Studies on influence of Cd2+ ions in unidirectional growth and characterization of l-Cysteine hydrochloride monohydrate single crystals

https://doi.org/10.1016/j.saa.2014.10.115Get rights and content

Highlights

  • Unidirectional growth resulted the crystals free from structural boundaries.

  • Increase of transparency w.r.t. undoped.

  • Cd based crystal exhibited 1.3 times better SHG value than standard KDP.

Abstract

Cadmium doped l-Cysteine hydrochloride monohydrate (Cd2+–C3H7NO2S⋅HCl⋅H2O), a non-linear optical crystal, was grown by conventional as well as unidirectional solution growth techniques. While the dimension of the conventionally grown crystal was 16 × 14 × 5 mm3, the dimension of the crystal grown unidirectional method was 32 mm long and 6 mm diameter. The grown crystals were studied using XRD for phase analysis, HRXRD for crystalline perfection and UV–Vis NIR spectroscopy for optical properties. The high crystalline perfection was found in the crystal grown by unidirectional method than that grown by conventional one. FTIR study indicates that Cd2+ ion was coordinated to l-Cysteine⋅HCl⋅H2O through S ligand. The nonlinear optical character of the title compound was observed by measuring the SHG efficiency, which is 1.35 times to that of KDP by Kurtz technique.

Introduction

In recent years tremendous efforts were made to grow large size single crystals of organic nonlinear optical (NLO) materials with increased perfection due to rapid development in laser related applications, optical tele communications, optical data storage and optical information processing [1]. The family of organic amino acids shows interesting NLO properties [2], [3]. l-Cysteine is a sulphur-containing amino acid which is characterized by the presence of the group (–SH). In the cysteine molecule, the functional groups, such as –NH2, –COOH and –SH, have a strong tendency to coordinate with inorganic cations and metals, which has been demonstrated by Burford and co-workers on the basis of the observations of mass spectrometry [4]. As per the double radical theory, the metal–organic coordination complexes can provide an enhancement of the physico-chemical stability, the breaking up of the centro-symmetry of the ligand in the crystal and an increase in NLO intensity, via metal–ligand bridging interactions [5], [6], [7], [8], [9], [10], [11], [12], [13]. The effects of metal dopants on the growth and properties of single crystals are investigated by many research groups on different materials [14], [15], [16], [17], [18], [19], [20], [21], [22]. The Cu2+ and Cd2+ metal ions doped in l-Cys⋅HCl crystals also provides a valuable information on the binding mechanism of Cd in l-Cys rich environments and the formation of phytochelatin metallothionein complexes [23]. Chapman et al. [24] reported that l-Cysteine hydrochloride monohydrate (l-Cys HCl⋅H2O) with molecular formula C3H7NO2S⋅HCl⋅H2O belongs to the orthorhombic crystal system with space group P212121 which indicates that the crystal is non-centrosymmetric. Recently, the unidirectional growth and characterization of l-Cysteine hydrochloride monohydrate have been reported by Bhagavannarayana et al. [25].

The title compound was grown by slow evaporation solution technique (SEST) and Sankaranarayanan–Ramasamy (SR) methods. In slow evaporation solution technique many growth induced defect structures were observed which comprises of low angle grain boundaries [26] dislocations, vacancies [27] faults [28] can be attributed to impurities. But in SR method grown crystals are free from such defects. Therefore, the Sankaranarayanan–Ramasamy (SR) method [29] was used to grow Cd2+doped l-Cysteine hydrochloride monohydrate single crystal with a specific orientation in an ampoule. Hence in the present work, an attempt has been made to study on growth and characterization of metal ion (Cd2+) doped l-Cysteine hydrochloride monohydrate single crystal. The structure, functional groups, crystalline perfection were revealed by using powder X-ray diffraction analysis, FTIR, HRXRD and UV–vis, SHG measurements were carried out to assess optical transparency, enhancement of NLO properties of the doped crystals compared to undoped l-Cysteine hydrochloride monohydrate.

Section snippets

Synthesis and conventional growth

The title compound was synthesized by adding 1 mol% cadmium chloride with l-Cysteine hydrochloride monohydrate and the chemical reaction given asC3H7NO2S·HCl·H2O+CdCl2Cd(C3H7NO2S·HCl·H2O)Cl2

The single crystals of Cd doped l-Cysteine hydrochloride monohydrate was grown from its saturated aqueous solution by slow evaporation solution growth technique. The saturated solution was prepared at 30 °C, filtered and placed inside a constant temperature bath (CTB) having an accuracy of ±0.01 °C. The

Powder X-ray diffraction analysis

Powder XRD measurements were carried out using a PW1830 Philips Analytical X-ray diffractometer with nickel-filtered Cu Kα radiation (35 kV, 30 mA) at a scan rate 0.02° s−1 for the 2θ angular range of 10–60° at room temperature. From the powder XRD spectra, it is found that the Cadmium doped l-Cys HCl H2O crystals belongs to orthorhombic system and space group is The recording spectrum is shown in Fig. 3. The determined lattice parameters are a = 19.328 Å, b = 7.249 Å and c = 5.521 Å which were calculated

Conclusions

The powdered-XRD, HRXRD, FTIR and Kurtz technique reveals the influence of Cd doped l-Cysteine⋅HCl⋅H2O single crystals. The powder X-ray diffraction analysis of doped samples shows some minute structural variations. FTIR study shows the incorporation of Cd2+ ions through S-group in l-Cysteine⋅HCl⋅H2O and also shows slight shifts in peak positions. High-resolution XRD studies revealed that the crystalline perfection of the unidirectional grown crystal is much better (without having any

Acknowledgements

The authors are grateful to Dr. G. Bhagavannarayana, NPL Delhi for HRXRD studies. KRR is grateful to Dr. V. Sudarsan, Baba Atomic Research Centre (BARC) for XRD and FTIR studies. He also wishes to thank Prof. P.K. Das, IASc, Bangalore and Dr.Ch. Mastanaiah, Principal, Government College (A), Rajahmundry, AP.

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