Available Online at http:// ASIAN JOURNAL OF SCIENCE AND TECHNOLOGY Asian Journal of Scien ce and Technology Vol. 1, Issue 11, pp.067-069, November, 2011 ISSN: 0976-3376 RESEARCH ARTICLE GROWTH OF NONLINEAR OPTICAL MATERIAL: 1-HYDROXYUREA HYDRATE CRYSTAL AND ITS CHARACTERIZATION 1,* Sakthivel, N. and 2Anbarasan, P.M.
1Department of Physics, Maha Barathi Engineering College, Villupuram - 606 201
2Department of Physics, Periyar University, Salem - 636 011
Received 8th March, 2011; Received in revised from; 7h April, 2011; Accepted 5th June, 2011; Published online 12th November, 2011 ABSTRACT
1-Hydroxyurea Hydrate an intriguing new organic material for frequency conversion has been grown by slow evaporation solution growth technique at room temperature. Their structural and physicochemical properties were characterized by X-ray powder diffraction, Dielectric studies, UV-Vis spectra and Hardness studies. The crystal belongs monoclinic symmetry with the space group P21/c, a well-known noncentrosymmetric space group thus satisfying the requirements for second-order NLO activity. The material has a wide transparency in the entire visible region. It is found that the cutoff wavelength lies in the UV region. The mechanical response of the crystal has been studied using Vickers microhardness technique.
Key words: Crystal Growth, Dielectric studies, UV-Vis studies, Hardness studies. INTRODUCTION
large value of hyperpolarizability. In this work 1-hydroxyurea
hydrate crystal was grown by slow evaporation technique. The
In recent years the need of nonlinear optical materials [1-3] is
grown crystals were subjected to Dielectric, Optical and
much more than other materials because of their applications
in optoelectronics and photonics. Second order nonlinear
optical materials have recently attracted much attention
Solubility Studies
because of their potential applications in emerging
optoelectronic technologies. Materials with large second order
The commercially available 1-hydroxyurea hydrate (CH6N2O3)
optical nonlinearities, short transparency cutoff wavelength
was further purified by repeated recrystallization process. In
and stable physico thermal performance are needed in order to
order to obtain organic single crystals of high quality,
realize many of these applications. Especially the organic NLO
purification of starting material was found to be an important
crystals are attracted attention because of the low cost and
step. The recrystallized salt was the charge material for the
flexibility of molecular design, which we need for applications
growth of 1-hydroxyurea hydrate. To grow bulk crystals from
with using suitable donor and acceptor. Organic crystals are
solution by slow evaporation technique, it is desirable to select
having some special properties of large optical nonlinearity[4-
a solvent in which it is moderately soluble. The size of a
5] and low cut-off wavelengths in UV region, therefore the
crystal depends on the amount of material available in the
organic NLO crystals are required for use in optical devices.
solution, which in turn is decided by the solubility of the
Organic materials are often formed by weak vander Waals and
material in that solvent. Hence, we have determined the
hydrogen bonds and hence possess a high degree of
solubility as deionized water. Solubility in deionized water
delocalization. However, these organic crystals have certain
was found good and the crystals grown were found to have
limitations such as poor mechanical and thermal stability. The
better shape and transparency. Good transparent single crystals
contribution from the delocalized π - electrons belonging to
were obtained after ten days. Fig. 1 shows the Solubility curve
the organic ligand results in wide optical transmittance and
of 1-hydroxyurea hydrate. Fig. 2 shows the grown crystal of 1-
high nonlinear electro - optic coefficients. Many device
hydroxyurea hydrate with an optimized solution pH value of
applications of NLO require single crystals in the bulk form. 1-
hydroxyurea hydrate is an organic NLO material possessing *Corresponding author: an.sakthivel@yahoo.co.in 068 Asian Journal of Science and Technology, Vol. 1, Issue 11, pp.067-069, November, 2011 Mechanical Behaviour Hardness of the material is a measure of resistance, It offers to deformation. The transparent crystals free from cracks were
indentation were made on the grown surface with the load
ranging from 25gms-200gms using Vickers microhardness
tester. Leitz-Wetzlar fitted with a Vickers diamond pyramidal
indenter and attached to an incident light microscope. The
indentation time was kept as 5s for all the loads. The Vickers
hardness number Hv was calculated from the following equation
Where P is the applied load in kg and d is the diagonal length of the indentation impression in micrometer and 1.8554 is
Fig. 1. Solubility curve of 1-hydroxyurea hydrate
constant of a geometrical factor for the diamond pyramid. Fig.
4 shows the variation of mechanical behaviour of 1-
hydroxyurea hydrate with applied load. In ideal circumstance the hardness value should be independent of applied load. But in practice the load dependence is observed. As the load is increased there is steep fall in hardness. The decrease of microhardness with increasing load is in agreement with normal indentation size effect (ISE) as observed by others.The decrease of microhardness in 1-hydroxyurea hydrate crystal is attributed to certain type of impurities incorporated into the lattice.
Fig. 2. Grown crystal of 1-hydroxyurea hydrate Powder X-ray diffraction analysis The XRD data of the crystal still possesses monoclinic
symmetry with the space group P21/C, a well-known noncentrosymmetric space
requirements for second-order NLO activity. The lattice
parameter values of the crystal have been calculated using
least-squares fit method and they are found to be a = 8.329 Ǻ ,
b = 4.662 Ǻ , c = 8.829 Ǻ, α=γ=90º, β=122.40º respectively.
Fig. 4. Plot of Hv versus Load of 1-hydroxyurea hydrate
The crystallographic data obtained in the present study were
found to be in good agreement with the data reported in
Dielectric Studies
literature.The chemical structure of 1-hydroxyurea hydrate
capacitance, C, and tan d, were obtained using a computer
controlled LCR HiTester (HIOKI,3532-50) for different
frequencies in the range100Hz-1MHz. The dielectric
constant[9-10] of a material is generally composed of four types of contributions, viz. ionic, electronic, orientational and space charge polarizations. All of these may be active at low
frequencies. The nature of variations of dielectric constant
with frequency and temperature indicates the type of contributions that are present in them. The dipolar orientational effect can be seen in some materials at high
frequencies and ionic and electronic polarizations below 103
Hz. The large value of εr at low frequency and at low
temperature is due to the presence of space charge
polarization, which depends on the purity and perfection of the
Fig. 3. Chemical Structure of 1-hydroxyurea hydrate
sample. Fig. 5 shows the variation of dielectric constant with
frequency measured at room temperature for the 1-
069 Asian Journal of Science and Technology, Vol. 1, Issue 11, pp.067-069, November, 2011
hydroxyurea hydrate crystal. The dielectric constant is a
takes place at a wavelength of 198 nm. This absorbance
maximum at low frequency and decreases with increasing of
maximum at 198 nm was assigned to -* transition and may
frequency for the crystals. The increase in the dielectric
be attributed to the excitation in the C=O group. The absence
constant at low frequency is attributed to space-charge
of the absorption in the visible region is the necessity for this
compound as it is to be exploited for NLO applications in the room temperature.
Conclusion
Good quality single crystals of 1-hydroxyurea hydrate were
grown by slow evaporation solution growth technique. The X-
ray diffraction revealed the crystallization of material in
transparency also adds to the possible application of the
material is the field of nonlinear optics. The results of optical transparency are encouraging. Moreover, its lower cutoff
wavelength with wide optical transparency window in the visible region makes this material suitable for extensive
investigations. These crystals have very good characteristics
for fabrication and the results of optical transparency in
suggesting the material with potential applications in nonlinear optics.
Fig. 5. Variation of dielectric constant with frequency for 1- hydroxyurea hydrate crystal Acknowledgement
The authors are thankful to Shri.Ch.Seshendra Reddy and
Shri.C.R. Kesavulu, Department of Physics, Sri Venkateswara University, Tirupati 517 502, India for measurements.
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the entire visible region and the transmittance takes place in
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