Single crystal growth and characterization of the nonlinear optical crystal l-arginine hydrofluoride

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Abstract

In this communication, single crystal growth of the nonlinear optical crystal l-arginine hydrofluoride C6H14N4O2. HF (here after abbreviated as LAHF) of dimensions up to 20×15×3 mm3 is reported. Crystals have been grown by the temperature lowering method and also by slow evaporation method at constant temperature 30°C from its aqueous solution with pH at 2.2. As-grown single crystals were then characterized by density measurement, solubility test, X-ray powder diffraction studies and infrared (IR) spectroscopy.

Introduction

Nonlinear optical (NLO) materials are attracting a great deal of attention because of their use in optical devices, such as optical switches, optical modulators, optical bistable devices, electrooptical devices. Organic materials have been of particular interest because the nonlinear optical responses in this broad class of materials is microscopic in origin, offering an opportunity to use theoretical modeling coupled with synthetic flexibility to design and produce novel materials [1]. However most organic NLO crystals have usually poor mechanical and thermal properties and are susceptible to damage during processing. In view of this, a new type of NLO materials have been built from organic-inorganic complexes in which the high optical non-linearity of a purely organic compound is combined with the favorable mechanical and thermal properties of an inorganic materials. l-arginine phosphate monohydrate (LAP) is one such semiorganic nonlinear optical material discovered by Xu et al. [2]. LAP has high nonlinear optical coefficients, high damage threshold, high angular sensitivity compared to potassium dihydrogen phosphate (KDP), the most widely used material for frequency conversion. Since the discovery of LAP [2], [3], it was considered to be a highly promising candidate for new polar materials. So scientists [4], [5], [6], [7] tried to synthesize and grow several other salts of l-arginine especially in respect of their non-linear optical properties. Monaco et al. [4] synthesized ten such salts of l-arginine and measured their linear and non-linear optical properties using crystals as small as 50–100 μm. Out of those ten salts the most attractive one was l-arginine hydrofluoride (LAHF). Arunmozhi et al. has reported [8] the growth of large crystal of LAHF and results of linear and nonlinear optical studies. However apart from the optical studies, no other studies on LAHF have been carried out till to date. So we have tried to grow large size single crystals of LAHF for the measurement of other physical properties. In this present paper we deal with the synthesis, solubility and growth of LAHF crystal from its aqueous solution by slow evaporation as well as by slow cooling method followed by characterization of the grown crystals by X-ray diffraction and infrared spectroscopy. At this stage it is necessary to access the quality of the grown crystals by chemical etching or by X-ray Lang topography and work in this direction will be reported in future publications.

Single crystal structure of LAHF has been solved by Karapetyan and Petrosyan [9]. They reported the following crystallographic data: a=5.445(1)Å, b=8.514(2)Å, c=10.221(2)Å, β=93.46°(3), space group P21.

Section snippets

Synthesis and purification

LAHF was synthesized by dissolving one equivalent amount of strongly basic amino acid, l-arginine (Lobachemie), (H2N)NHCNH(CH2)3CH(NH2)COOH in twice distilled water containing one equivalent of hydrofluoric acid. The synthesized salt was then purified by repeated crystallization.

Crystal growth

Single crystals of LAHF were grown from saturated aqueous solutions of the salt of LAHF by the slow evaporation technique at constant temperature 30°C. The solution was kept in a plastic container covered with a

Solubility test

The solubility of LAHF in water was determined by saturating the solutions at high temperature and then slowly cooling the solution in the presence of precipitated solid to maintain equilibrium and then sampling and analyzing the solution at defined temperatures. The resulting solubility curve is shown in Fig. 2.

Density measurement

The density of an as-grown crystal was measured by the flotation method in a mixture of carbon tetrachloride (CCl4) and chloroform (CHCl3) and found to be 1.364 g cm−3. This agrees well

Conclusion

In this paper the synthesis and growth of LAHF, a nonlinear crystal has been described. Solubility curve of LAHF in water is also determined which is exponential in nature. The identity of the synthesized material is then confirmed by X-ray diffraction study. pH value of the solution of the salt plays a dominant role in the growth of the crystal and the the optimize pH value for the growth of optically clear crystal of appreciable size is found to be 2.2. FTIR results confirmed the zwitterionic

References (11)

  • S.B. Monaco et al.

    J. Crystal Growth

    (1987)
  • A.M. Petrosyan et al.

    J. Crystal Growth

    (2000)
  • D.S. Chemla et al.

    Nonlinear Optical Properties of Organic Molecules and Crystals

    (1987)
  • D. Xu et al.

    Acta Chem. Sinica.

    (1983)
  • D. Eimerl et al.

    IEEE J. Quantum Electron QE

    (1989)
There are more references available in the full text version of this article.

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