ARTICLE IN PRESS

Physica B 405 (2010) 3248–3252

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Physica B
journal homepage: www.elsevier.com/locate/physb

Spectral, optical and mechanical studies on L-histidine hydrochloride

monohydrate (LHC) single crystals grown by unidirectional
growth technique
R. Robert a, C. Justin Raj c, S. Krishnan b, R. Uthrakumar c, S. Dinakaran c, S. Jerome Das c,n
a
Department of Physics, Government Arts College (Men), Krishnagiri, India
b
Department of Physics, R.M.K. Engineering College, Kavaripettai 601 206, India
c
Department of Physics, Loyola College, Chennai 600 034, India

a r t i c l e in f o a b s t r a c t

Article history: Single crystals of nonlinear optical L-histidine hydrochloride monohydrate (LHC) were grown in an
Received 13 January 2010 aqueous solution by the unidirectional crystal growth method within a period of 45 days along (1 0 1)
Received in revised form plane. The grown crystals were subjected to single crystal X-ray diffraction analysis to confirm their
21 February 2010
orthorhombic structure having space group P212121. Values of several physical parameters were
Accepted 22 April 2010
determined for the grown crystal. Optical transmission studies revealed very low absorption and band
gap energy was calculated for the LHC crystals. Further, some optical constant were also determined for
Keywords: the grown crystals. Anisotropy in Vicker’s microhardness led to the assessment of fracture toughness,
Growth from solutions brittleness index and yield strength for the synthesized crystals. Nonlinear optical studies were carried
Optical properties
out for the grown crystal and second harmonic generation (SHG) efficiency was found to be three times
Optical constant
that of KDP crystals.
Mechanical properties
& 2010 Elsevier B.V. All rights reserved.

1. Introduction crystals were subjected to theoretical, optical and mechanical

studies.
In the recent years, there has been considerable interest among
scientists in the development of novel nonlinear optical (NLO)
materials, which combine high optical nonlinearity and chemical 2. Experiment
flexibility of organics with high mechanical strength of inorganics
[1–3]. The key factors for material selection depend not only on 2.1. Synthesis and growth of seed crystals
laser conditions but also on physical properties of the crystal, such
as transparency, damage threshold, phase matching, conversion L-Histidine hydrochloride monohydrate crystals were synthe-

efficiency and temperature stability [4,5]. In view of this,
considerable interest has been evidenced in the synthesis of
semi-organic materials due to their high nonlinearity, high
resistance to laser induced damage, low angular sensitivity and
good thermal and mechanical properties [6–8]. Besides second
harmonic generation (SHG), such kinds of crystals may be
interesting for field-induced optical and nonlinear optical effects
[9,10]. L-Histidine hydrochloride monohydrate (C6H9N3O2
HCl.H2O) (LHC) belongs to one such class of semi-organic
nonlinear optical crystal, which crystallizes in the orthorhombic
structure with the space group P212121 [11,12]. In the present
work, using a modified Sankaranarayanan–Ramasamy (mSR)
method [13,14], single crystals of LHC were grown and the grown
n
Corresponding author. Tel.: + 91 44 2817 5662; fax: + 91 44 2817 5566.
E-mail addresses: sjeromedas2004@yahoo.com, jerome@loyolacollege.edu
(S. Jerome Das).
sized by mixing L-Histidine (Merck) and hydrochloric acid
(AR grade) in an aqueous solution in the ratio of 1:1. By repeated
re-crystallization, purity of the synthesized salt was further
increased and the supersaturated solution of LHC was kept
undisturbed at room temperature. Optically transparent defect
free seed crystal was obtained within a period of 20 days, which
was chosen for unidirectional growth along (1 0 1) plane.
2.2. Experimental setup and crystal growth
An optically good quality seed crystal was mounted on the
bottom of an ampoule, filled with supersaturated solution of LHC
and placed along the axis of the growth assembly. Here,
an assembly of alternating 40 W filament lamps provides a
temperature gradient for the growth. Temperature at the top of
the ampoule was maintained at 45 1C using a temperature
controller setup for evaporation of the saturated solution.

0921-4526/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2010.04.053
 ARTICLE IN PRESS
R. Robert et al. / Physica B 405 (2010) 3248–3252 3249

The value of a so obtained agrees well with that of Clausius–

Mossotti equation, which is given by
 
3M e1 1
a¼ ð6Þ
4pNa r e1 þ 2
All these calculated data for the grown crystal are shown in
Table 1.

3.2. Optical transmission studies

The optical transmission spectrum of L-histidine hydrochloride

Fig. 1. Photograph of grown LHC single crystals.
To maintain steady temperature around the ampoule, it was
rotated 901 per second using a stepper motor along the axis of the
growth setup. The temperature gradient makes the concentration
gradient maximum at the bottom and minimum at the top of the
ampoule for avoiding spurious nucleation along the axis
of the ampoule. Growth rate of the crystal was found to be
around 1.45 mm per day. Crystals of 65 mm length and
12 mm diameter have been grown successfully within a period
of 45 days. Morphology of the grown crystal is like that of
the growth vessel. A photograph of the grown crystal is shown in
Fig. 1.
3. Results and discussion
3.1. Single crystal X-ray diffraction analysis
Single crystal X-ray diffraction analysis for the grown crystal
monohydrate (LHC) single crystal was recorded in the wavelength
region 200–1100 nm and is shown in Fig. 2. For optical
fabrications, the crystal should be highly transparent in the
considered region of wavelength [18,19]. Favorable transmittance
of the crystal in the entire visible region suggests its suitability for
second harmonic generation [20,21]. The UV absorption edge for
the grown crystal was observed to be around 240 nm. The
dependence of optical absorption coefficient on photon energy
helps to study the band structure and type of transition of
electrons [22].
Optical absorption coefficient (a) was calculated from trans-
mittance using the following relation:
 
1 1
a ¼ log ð7Þ
t T
where T is the transmittance and t the thickness of the crystal.
As a direct band gap material, the crystal under study has an
absorption coefficient (a) obeying the following relation for high
photon energies (hn):
AðhnEg Þ1=2
a¼ ð8Þ
hn
where Eg is the optical band gap of the crystal and A is a constant.
A plot of variation of (ahn)2 versus hn is shown in Fig. 3. Eg is
evaluated using extrapolation of the linear part [23]. The energy
Table 1
Theoretical data on LHC single crystals.

was carried out using an ENRAF NONIUS CAD-4 X-ray diffract- Parameters Values
ometer. This analysis reveals that the LHC crystal had the
orthorhombic structure with the space group P212121 and lattice Plasma energy (eV) 12.34
parameters in Å are found to be a¼ 6.729, b¼15.116 and c¼8.513, Penn gap (eV) 2.83
Fermi energy (eV) 28.51
which agree well with reported values [15]. Valence electron
Polarizability (cm3)
plasma energy, Zop , is given by Penn analysis 0.9279  10  22
1=2 Clausious–Mossotti 0.9324  10  22
Zop ¼ 28:8ðZ r=MÞ ð1Þ

where Z ¼(6ZC)+ (12ZH)+(3ZN)+(3ZO) +(1ZCl)¼50 is the total

number of valence electrons, r the density and M the molecular
weight of the LHC crystal. Explicitly dependent on Zop are Penn
gap and Fermi energy [16], as given by
Zop
Ep ¼ ð2Þ
ðe1 1Þ1=2
and

EF ¼ 0:2948ðZop Þ4=3 ð3Þ

Polarizability a is obtained using the relation [17]

" #
ðZop Þ2 S0 M
a¼  0:396  1024 cm3 ð4Þ
ðZop Þ2 S0 þ3Ep 2 r

where S0 is a constant for the material, which is given by

   
Ep 1 Ep 2
S0 ¼ 1 þ ð5Þ
4EF 3 4EF Fig. 2. Optical transmission spectrum of LHC crystals.
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3250 R. Robert et al. / Physica B 405 (2010) 3248–3252

600

500

400
(αhυ)2

300

200

100

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
hυ (eV)

Fig. 3. Plot of a versus photon energy for LHC single crystals.

absorption gap is of direct type and the band gap energy is found
to be 3.70 eV. As a consequence of a wide band gap, the grown
crystal has a large transmittance in the visible region [24].

3.3. Determination of optical constant

Optical behavior of materials is important to determine its

usage in optoelectronic devices [25]. Knowledge of optical
constant of a material such as optical band gap and extinction
coefficient is quite essential to examine the material’s potential
optoelectronic applications [26]. Further, the optical properties
may also be closely related to the material’s atomic structure, Fig. 4. Plots of (a) reflectance (R) and (b) extinction coefficient (K) versus a.
electronic band structure and electrical properties. An accurate
measurement of optical constants can be easily performed on 3.4. Microhardness
inorganic crystals. In such crystals, photonic density of states and
photonic mode spatial distribution can be tailored to great Microhardness studies of any system have a direct correlation
accuracy. with crystal structure, and is very sensitive to the presence of any
Optical constant (n, K) are determined from the transmission other phase or phase transition and lattice perfections prevalent
(T) and reflection (R) spectra based on the following relations in the system. Hardness of the material depends on different
[27]: parameters such as lattice energy, Debye temperature, heat of
ð1RÞ2 expðatÞ formation and interatomic spacing. Thus microhardness plays the
T¼ ð9Þ principle role in electron–phonon anharmonicities due to the
1R2 expð2atÞ
crucial role of inter-molecular interactions.
where t is the thickness and a is related to extinction coefficient The hardness test for LHC crystal was carried out by a Leitz
K by Wetzler microhardness tester with a diamond pyramidal inden-
al ter. Diagonal length of indentations for various applied loads in kg
K¼ ð10Þ is measured for a constant indentation period of 15 s. Vicker’s
4p
hardness number (Hv) is calculated using the relation
The refractive index (n) can be determined from the reflec-
tance (R) data using the relation [28] 1:8544P
Hv ¼ kg=mm2 ð14Þ
2
d2
ðn1Þ
R¼ ð11Þ where P is the applied load in kg and d the diagonal length in mm.
ðn þ 1Þ2
The variation of Hv with applied load P is shown in Fig. 5. From the
Reflectance in terms of absorption coefficient can be written as graph it becomes clear that the hardness value decreases with
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi increasing load, thus satisfying the normal indentation size effect.
1expðatÞ þ expðatÞ
R ¼ 17 ð12Þ A plot of log P versus log d yields a straight line graph (Fig. 6) and
1þ expðatÞ
its slope gives the work hardening index n, and is found to be 1.44,
and from the above equation, refractive index n can also be according to Meyer’s relation
derived as
P ¼ K1 dn ð15Þ
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ðR þ1Þ 7 3R2 þ 10R3
n¼ ð13Þ where K1 is the standard hardness value, which can be found out
2ðR1Þ
from the plot of P versus dn (Fig. 7). Since the material takes some
Fig. 4 (a) and (b) shows the variation of reflectance (R) and time to revert to the elastic mode after every indentation, a
extinction coefficient (K) as a function of absorption coefficient, correction x is applied to the d value and Kick’s law is related as
respectively. From the graphs, it is clear that both reflectance and
extinction coefficients depend on absorption coefficient. Internal P ¼ K2 ðd þxÞ2 ð16Þ
efficiency of the device also depends on absorption coefficient. From Eqs. (15) and (16), we get
Hence, by tailoring absorption coefficient, one can achieve a  1=2  
desired material for the fabrication of electro-optic and K2 K2
dn=2 ¼ dþ x ð17Þ
optoelectronic devices. K K1
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R. Robert et al. / Physica B 405 (2010) 3248–3252 3251

80 14
12

60 10
8
Hv kg/mm2

dn/2
6
40
4
2
20
0
20 40 60 80 100 120 140 160
0 d
0 10 20 30 40 Fig. 8. Plot of d versus dn/2.
Load P x 10-3 kg

Fig. 5. Plot of Hv versus load P. Table 2

Microhardness values on LHC single crystals.

Parameters Values
1.6
n 1.44
1.4
K1 (kg/mm) 20.4  10  2
1.2 K2 (kg/mm) 6.75  10  4
Kc (MNm  3/2) 0.015587
1 B (m  1/2) 5.26  103
log P

0.8 sv (MPa) 575.67

0.6
0.4 Yield strength sv of the material can be found out using the
0.2 relation
0  
H   12:5ð2nÞ 2n
0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 sv ¼ v 1ð2nÞ ð20Þ
2:9 1ð2nÞ
log d
Load dependent hardness parameters n, K1, K2 and fracture
Fig. 6. Plot of log P versus log d. toughness (Kc), brittleness index (B) and yield strength (sv) are
calculated for the LHC crystal and are given in Table 2.

3.5. Nonlinear optical studies

35
30 The SHG property in LHC single crystals was studied using a
Q-switched Nd:YAG laser by employing the Kurtz powder test.
25 The fundamental beam of a Nd:YAG laser emitting a fundamental
Load P

20 laser of 1064 nm wavelength, pulse duration 35 ps and 10 Hz

repetition rate was focused onto the powdered sample. Second
15
harmonic generations were confirmed by the emission of green
10 radiation at 532 nm and SHG efficiency was found to be three
5 times that of KDP crystals [29].

0
0 20 40 60 80 100 120 140 160 4. Conclusions
dn
Optically good quality single crystals of L-histidine hydro-
Fig. 7. Plot of load P versus dn. chloride monohydrate of dimensions 65 mm length and 12 mm
diameter were grown along (1 0 1) plane by a modified
The slope of dn/2 versus d yields (K2/K1)1/2 and the intercept is a Sankaranarayanan–Ramasamy (mSR) method within a period of
measure of x and is shown in Fig. 8. 45 days. The grown crystal was subjected to single crystal X-ray
Fracture toughness (Kc) is given by diffraction analysis, and several physical parameters such as
valence electron plasma energy, Penn gap, Fermi energy and
P
Kc ¼ ð18Þ electronic polarisability were determined for the grown crystal.
bC 3=2 Band gap energy for the grown crystal was found to be 3.70 eV.
where C is the crack length measured from the centre of Optical constants such as extinction coefficient (K) and reflectance
indentation mark to the crack tip, P the applied load and (R) indicate high transparency of the crystal and confirm its
geometrical constant b ¼7 for Vicker’s indenter. Brittleness index suitability for optical device fabrication. Mechanical hardness
(B) is given by studies reveal that Vicker’s hardness number decreases as load
increases, satisfying the normal indentation size effect (ISE).
Hv Several hardness parameters have been calculated for the grown
B¼ ð19Þ
Kc crystals. These studies confirm that the LHC crystals are found to
 ARTICLE IN PRESS
3252 R. Robert et al. / Physica B 405 (2010) 3248–3252
be prospective materials for the fabrication of electro-optic and
optoelectronic devices. NLO studies were carried out using the
Kurtz powder technique and SHG efficiency is found to be 3 times
that of KDP crystals.
Acknowledgements
The encouragements and support rendered by the research
scholars of the Department of Physics, Loyola College and the
cooperation extended by Prof. I. Jeyadoss, Loyola College, Chennai,
are gratefully acknowledged.
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