Effect of solvents on the growth morphology and physical characteristics of nonlinear optical γ-glycine crystals

doi:10.1016/S0022-0248(02)01327-1

Journal of Crystal Growth

Volume 242, Issues 1–2, July 2002, Pages 245-252

https://doi.org/10.1016/S0022-0248(02)01327-1 Get rights and content

Abstract

Bulk crystals of γ-glycine have been grown at ambient temperature by solvent evaporation from a mixture of water–sodium salt as a solvent. The chemical composition of the grown crystal was determined by NMR and laser Raman spectra. The morphology of the crystals grown from various solvents showed a marked difference. The temperature of transition from γ- to α-phase was determined using differential scanning calorimetry. It was observed that all the crystals except the one grown from a mixture of water and sodium hydroxide change from γ- to α-phase at 168°C. The transition temperature of the glycine crystal grown from the mixture of glycine and sodium hydroxide was 172°C and the transition takes place at a lower rate. The microhardness of the crystals grown from various solvents was determined. It was found that the crystals grown from various solvents had the same hardness number. The second harmonic conversion efficiency of the grown crystals was measured relative to potassium dihydrogen phospahte. It was observed that the conversion efficiency of the crystals grown from various solvents vary slightly.

Introduction

γ-Glycine is one of the polymorphic forms of the amino acid glycine. While other two polymorphic forms α-glycine and β-glycine crystallize in centrosymmetric space group P2₁/c [1], [2], γ-glycine crystallizes in noncentrosymmetric space group P3₁ with cell parameters a=b=7.04065 Å and c=5.4842 Å making it a candidate for piezo electric and nonlinear optical (NLO) applications [3]. The carboxylic acid group present in the γ-glycine donates its proton to the amino group to form a salt of the structure CH₃CH-COO⁻NH₃⁺. Thus, in solid state, γ-glycine exists as a dipolar ion in which carboxyl group is present as a carboxylate ion and amino group is present as ammonium ion. Due to this dipolar nature, glycine has a high melting point. Moreover, the chromophores present in glycine, viz. amino group and carboxyl groups, are transparent and show almost no absorption in the UV region. As a result the UV cutoff of γ-glycine is below 300 nm which is sufficiently low for second harmonic generation (SHG) from a laser operating at 1064 nm or other applications in the blue region. All these properties make γ-glycine an ideal candidate for NLO applications and hence there is a need to grow bulk crystals of γ-glycine.

All the polymorphic forms of glycine are water soluble and bulk crystals can be grown from aqueous solution either by slow evaporation or slow cooling techniques. But the growth mechanism of glycine is complicated. It grows in many forms including the unstable β-form. Ever since the first report in 1962 [3], no work has been reported on the growth of γ-glycine. In order to obtain large single crystals of γ-glycine with adequate size for nonlinear applications, a systematic investigation has been carried out in our laboratory. The growth of γ-glycine in the presence of small amount of sodium chloride is reported [4]. In this paper, the growth of γ-glycine from a mixture of water and (i) sodium hydroxide, (ii) sodium flouride (iii) sodium nitrate and (iv) sodium acetate is reported. The changes in crystal growth morphology and physical characteristics of the crystals grown from different solvents are also discussed.

Section snippets

Crystal growth

Analytical grade glycine was dissolved in double distilled water. This solution was distributed in various beakers. Pre-determined amounts of analytical grade reagents sodium hydroxide, sodium flouride, sodium nitrate and sodium acetate, respectively, were added to these beakers such that the concentration of these salts ranges from 2% to 10%. The resulting solution was filtered twice and then heated on a water bath maintained at constant temperature until the volume was sufficiently reduced.

XRD

Powder XRD of the crystals grown from various solvents was recorded in order to ascertain that the crystal is in γ-phases of glycine. We have recorded the powder XRD pattern using SCINTAG powder X-ray diffractometer with Cu K_α radiation (λ=1.5418 Å) and index them. The sample was scanned in the 2θ values from 10° to 60° at a rate of 2°/min. Figs. 6(a)–(d) show the indexed powder XRD pattern of the glycine crystals grown from a mixture of water and (i) sodium hydroxide, (ii) sodium flouride (iii)

Second harmonic conversion efficiency

The SHG conversion efficiency of γ-glycine was determined by the modified version of the powder technique developed by Kurtz and Perry [13]. The experimental setup is shown in Fig. 11. The crystal was ground into powder and densely packed between two transparent glass slides. An Nd:YAG laser beam of wavelength 1064 nm was made to fall normally on the sample cell S. The transmitted fundamental wave was absorbed by a CuSO₄ solution (F₁) which removes the incident 1064 nm light. F₂ is a BG-38

Conclusion

Bulk crystals of γ-glycine have been grown at ambient temperature by solvent evaporation from various solvents. The morphology of the crystals grown from various solvents showed a marked difference. It was observed that All the crystals except the one grown from a mixture of water and sodium hydroxide changed from γ- to α-phase at 165°C. The microhardness of the crystals grown from various solvents was the same. The relative conversion efficiency of the crystals grown from various solvents

Acknowledgments

N.B is thankful to U.G.C for the teacher fellowship. We are grateful to Prof. P.K. Das, IPC lab of I.I.Sc. for the laser facilities and the centre director of IUC Indore for providing the DSC facilities.

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Effect of solvents on the growth morphology and physical characteristics of nonlinear optical γ-glycine crystals

Abstract

Introduction

Section snippets

Crystal growth

XRD

Second harmonic conversion efficiency

Conclusion

Acknowledgments

Acta Crystallogr. B

Acta Crystallogr.

J. Crystal Growth

Contemp. Phys.

Nature