimen crystal is insignicant. The rocking or
diffraction curves were recorded by changing the glancing angle
(the angle between the incident X-ray beam and the surface of the
specimen) around the Bragg diffraction peak position y
B
(taken as
zero for the sake of convenience) starting from a suitable arbitrary
glancing angle and ending at a glancing angle after the peak so
that all the meaningful scattered intensities on both sides of the
peak were included in the diffraction curve. The specimen was
rotated about the vertical axis, which is perpendicular to the
plane of diffraction, with a minimum angular interval of 0.4
00
. The
DC was recorded by the so-called o scan wherein the detector
was kept at the same angular position 2y
B
with wide opening.
This arrangement is very appropriate for recording the short-
range order scattering caused by defects or by the scattering from
local Bragg diffractions from agglomerated point defects or from
low angle and very low angle structural grain boundaries [16].
Before recording the diffraction curve, to remove the non-crystal-
lized solute atoms that remained on the surface of the crystal and
also to ensure the surface planarity, the specimen was rst lapped
and chemically etched in a non-preferential etchant of water and
acetone mixture in the 1:2 volume ratio. This process also ensures
the removal of possible complexating surface layers [7].
The optically polished single crystal of LHN was subjected to
birefringence measurements using the channeled spectrum
method [17] with a halogen lamp of 1000 W as a source. The
experimental set-up used in the present study is shown in Fig. 2.
The beam obtained from the source (S) was collimated by the
collimator (C) and optically polarized by a polarizer (P). The
polarizer and analyzer (A) were placed in crossed positions, and
the crystal (Cr) was placed in between them in such way that its
optic axis was perpendicular to the incident ray. The transmitted
light components from the analyzer interfere and interference
patterns were observed through the constant deviation spectro-
meter (CDS). For each dark band, the corresponding wavelength
was read out directly from the drum of the CDS.
The UVvis absorption study was carried out using a
JASCO V-570 spectrophotometer in the wavelength range of
190900 nm. The photoluminescence excitation and emission
Fig. 1. Photograph of the SEST grown LHN single crystal. The arrow indicates the
(0 0 1) face of the crystal.
S CDS C P A Cr
Fig. 2. Block diagram of the birefringence set-up.
B. Riscob et al. / Physica B 406 (2011) 44404446 4441
Author's personal copy
spectra were recorded for the single crystals using a Perkin Elmer
LS-55 Fluorescence spectrouorometer. To measure the SHG
efciency of the LHN single crystals, well crushed powders of
as-grown crystals were sieved with standard test sieves of
different sizes 25, 50, 100 and 125 mm, respectively, to achieve
homogeneous particles. These powders were lled properly in a
glass microcapillary of 1 mm inner diameter and subjected to the
Kurtz and Perry powder technique [18]. A standard potassium
dihydrogen phosphate (KDP) crystal was used as a reference to
compare the SHG values. A Q-switched Nd:YAG [Spectra Physics
(DCR-II)] laser with a fundamental wavelength 1064 nm, input
energy 5.15 mJ pulse
1
, 8 ns pulse duration, 10 Hz repetition rate
and 1 mm spot diameter was used in 901 scattering geometry as a
source. The laser radiation was made incident on the specimen
sample, and the produced green output radiation from the speci-
men was detected by a photomultiplier tube (PMT) coupled with
a lter. The signal from the PMT was used to assess the relative
SHG efciency of the grown crystals of different particle sizes in
comparison to that of the KDP reference crystals. The experi-
mental conditions were kept the same for all the samples.
The dielectric properties of the grown crystals as a function of
temperature were studied using a PSM1735 NumetriQ high
frequency impedance analyzer. Before subjecting to the analyzer,
the electrodes were made using silver paste on the parallel
opposite surfaces of a rectangular specimen. The specimen holder
with crystal was housed in a furnace with the temperature
stability up to 71.0 1C controlled by a Eurotherm temperature
controller.
3. Results and discussion
3.1. Powder X-ray diffraction
The recorded Powder X-ray diffraction pattern for LHN is
shown in Fig. 3. The sharp nature of the diffraction peaks indicates
good crystallinity of the grown crystals. The recorded data was
used to calculate lattice parameters using Proszki software from
which it was conrmed that the grown crystals belong to
orthorhombic system with non-centrosymmetric space group
P2
1
2
1
2
1
. The calculated lattice parameters are a5.2601,
b7.1379 and c25.0209

A and found to be in good agreement
with the earlier reported values [12].
3.2. Vibrational studies
The recorded FT-Raman spectrum for LHN single crystal is
shown in Fig. 4. The unused portion of the spectrum was removed
to visualize the analyzed peaks with clarity. The observed peaks
in the spectrum are assigned to their corresponding bonds and
functional groups and tabulated in Table 1. The peaks at 1316,
1174, 1040, 843 and 722 cm
1
correspond to asymmetric stretch-
ing, symmetric as well as asymmetric deformation, symmetric
stretching, symmetric and asymmetric bending, respectively. The
peaks corresponding to ring deformation conrm the proper
synthesis of LHN. The peaks at 224 and 202 cm
1
are due to
lattice vibrations. The sharpness with high intensity of the peaks
indicates that the grown crystals are almost free from the
structural defects [19], which is further elucidated by the follow-
ing HRXRD analysis.
3.3. High resolution X-ray diffractometry
Fig. 5 shows the high-resolution diffraction curve (DC)
recorded for a typical SEST grown LHN single crystal using
(0 0 4) diffracting planes in the symmetrical Bragg geometry by
employing the multicrystal X-ray diffractometer with MoKa
1
radiation. As seen in the gure, the DC contains a single peak
and indicates that the specimen is free from structural grain
boundaries. The FWHM (full width at half maximum) of the curve
is 75
00
, which is somewhat more than that expected for an ideally
perfect crystal from the plane wave theory of dynamical X-ray
diffraction [20] but close to that expected for a nearly perfect
crystal. It is interesting to see the asymmetry of the DC. For a
particular angular deviation (Dy) of glancing angle with respect to
the peak position, the scattered intensity is much more in the
positive direction in comparison to that in the negative direction.
This feature clearly indicates that the crystal contains predomi-
nantly interstitial type of defects than that of vacancy defects.
This can be well understood by the fact that due to interstitial
defects (self-interstitials or impurities at interstitial sites), which
may be due to fast growth and/or impurities present in the raw
material, the lattice around these defects undergoes compressive
stress [21], the lattice parameter d (interplanar spacing) decreases
and leads to gives rise to more scattered (also known as diffuse
X-ray scattering) intensity at slightly higher Bragg angles (y
B
) as d
and sin y
B
are inversely proportional to each other in the Bragg
equation (2d sin y
B
nl; n and l being the order of reection and
Fig. 3. Powder XRD pattern for the LHN crystals. Fig. 4. FT-Raman spectra for LHN single crystal.
B. Riscob et al. / Physica B 406 (2011) 44404446 4442
Author's personal copy
wavelength, respectively, which are xed). However, the single
diffraction peak with reasonably low FWHM indicates that the
crystalline perfection is fairly good. The density of such interstitial
defects is however very meager and in almost all real crystals,
including nature gifted crystals, such defects are commonly
observed [22] and are many times unavoidable due to thermo-
dynamical conditions and hardly affect the device performance.
More details may be obtained from the study of high-resolution
diffuse X-ray scattering measurements [15], which is however not
the main focus of the present investigation. It is worth mention-
ing here that the observed scattering due to interstitial defects is
of short order nature as the strain due to such minute defects is
limited to the very defect core, the long range order could not be
expected and hence the change in the lattice parameter of the
crystal is not possible [23]. It may be mentioned here that the
minute information like the asymmetry in the DC could be
possible as in the present sample only because of the high-
resolution of the multicrystal X-ray diffractometer used in the
present investigation.
3.4. Birefringence analysis
Birefringence is the difference between the magnitudes of
refractive indices of ordinary ray and extraordinary ray. This
characteristic behavior of birefringence crystal can be used in
polarization devices and beam reector [24]. The birefringence of
the grown crystal was calculated using the formula Dnkl/t [25],
l being the wavelength, t is the thickness of the crystal and k is
the fringe order. In the present experimental study, the thickness
of the crystal was around 0.19 mm. The graph drawn between
birefringence and wavelength is shown in Fig. 6. As seen in the
graph, the value of birefringence lies between 0.3432 and 0.3406
over the wavelength region of 54805630

A. Such a nominal
variation of birefringence shows the suitability of LHN crystals
for efcient second harmonic generation (SHG) and optical
devices like polarizers and beam reectors. The birefringence
value of the titled material is 10 times higher than that of the
standard KDP crystal. The average value of retardation ! (thick-
ness of the sample birefringence) was also calculated and it was
found to be 6.49610
5
. LHN crystal shows high birefringence
value compared to other materials like calcite [10], potassium
acid phthalate (KAP) [26], L-histidine bromide (LHB) [27], etc.
3.5. UVvis spectroscopy analysis
To calculate the optical band gap, the absorption spectra of the
grown crystal were recorded. First the optical absorption coefcient
(a) was calculated from the absorbance [Fig. 7(a)] using the relation
a Absorbance=t 1
t being the thickness of the crystal. The relation between the optical
band gap (E
g
) and the optical absorption coefcient (a) near the
absorption edge can be written as [28]
ahn AhnE
g

1=2
2
Table 1
FT-Raman peak positions with their assignments for LHN crystal.
Peak Position (cm
1
) Assignments
3157 CH stretching
2974 CH
2
asymmetric stretching
2948 CH
2
symmetric stretching
1629 NH
3
symmetric deformation
1495 CN stretching
1431 CH
2
deformation
1353 CH bending
1316 NO
3
asymmetric stretching
1272 CH wagging
1245 CH
2
twisting
1201 RingNH stretching
1174 NO
3
symmetricNO
3
asymmetric deformation
1086 CN symmetric stretching
1040 NO
3

symmetric stretching
992 Ring deformation
944 CC stretching
926 CC stretching
900 Ring deformation
843 NO
3

symmetric bending
814 OCO deformation
742 OCO deformation
722 NO
3

asymmetric bending
704 OCO deformation
626 Ring puckering
544 CCO deformation
397 CCC in plane vibration
370 CCC in plane vibration
356 CCC in plane vibration
247 lattice vibrations
202 lattice vibrations
Fig. 5. High-resolution diffraction curve recorded for a typical LHN single crystal
using (0 0 4) diffracting planes in symmetrical Bragg geometry with MoKa
1
radiation. The inset shows the schematic of the compressed lattice around an
interstitial defect core.
Fig. 6. Birefringence vs. wavelength for LHN crystal.
B. Riscob et al. / Physica B 406 (2011) 44404446 4443
Author's personal copy
A is a constant, E
g
is the optical band gap, h is the Planks constant
and n is the frequency of incident photon. The plot of (ahn)
2
vs. hn is
shown in Fig. 7(b). The band gap of the grown crystal was obtained
as 3.73 eV from the intercept on the X-axis with the extrapolated
straight line. The transparency of the grown crystal was found to be
in good agreement with the reported one [12]. The high transmis-
sion in the entire visible region also conrmed the colorless nature
of the grown crystal. Hence the titled compound could be a good
candidate for fabrication of NLO devices.
3.6. Photoluminescence studies
The PL excitation spectrum [Fig. 8(a)] of LHN single crystal was
recorded in the ultra violet region, corresponding to the emission
wavelength 385 nm. A strong absorption band was observed at
241 nm. The PL emission spectrum [Fig. 8(b)] for the excitation
of the specimen crystal at 241 nm was recorded in the wave-
length range from 300 to 700 nm. A strong emission band was
observed at 385 nm. The emission spectrum indicates that the
LHN crystal is efcient for the absorption of ultraviolet light and
emission of light in violet region. The small band at 595 nm
may be due to minute lattice defects, whereas high intensity and
discrete nature of the major emission band at 385 nm indicate
that the grown crystals are free from the major defects like grain
boundaries as revealed by HRXRD results.
3.7. Second harmonic generation (SHG) studies
Depending upon the coherence length of the laser beam, the
SHG efciency increases with increasing particle size and attains
constant value at higher particle sizes [29]. Different SHG values
are reported previously for the title material [12,13]. The
observed values of SHG efciency with different particle sizes
are given in Table 2. The variation of SHG with particle size is
shown in Fig. 9. We have repeated our experiments several times
on the title material with different particle sizes to get the actual
value of SHG. The observed saturated value of SHG is found to be
0.8 times to that of standard KDP and seems to be the correct
value, which is well matched with that of Ref. [13]. This kind of
particle size dependency on SHG intensity exists only in phase-
matchable materials [30]. Hence this crystal can be used as an
efcient frequency doubler and optical parametric oscillator.
Fig. 7. (a) Absorption spectrum and (b) Optical band gap for the LHN crystal.
Fig. 8. The recorded photoluminescence: (a) excitation spectrum with peak at
241 nm and (b) emission spectrum with peak at 385 nm, for LHN single crystals.
Table 2
Particle size dependent SHG intensities for LHN crystals.
Sample/Particle size SHG Signal 2o (mv) Efciency with respect to KDP
Pure KDP (standard size) 26.0 1.0000
LHN25 mm 9.5 0.3653
LHN50 mm 19.0 0.7308
LHN100 mm 20.9 0.8038
LHN125 mm 20.8 0.8000
B. Riscob et al. / Physica B 406 (2011) 44404446 4444
Author's personal copy
3.8. Dielectric studies
The dielectric properties of the nonconducting optical single
crystals are well correlated with electro-optic properties [31].
Dielectric constant (e
r
) and dielectric loss (tan d) for LHN crystal
recorded on the prominent face of crystal (0 0 1) with different
temperatures over a wide range of frequency (10 kHz15 MHz)
are shown in Fig. 10(a) and (b), respectively. The dielectric
constant is higher at lower frequencies, then decreases sharply
with frequency and after that it remains almost constant over the
entire higher frequency range. The decrease of dielectric constant
in higher frequency region may be due to the fact that the dipoles
cannot follow up the fast variation of the applied eld. The higher
values of e
r
at lower frequencies may be due to contribution from
all the four types (space charge, dipolar, ionic and electronic
polarization) of polarizations, but at higher frequencies, only ionic
and electronic polarizations contribute. At room temperature,
e
r
has a smaller value over the entire frequency range. As the
temperature increases, e
r
also increases at lower frequencies
whereas at higher frequencies it remains the same as that of room
temperature. From Fig. 10(b) it is clearly visible that the dielectric
loss (tan d) for LHN at room temperature is almost zero. At
elevated temperatures, tan d increases at lower frequencies but
at higher frequencies it remains almost negligible. Fig. 10(c) shows
the ac conductivity s
ac
vs. applied frequency, which was calcu-
lated from the following formula:
s
ac
2pne
o
e
r
tand
e
o
is the vacuum dielectric constant, e
r
the relative dielectric
constant for the LHN crystal and n is the frequency of applied ac
eld. The Nyquist/colecole plots at 300 and 323 K were calcu-
lated and are shown in Fig. 11(a), which show the near semicircle
shape. However, at the higher temperatures we could not achieve
the proper shape of the curves and they could not be tted with
any available model. The slight change in the radius may be
attributed to the increase in dc part of conductivity [32], as shown
in ac conductivity plots. The relaxation time (t) corresponding to
the peak of ColeCole plots have been calculated using the relation
o
M
t1; o
M
(2pf
M
) is the frequency at which Z
00
is maximum.
For both the temperatures 300 and 323 K there is no shift in the
peak positions and the value of t is found to be 1.8910
5
s. The
data points are well tted with the simulated plots by electro-
chemical impedance spectroscopy (EIR) analyzer software (http://
www.abc.chemistry.bsu.by/vi/analyser/). The evaluated constant
phase element (CPE) coefcient n at 300 and 323 K are 0.65 and
0.6, respectively. To get the correct value of f
M,
which is 8422 Hz,
frequency dependent plots of Z
00
were used [Fig. 11(c)]. The
activation energy (DE) calculated using the relation s
ac
s
o
exp(DE/kT) (s
o
being a constant, T the absolute temperature
Fig. 9. Variation of SHG with particle size of LHN sample.
Fig. 10. (a) Dielectric constant and (b) dielectric loss curves with frequency for
LHN single crystals at different temperatures.
B. Riscob et al. / Physica B 406 (2011) 44404446 4445
Author's personal copy
and k the Boltzmann constant) at various temperatures is shown
in Fig. 11(b).
4. Conclusions
Single crystals of LHN have been grown by the conventional SEST
method. The crystal structure and synthesis of the compound have
been conrmed by powder XRD and FT-Raman, respectively. Crystal-
line perfection of the grown crystals has been assessed using a
HRXRD and the results revealed that the grown single crystals are
free from the major defects like grain boundaries. The birefringence
value was found to be 10 times higher than that of KDP and is stable
over the characterized wavelength range. The optical band gap was
determined from UVvis studies and found to be 3.73 eV. The
photoluminescence excitation and emission spectra revealed that the
crystals show the prominent emission for the violet radiation at 385
nm. The SHG efciency of LHN samples was conrmed as 0.8 times
that of standard KDP. The ambiguity in the reported values has been
removed by studying the SHG at different particle sizes. Dielectric
constant and dielectric loss studies over a wide range of frequency
indicate that the grown LHN single crystals are free from the major
defects in tune with HRXRD. The present studies on LHN single
crystals reveal excellent optical and dielectric properties along with
good crystalline perfection and hence LHN may be a good candidate
for the fabrication of optical devices.
Acknowledgement
Authors are thankful to the Director, NPL for his continuous
encouragement to carry out the present investigation. They are
also grateful to Dr. Manju Arora, NPL, for recording FT-Raman
spectra. Riscob acknowledges Director, NPL, for giving him an
opportunity to work at NPL during his M.Phil. project work in
Crystal Growth and Crystallography Section.
References
[1] N.P. Prasad, Polymer 32 (1991) 1746.
[2] S.R. Marder, J.E. Sohn, G.D. Stucky (Eds.), Material for Nonlinear Optics,
American Chemical Society, Washington, DC, 1991.
[3] B.E.A. Saleh, M.C. Teich, Fundamentals of Photonics, Wiley, New York, 1991.
[4] B.G. Penn, B.H. Cardelino, C.E. Moore, A.W. Shields, D.O. Frazier, Prog. Cryst.
Growth Charact. mater. 22 (1991) 19.
[5] R.J. Hoss, Fibre Optical Communication Handbook, Prentice-Hall, Englewood
Cliffs, NJ, 1992.
[6] D. Kalaiselvi, R. Mohan Kumar, R. Jayavel, Mater. Lett. 62 (2008) 755.
[7] J. Madhavan, S. Aruna, P.C. Thomas, M. Vimalan, S.A. Rajasekar, P. Sagayaraj,
Cryst. Res. Technol. 42 (2007) 59.
[8] Tapati Mallik, Tanusree Kar, Mater. Lett. 61 (2007) 3826.
[9] C. Ramachandra Raja, A.Antony Joseph, Mater. Lett. 64 (2010) 108.
[10] C.H. Huang, J. Cryst. Growth 229 (2001) 184.
[11] Xiu-li Yan, Xing Wu, Jian-fei Zhou, Zhi-guo Zhang, Xiao-ming Wang,
Pan-ming Fu, Yan-dao Jiang, Jing Hu, Jun-lin Qiu, J. Cryst. Growth 212
(2000) 204.
[12] Yun Zhang, Hua Li, Bin Xi, Yunxia Che, Jimin Zheng, Mater. Chem. Phys. 108
(2008) 192.
[13] S.A. Martin Britto Dhas, S. Natarajan, Opt. Commun. 281 (2008) 457.
[14] H.A. Petrosyan, H.A. Karapetyan, A.M. Petrosyan, J. Mol. Struct. 794 (2006)
160.
[15] K. Lal, G. Bhagavannarayana, J. Appl. Crystallogr. 22 (1989) 209.
[16] G. Bhagavannarayana, S.K. Kushwaha, J. Appl. Crystallogr. 43 (2010) 154.
[17] K. Nagarajan, C.K. Shashidharan Nair, Opt. Commun. 275 (2007) 348.
[18] S.K. Kurtz, T.T. Perry, J. Appl. Phys. 39 (1968) 3798.
[19] N.V. Sidorov, M.N. Palatnikov, V.T. Gabrielyan, P.G. Chufyrev, V.T. Kalinnikov,
Inorg. Mater. 43 (2007) 60.
[20] B.W. Batterman, H. Cole, Rev. Mod. Phys. 36 (1964) 681.
[21] G. Bhagavannarayana, S. Parthiban, Subbiah Meenakshisundaram, Cryst.
Growth Des. 8 (2008) 446.
[22] G. Bhagavannarayana, P. Rajesh, P. Ramasamy, J. Appl. Crystallogr. 43 (2010)
1372.
[23] G. Bhagavannarayana, S.K. Kushwaha, Mohd Shakir, K.K. Maurya, J. Appl.
Crystallogr. 44 (2011) 122.
[24] K. Buse, M. Luennemann, Phys. Rev. Lett. 85 (2000) 3385.
[25] D.W. Fischer, M.C. Ohmer, P.G. Schunemann, T.M. Pollak, J. Appl. Phys. 77
(1995) 5943.
[26] N. Balamurugan, M. Lenin, P. Ramasamy, Mater. Lett. 61 (2007) 1896.
[27] N. Vijayan, G. Bhagavannarayana, K. Nagarajan, V. Upadhyaya, Mater. Chem.
Phys. 115 (2009) 656.
[28] A. Ashour, N. El-kadry, S.A. Mahmoud, Thin Solid Films 269 (1995) 117.
[29] Y. Porter, O.K. Kang Min, N.S.P. Bhuvanesh, S. Halasyamani, Chem. Mater. 13
(2001) 1910.
[30] K. Naseema, Vijayalakshmi Rao, K.V. Sujith, Balakrishna Kalluraya, Curr. Appl.
Phys. 10 (2010) 1236.
[31] S. Boomadevi, R. Dhanasekaran, J. Cryst. Growth 261 (2004) 70.
[32] Fathy Salman, Turk. J. Phys. 28 (2004) 41.



0.0 5.0M 10.0M 15.0M 20.0M
0.0
2.0M
4.0M
6.0M
8.0M
10.0M
300 K
323 K
Z
"
Z'

M
= 1
= 5.13x10
-5
s
Simulated 300 K
Simulated 323 K
1k 10k 100k 1M 10M
0.0
2.0M
4.0M
6.0M
8.0M
Z
"
Frequency (Hz)
300 K
323 K
300 320 340 360 380 400 420
5.0x10
-7
1.0x10
-6
1.5x10
-6
2.0x10
-6
2.5x10
-6
3.0x10
-6
a
c
t
i
v
a
t
i
o
n

e
n
e
r
g
y

(
e
V
)
T (K)
Fig. 11. (a) Nyquist/ColeCole plots at temperatures 300 and 323 K, (b) Z
00
vs.
frequency plots at temperatures 300 and 323 K and (c) activation energy for the
grown LHN single crystal at different temperatures.
B. Riscob et al. / Physica B 406 (2011) 44404446 4446