Cryst. Res. Technol. 42, No. 1, 59 64 (2007) / DOI 10.1002/crat.

200610771

Growth and characterization of L-histidine hydrochloride

monohydrate single crystals
J. Madhavan1, S. Aruna1, P. C. Thomas1, M. Vimalan1, S. A. Rajasekar2, and P. Sagayaraj*1
1
2

Department of Physics, Loyola College, Chennai 600 034, India

Department of Physics, Vellore Institue of Technology, Vellore, India

Received 17 May 2006, revised 18 July 2006, accepted 25 July 2006

Published online 15 December 2006
Key words NLO, solution growth, LHC, thermal analysis.
PACS 78.40.-q, 65.40.-b, 62.20.x, 77.22.-d, 72.40.+w
Good optical quality single crystal of L-histidine hydrochloride monohydrate (LHC) a novel semi organic
NLO material was grown by slow solvent evaporation technique. The crystal was characterized by X-ray
diffractometry (XRD), Fourier Transform Infra-red (FTIR), UV-Vis-NIR, TGA, DTA, microhardness and
solubility studies. The SHG efficiency is found to be higher than that of KDP crystal. The dielectric constant
and dielectric loss of the crystal was studied as function of frequency and the results are discussed.
Photoconductivity studies were also carried out which reveals the positive photoconducting properties of the
sample.

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Introduction

In the last decade, organic nonlinear optical crystals with aromatic rings have attracted much attention because
of their high nonlinearity, fast response and tailor made flexibility. However, the shortcomings of aromatic
crystal, such as poor physico chemical stability, low hardness and cleavage tendency hinder their device
application. In order to keep the merits and overcome the shortcomings of organic materials, some new classes
of NLO crystals such as metal organic or semiorganic crystals have been developed [1]. Amino acids are
interesting materials for NLO applications. Complexes of amino acids with inorganic salts are promising
materials for optical second harmonic generation (SHG) as they tend to combine the advantages of the organic
amino acid with that of the inorganic salt. In recent years semiorganic crystals have emerged as extremely
promising building blocks for NLO materials. They share the properties of both organic and inorganic
materials. Hybrid crystals substantial role may have acoustically induced birefringent effects as it was
established for the Ru-complexes [2]. These materials can be used as better alternative for KDP crystals in
frequency doubling and laser fusion experiments due to their higher values of laser damage threshold [3]. Lhistidine analogs have attracted attention as promising NLO materials after it was found that L-histidine
tetrafluoroborate have higher NLO properties than LAP by Marcy et al. [4]. Recently our research group has
grown single crystals of a new promising nonlinear optical crystal L-histidine bromide (LHB) by slow
evaporation technique. The grown crystals were characterized by X-ray diffraction studies, FTIR, UN-Vis-NIR
and solubility studies. Besides these, the morphology, hardness along with differential thermal analysis (DTA),
thermogravimetric analysis (TGA), Differential Scanning Calorimetry (DSC) and photoconductivity studies
have also been done and reported by us [5,6]. LHC is one such promising semiorganic nonlinear optical
material that belongs to the histidine-complex family which is isostructural to LHB [7]. A thorough scan of
literature reveals that neutron and x-ray diffraction studies have already been reported [8, 9], the compound
was further refined on the basis of the intensity data collected by the diffractometer method [10]. The IR
____________________

* Corresponding author: e-mail: psagayaraj@hotmail.com

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

60

J. Madhavan et al.: L-histidine hydrochloride monohydrate single crystals

spectra of both LHB and LHC was studied by Petrosyan et al. [7] and confirmed that they are isostructural.
Interestingly these works on LHC were restricted to the solving of crystal structure and SHG preliminary
studies only, other properties are not yet reported.
In the present investigation, the growth aspects of bulk crystals of LHC were studied using slow
evaporation technique. The grown crystals were characterized by single crystal XRD, FTIR, UV-Vis-NIR,
thermal, microhardness, dielectric and photoconductivity studies.

Experimental procedures

Solubility and synthesis By reacting equimolar proportion of L-histidine (kemphasol 98% and
Hydrochloric acid (AR grade) in aqueous solution, the compound L-His.HCl.H2O was formed. The solubility
(g LHC / 100ml H2O) of LHC was measured by the method described earlier [11]. The variation of solubility
with temperature was studied and as shown in figure 1. Large amount of small crystals were formed due to
spontaneous nucleation at the bottom of the container with the solution. Among these tiny crystals, the ones
having very good transparency were selected as the seed crystals for growth experiments. Crystals were grown
using the slow solvent evaporation technique at room temperature. Crystals of dimension up to 11 mm x 10
mm x 9 mm were obtained after a period of 45 days. Figure 2 shows the photograph of an as grown crystal.

Fig. 1 Solubility curve of LHC crystal.

Fig. 2 Photograph of as grown

LHC single crystal.

Characterization The single crystal X-ray diffraction studies of the crystals were carried out using
ENRAF NONIUS CAD4 single X-ray diffractometer with MoK ( = 0.717 ) radiation. The structure was
solved by the direct method and refined by the full matrix leastsquare technique using the SHELXL program.
The optical absorption spectrum was recorded in the range of 200 - 2500 nm using VARIAN CARRY 5E, UVVIS-NIR SPECTROMETER. The FTIR spectrum was recorded in the range of 4000450cm-1 using BRUKER
IFS 66V, FT-IR SPECTROMETER. The NLO efficiency of LHC crystal was evaluated by the Kurtz and Perry
powder technique [12] using a Q-switched, mode locked Nd : YAG laser emitting 1.06m, 8ns laser pulses
with spot radius of 1mm. The input laser beam was passed through an IR reflector and then directed on the
powdered sample. The light emitted by the sample was measured by the photo diode detector and oscilloscope
assembly. DTA and TGA studies of the crystals were carried out using the instrument NET SZCH STA 409C.
Microhardness studies have been carried out on LHC crystal using a Leitz Wetzlar Vickers microhardness
tester fitted with a Vickers diamond pyramidal indenter attached to an incident light microscope. The static
indentations were made at room temperature with a constant indentation time of 15 seconds for all
indentations. The indentation marks were made on the surfaces by varying the load from 5 to 25g. The Vickers
microhardness number Hv of the crystal was calculated using the relation Hv = 1.8544 P/d2 Kg-mm-2. The
dielectric constant and the dielectric loss of the LHC sample were studied at room temperature using HIOKI
3532 LCR HITESTER in the frequency region 500 Hz to 5 MHz. LHC sample of uniform cross sectional area
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.crt-journal.org

Cryst. Res. Technol. 42, No. 1 (2007)

61

5x3 mm2 and 2 mm thickness was coated with silver paint to provide good electrical contact. The dielectric
constant and dielectric loss were measured with varying frequency, for a fixed applied voltage. The
photoconductivity study was carried out using Keithley 485 picoammeter. A well polished sample of LHC was
attached to a microscopic slide on which two copper electrodes were fixed rigidly at known distance, using
silver paint. The sample LHC was connected in series to a variable d.c power supply and a Keithley 485
picoammeter. After shielding the sample from all surrounding radiation, the applied voltage was increased
from 0 to 400 V in steps of 20 V and the corresponding darkcurrents were noted. During the second stage, the
photocurrent of the same sample was measured by exposing it to the radiation from a 100W halogen bulb
containing iodine vapor. The rays from the halogen bulb were focused on the sample by a short range focal
length convex lens.

Results and discussion

Single Crystal XRD From the X-ray diffraction data, it is observed that the LHC crystal is orthorhombic
in structure with space group P212121. The lattice parameters are a = 6.849 , b = 8.928 , c = 15.302 and
Volume = 935.685 3. The crystal data for LHC is presented in table 1 and it agrees well with the reported
values [10].
Table 1 Crystal data of LHC crystal.
Empirical formula
Crystal system
Space group
a()
b()
c()
(deg)
(deg)
(deg)
Volume 3

Fig. 3 FTIR spectrum of LHC crystal.

C6H9N3O2.HCl.H2O
Orthorhombic
P212121
15.302
8.928
6.849
90
90
90
935.685

Fig. 4 UV-Vis-NIR spectrum of LHC crystal.

FTIR spectroscopic analysis The recorded FTIR spectrum of LHC is as shown in figure 3. The
stretching frequency around 3366 cm-1 clearly indicates O-H stretching of carboxylic acid group and the
presence of hydrogen bonding and water molecule in the crystal lattice. In addition, stretching frequency at
3138 cm-1 shows the presence of NH group in amine functionality. The presence of unprotected C=O group
gives its stretching frequency around 1635 cm-1 and C-O at 1086-1097cm-1. Asymmetric bend of NH3+
(1608 cm-1) and its symmetric bend (1499 cm-1) are also clearly seen in the crystal. The peaks at 1566 cm-1 and
1416 cm-1 are assigned to asymmetric and symmetric stretching modes of COO-. The torsional NH oscillation
of NH3+ is obtained at 536 cm-1. The frequency assignment for LHC with various functional groups is
presented in table 2.
www.crt-journal.org

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

62

J. Madhavan et al.: L-histidine hydrochloride monohydrate single crystals

UV-Vis-NIR spectra Figure 4 shows the UV-Vis-NIR spectra recorded with highly transparent and defect
free single crystal of LHC of thickness 2 mm. From absorption spectra it is seen that the crystal is transparent
in the range of 240-2000 nm with out any absorption peak, which is an essential parameter for NLO crystals.
The low percentage of absorbance in the entire visible region is a desirous property for NLO application.
Minimum absorbance is also revealed in the near infrared region.
Table 2 FTIR spectral assignments for LHC single crystal.
Wave number (cm-1)
3450
2870
1635
1608
1566
1499
1416
1086
1000
536

Assignment
O-H stretch of water
C-H aliphatic stretch
C=O stretching
asymmetric bend of NH3+ and C=N stretching
asymmetric mode of COO- and C=C stretching
symmetric bend of NH3+
symmetric mode of COO- and C-N stretching
C-O stretching of carboxyl group
O-H stretching of carboxylic acid
torsional NH oscillation of NH3+

NLO studies The fundamental laser beam of 1064nm was used as a source. For a laser input pulse of
6.2mJ, the second harmonic signal (532 nm) of 91.66mW and 279.20mW respectively were obtained through
KDP and LHC samples. Thus the SHG efficiency of LHC is three times higher than KDP.
Thermal studies Figure 5 shows the TGA and DTA thermogram of LHC. Weight loss of about 35%
between 104C and 148C is attributed to the loss of lattice water. The next stage between 148C and 313C
with a total loss of 58% is assigned to the decomposition of LHC. The resulting residue gives a weight loss for
a wider range of temperature between 330C and 1000C. The weight loss corresponds to 42% and no residue
remains. The endothermic peaks of the DTA trace coincide with the decomposition in the TGA trace.

Fig. 5 TGA and DTA thermogram of LHC crystal.

Fig. 6 Variation of dielectric constant with frequency.

Microhardness test Vickers microhardness test was performed on LHC single crystal to test the hardness
of the sample. Indentations were made on the (010) face of the crystal. Vickers Hardness number was
calculated for the applied loads varying from 5 to 25 g. Development of cracks at higher loads made the
indentation to be restricted to 25 g. A decreasing trend is observed in the hardness values with increasing
applied load and hence the indentation size effect (ISE) is satisfied. The work hardening coefficient value n is
found to be 1.79 for the (0 1 0) plane.
Dielectric studies The dielectric study on LHC single crystal was carried out using the instrument, HIOKI
3532-50 LCR HITESTER. A sample of dimension 5 x 2 x 1 mm3 having silver coating on the opposite faces
was placed between the two copper electrodes and thus a parallel plate capacitor was formed. The capacitance
of the sample was noted for the applied frequency that varies from 500 Hz to 5 MHz. Figure 6 shows the plot
of dielectric constant (r) versus log frequency. The dielectric constant has high values in the lower frequency
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.crt-journal.org

Cryst. Res. Technol. 42, No. 1 (2007)

63

region and then it decreases with the applied frequency. The very high value of r at low frequencies may be
due to the presence of all the four polarizations namely, space charge, orientational, electronic and ionic
polarization and its low value at higher frequencies may be due to the loss of significance of these polarizations
gradually. The variation of dielectric loss with frequency is shown in figure 7. The characteristic of low
dielectric loss with high frequency for a given sample suggests that the sample possess enhanced optical
quality with lesser defects and this parameter is of vital importance for nonlinear optical materials in their
application [13].

Fig. 7 Variation of dielectric loss with log frequency.

Fig. 8 Variation of dark and photo current with

applied field.

Photoconductivity studies Photocurrent and dark current are plotted as a function of the applied field as
shown in figure 8. It is observed from the plot that the photocurrent is always higher than the dark current,
hence it can be concluded that LHC exhibits positive photoconductivity. This phenomenon can be attributed to
generation of mobile charge carriers caused by the absorption of photons [14].

Conclusion

Single crystals of LHC were grown by slow evaporation technique at 301K. From the single crystal X-ray
analysis, lattice parameters are estimated. The UV-Vis-NIR spectra confirm that the crystal is transparent in the
entire visible region. The TGA and DTA studies ascertain the thermal stability of sample up to 104C and the
mechanism responsible for the weight losses is discussed. The NLO studies predict that the SHG of LHC to be
three times more than that of KDP. It is found that both dielectric constant and loss decrease with increase in
frequency. Photoconductivity studies show that LHC exhibits positive photoconductivity. Based on these
observations we can say that LHC can be a promising non linear material, which can be possibly used for
fabrication of photon devices.
Acknowledgements The authors thank, University Grants Commission (UGC) for funding this research project and the
Department of Physics, Loyola College and Loyola Institute of Frontier Energy, Chennai for providing the experimental
facilities. One of the authors (J. Madhavan) thanks University Grants Commission, Government of India, for
granting UGC tenth plan FIP teacher fellowship.

References
[1]
[2]
[3]

D. Yuan, Zhenwu Zhong, Mingguo Liu, Dong Xu, Qi Fang, Yonghong Bing, Suoying Sun, and Minhua Jiang, J.
Cryst. Growth 186, 240 (1998).
G. Lemercier, C. Andraud, I. V. Kityk, J. Ebothe, and B. Robertson, Chem. Phys. Lett. 400, 19 (2004).
D. Eimerl, D. Velsko, S.Davis, L.Wang, F.Loiacono, and G. Kenndy, IEEE J. Quantum Electronics 25, 179 (1989).

www.crt-journal.org

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

64
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]

J. Madhavan et al.: L-histidine hydrochloride monohydrate single crystals

H. O. Marcy, M. J. Rosker, L. F. Warren, P. H. Cunnigham, C. A. Thomas, L. A. Deloach, S. P. Velsko, C. A.
Ebbers, J. H. Liao, and M. G. Konatzidis, Opt. Lett. 20, 252 (1995).
Reena Ittyachan and P. Sagayaraj, J. Cryst. Growth 249, 557 (2003).
Reena Ittyachan, Preema C. Thomas, D. Prem Anand, M. Palanichamy, and P. Sagayaraj, Mat. Chem. Phys. 93,
272 (2005).
H. A. Petrosyan, H. A. Karapetyan, M. Yu. Antipin, and A. M. Peosyan, J. Cryst. Growth 275, 1919 (2005).
H. Fuess and H. D. Bartunik, Acta Cryst. B 32, 2803 (1976).
J. Donohue and A. Caron, Acta Cryst. 17, 1178 (1964).
K. Oda and H. Koyama, Acta Crystallogr. B 28, 639 (1972).
W. S. Wang, K. Sutter, Ch. Bosshard, Z. Pan, H. Arend, P. Gunter, G. Chapouis, and F. Nicolo, Jpn. J. Appl. Phys.
27, 138 (1988).
S. K. Kurtz and T. T. Perry, J. Appl. Phys. 39, 3798 (1968).
C. Balarew and R. Duhlew, J. Solid Sate Chem. 55, 1 (1984).
V. N. Joshi, Photoconductivity, Marcel Dekker, New York 1990.

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.crt-journal.org