Crystal Growth, Optical and Dielectric Properties of L-Histidine Hydrochloride Monohydrate Nonlinear Optical Single Crystals

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Journal of Minerals and Materials Characterization and Engineering, 2012, 11, 813-816

Published Online August 2012 (http://www.SciRP.org/journal/jmmce)

Crystal Growth, Optical and Dielectric Properties of

L-Histidine Hydrochloride Monohydrate Nonlinear

Optical Single Crystal

P. Koteeswari1, S. Suresh2*, P. Mani1

1Department of Physics, Hindustan Institute of Technology, Padur, India

2Department of Physics, Loyola College, Chennai, India

Email: *[email protected]

Received April 25, 2012; revised June 10, 2012; accepted July 1, 2012

ABSTRACT

Optically transparent and bulk single crystal of l-histidine hydrochloride monohydrate (LHHM) was successfully grown

by slow evaporation technique. The cell parameters and the crystallinity of the grown crystal were estimated by the sin-

gle crystal XRD. Optical transmittance of the crystal was recorded using the UV-vis-NIR spectrophotometer. The opti-

cal band gap and optical constant of the material were determined by using transmission spectrum. The dielectric loss

and dielectric constant measurements as a function of frequency and temperature were measured for the grown crystal.

Keywords: Single Crystal; Slow Evaporation Technique; XRD; UV and Dielectric Studies

1. Introduction

The organic NLO materials are attracted by many scien-

tists due to their frequency conversion efficiency, piezo-

electric, pyro-electric properties and their wide applica-

tions in the recent technologies like lasers, optical com-

munications and data storage [1]. New materials with

high optical nonlinearities are quite important due to

their extensive application in harmonic generation, am-

plitude and phase modulation, switching and other signal

processing device [2-4]. The main goal to design the

molecules with the third order nonlinearities is to incor-

porate them into the devices used in all types of optical

signal processing [5-6]. Nonlinear optical (NLO) materi-

als have shown potential application in optical informa-

tion storage, optical logic gates, laser radiation protection

and phase locked laser mode. Hence the interest in

searching for NLO materials has increased gradually [7].

In addition to that organic molecules also have a great

attention owing to their potential application in the frontier

areas such as nonlinear optics (NLO), optical switching

and light emitting diodes. Thus, the potential use of or-

ganic device materials in optoelectronics has now be-

come a serious matter [8]. The present investigation is

aimed at the growth of bulk LHHM single crystal by

slow evaporation technique. The grown crystal has been

subjected to single X-ray diffraction analysis, UV-vis

transmission spectral analysis, optical band gap meas-

urements, and dielectric studies.

2. Experimental Procedure

The l-histidine and hydrochloric acid were taken in equi

molar ratio in double distilled water to prepare the satu-

rated solution of l-histidine hydrochloride monohydrate

(LHHM). The solution obtained is stirred well at room

temperature using a temperature controlled magnetic stir-

rer to yield a homogenous mixture of solution. Then the

solution is filtered using a Whatmann filter paper and

was allowed to evaporate at room temperature. The solu-

tion is recrystallized several times in order to increase the

purity of the crystal. Optically clear and good quality

seed crystal is kept inside the purified saturated solution

and the solution is allowed to evaporate at room tem-

perature, which produces an improved optically high

quality within a period of 30 days. The photograph of the

as grown single crystal is shown in Figure 1.

3. Results and Discussion

3.1. Single Crystal X-Ray Diffraction

Single crystal X-ray diffraction analysis was carried out

to determine the lattice parameters. The grown crystals

have orthorhombic structure with P212121 space group.

The lattice parameter values of the grown crystals are a =

6.82 Å, b = 8.91 Å, c = 15.286 Å. The single crystal data

are in good agreement with reported values [9].

*Corresponding author.

P. KOTEESWARI ET AL.

814

3.2. Optical Transmittance Spectrum Study





Ahv E











The optical transmission spectrum of LHHM single crys-

tal was recorded in the wavelength region 300 - 900 nm

and is shown in Figure 2. For optical fabrications, the

crystal should be highly transparent in the considered

region of wavelength [10] and [11]. Favorable transmit-

tance of the crystal in the entire visible region suggests

its suitability for second harmonic generation [12]. The

UV absorption edge for the grown crystal was observed

to be around 260 nm. The dependence of optical absorp-

tion coefficient on photon energy helps to study the band

structure and type of transition of electrons [13].

Optical absorption coefficient (α) was calculated from

transmittance using the following relation:

log









(1)

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 (α) obeying the fol-

lowing relation for high photon energies (hν).

Figure 1. Photograph of as grown crystal.

Figure 2. Transmission spectrum of the grown crystal

(LHHM).

(2)

where Eg is the optical band gap of the crystal and A is a

constant. A plot of variation of (αhν)2 versus hν is shown

in Figure 3. Eg is evaluated using extrapolation of the

linear part [14]. The energy absorption gap is of direct

type and the band gap energy is found to be 3.90 eV.

3.3. Determination of Optical Constant

The dependence of optical absorption co-efﬁcient with

photon energy helps to study the band structure and the

type of transition of the electron. The absorption coefﬁcient

(α) and the optical constant (n, k) are determined from

the transmission (T) and reﬂection (R) spectrum based on

the following relations, [15,16].

1exp

1exp2

TRt







 

(3)

Reflectance can also be written in terms of absorption

coefficient and from the ab



11exp exp

1exp



 





(4)

and from the above equation, refractive index (n) can also

be derived as



13103

RRR





  (5)

Figure 4 show the variation of refractive index (n) as a

function of wavelength (λ), respectively. From the graphs,

it is clear that refractive index (n) depend on wavelength (λ).

3.4. Dielectric Studies

The dielectric characteristics of the material are important

Figure 3. Plot of (αhν)2 vs photon energy of the title crystal.

P. KOTEESWARI ET AL. 815

to study the lattice dynamics in the crystal. Hence, the

grown crystal was subjected to dielectric studies using a

HIOKI HITESTER model 3532-50 LCR meter in the

frequency range from 50 Hz to 5 MHz for different tem-

peratures. The surface of the sample was electrode with

silver paste for electrical contact. Figure 5 shows the

plot of dielectric constant (εr) versus log frequency. The

dielectric constant has high values in the lower frequency

region and then it decreases with the increase in fre-

quency. The very high value of εr 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. From the plot, it is also observed that dielec-

tric constant increases with an increase in temperature,

and this is attributed due to the presence of space charge

polarization near the grain boundary interfaces, which

depends on the purity and perfection of the sample [17].

Figure 6. Variation of dielectr ic loss with log frequency.

he variation of dielectric loss with frequency is shown

4. Conclusion

l of semi-organic LHHM was grown

[1] N. B. Singh, Tetz, R. Hamacher,

Figure 4. Variation of refractive index with wavele ngth.

in Figure 6. The characteristics of low dielectric loss

with high frequency for the sample suggest that it pos-

sesses enhanced optical quality with lesser defects and

this parameter is of vital importance for nonlinear optical

applications [18].

Bulk single crysta

from aqueous solution by a slow evaporation technique.

Single crystal X-ray diffraction studies confirm that the

grown crystal belongs to orthorhombic crystal system

with space group P212121. The optical transmission

analysis indicates that LHHM has a wide transparency

window in the entire visible and near IR regions with a

lower cutoff wavelength at 260 nm. The band gap was

estimated to be 3.90 eV. The variation of dielectric con-

stant (ε′), dielectric loss and imaginary dielectric constant

(ε″) were studied as a function of frequency at different

temperatures.

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