Investigation on Pure and L-lysine Doped Glycine Barium Chloride Single Crystal

Mechanics, Materials Science & Engineering, March 2017

ISSN 2412-5954

Investigation on Pure and L-lysine Doped (Tri) Glycine Barium Chloride (TGBC) Single Crystal for Nonlinear Optical Applications 2 S. Chennakrishnan1, S.M. Ravikumar2, D. Sivavishnu2, M. Packiya Raj3, S.Varalakshmi4 1

Dept. of physics, Idhaya Arts & science College for women, Tiruvannamalai-606 603, Tamil Nadu, India

2

Department of physics, Government Arts College, Tiruvannamalai-606 603, Tamil Nadu, India

3

Department of Physics, S.K.P. Engineering College, Tiruvannamalai 606 611, Tamil Nadu, India

4

Department of physics, Kamban College of Arts & Science for Women, Tiruvannamalai 606 601. Tamil Nadu, India DOI 10.2412/mmse.05.501.447 provided by Seo4U.link

Keywords: solution growth, X-ray diffraction, nonlinear optical material, thermal study.

ABSTRACT. Single crystals of pure and L-lysine doped (tri) glycine barium chloride (TGBC) were grown by slow solvent evaporation technique with the vision to improve the physicochemical properties of the sample. Single crystal Xray diffraction analysis of both pure and doped samples was carried out and the results are compared. Optical absorption and FTIR spectroscopic studies are performed to identify the UV cut-off wavelength range and the presence of various functional groups in the grown crystals. The thermos-gravimetric (TG) analysis of L-lysine doped TGBC indicates a marginal increase in the thermal stability of the crystals. The SHG efficiency of pure and doped TGBC was discussed.

1. Introduction. A novel nonlinear optical (NLO) crystal is attracting many theoretical and experimental researchers recently because NLO crystals are used in various applications in the areas like high speed information processing, optical communication, optoelectronics and optical data storage [1-3]. Materials with large second order harmonic optical nonlinearities, transparency at required wavelength and stable physicochemical performance are needed to realize the many of these applications. Currently there is a need for materials with large non linearity, which efficiently double the low peak power sources such as diode laser [4]. Among the different varieties of NLO crystals, semi-organic crystals are gaining rapid interest due to their interesting and intriguing properties.

Optical non-linearity of inorganic crystals is generally lower than that of optical device demand organic compounds are often formed by weak Vander walls, hydrogen bond and process a high degree of delocalization [5-8]. A major drawback of organic NLO crystals is the difficulty in growing large size good optical quality and high mechanical stability single crystal [9]. In fact, considerable effort has been made on semi-organic crystals due to their having the combined properties of both inorganic and organic crystals also high damage threshold, wide transparency range, high mechanical strength and chemical stability. Hence, the semi-organic crystals are suitable for the device fabrication [1012].

Amino acid based semi-organic compounds have been recently recognized as potential candidates for second harmonic generation (SHG) [13 15]. Amino acids are interesting materials for NLO applications as they contain proton acceptor carboxyl acid (-COOH) group and the proton donor amino (NH2) group. Glycine (NH2-CH2-COOH) is the simplest amino acid. Unlike other amino acids, it has as symmetric carbon atom and is optically inactive. Also, glycine can be readily combined with variety of acids, organic and inorganic components to produce a host of materials with interesting properties [16-17]. Glycine mixed with metal chlorides such as zinc chloride [18], calcium chloride [19], potassium chloride [20], sodium chloride [21] and lithium chloride [22] has been reported in the 22

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Mechanics, Materials Science & Engineering, March 2017

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recent years. Interest have been centered on semiorganic crystal which have the combined properties of both inorganic and organic crystals like high damage threshold, wide transparency range, less deliquescence, higher mechanical strength and chemical stability which make them suitable for device fabrication [23]. The advantage of semi-organic materials is that they can be grown from aqueous solution and form large three dimensional crystal of excellent physico-chemical properties.

Hence, it is necessary to synthesize and grow novel semiorganic crystals. Hence, the interest has been centered on Glycine Barium chloride and suitable dopants. In this present investigation, we report bulk growth of pure and L-lysine doped (tri) glycine barium chloride crystal by solution growth technique. The grown crystals were characterized using single crystal XRD and powder X-ray diffraction, Fourier transform infrared (FT-IR) analysis, UV-vis-NIR spectroscopy and thermosgravimetric analysis (TGA), differential thermal analysis (DTA).

2. Materials and Methods 2.1. Synthesis for pure TGBC The title compound of (tri) glycine barium chloride was synthesized by reacting glycine (Merck, GR grade) and barium chloride (Merck, GR grade) with stoichiometric ratio of 3:1 at room temperature.

A necessary quantity of glycine is dissolved in double distilled water at room temperature until it attains saturated condition. After preparing saturated solution of glycine, the proportionate amount of barium chloride was added with glycine solution while continuous stirring for 4 hours to bring a homogenous mixture of solution of (tri)glycine barium chloride. The (tri) glycine barium chloride was synthesized on the following chemical reaction.

3(NH2-CH2-COOH) + BaCl2

Ba (NH2-CH2-COOH)3Cl2

2.2. Synthesis for doped TGBC An appropriate amount of analytical reagent grade of L-lysine were added with saturated mother solution of (tri) glycine barium chloride to form a aqueous solution of L-lysine doped TGBC. The solution was stirred using magnetic stirrer for 6 hours to obtain the homogeneous solution at room temperature.

The chemical reaction of synthesized compound was shown below, CH2N (CH2)4CH (NH2) + Ba (NH 2-CH2-COOH)3 Cl2

BaCH2N(CH2)4CH(NH2) (NH2-CH2-COOH)3 Cl2)

2.3. Crystal Growth for Pure and Doped TGBC The saturated solution of pure TGBC and L-lysine doped TGBC were filtered using whattman filter paper to remove impurities. The super saturated solution of pure and doped TGBC was tightly covered with polyethylene sheet, to keep out from dust free area and the solution were allowed to evaporate at room temperature. After 15 to 20 days good quality seed crystal of pure TGBC were obtained whereas the L-lysine doped TGBC has taken 10 days later to get the seed crystal . The good quality and defect free seed crystal of pure and doped TGBC was selected for bulk growth. The (tri) 3 has been harvested in the period of 25 to 35 days but L-lysine doped TGBC were grown with dimension 7 x 9 x 2 mm3 in the period of 45 days with different morphology and the grown crystals are highly transparent. As grown crystal of pure TGBC and L-lysine doped TGBC was shown in Figure 1. The optimized growth condition of pure and L-lysine doped (tri) glycine barium chloride is given the table 1.

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Mechanics, Materials Science & Engineering, March 2017

Pure TGBC crystal

ISSN 2412-5954

Doped TGBC Crystal

Fig. 1. As grown crystal of pure and doped TGBC. Table 1. The optimized growth condition of pure and doped TGBC. Pure TGBC

Doped TGBC

Growth method

Slow evaporation

Slow evaporation

Solvent used

Double distilled water

Double distilled water

Molecular formula

Ba(NH2-CH2-COOH)3 Cl2

Ba CH2N(CH2)4CH(NH2) (NH2- CH2 COOH)3 Cl2

Molar ratio

Glycine + Barium chloride

L-lysine +Glycine + Barium chloride

Temperature

Room temperature

Room temperature

Period of growth

25 to 35 days

45 days

Dimension of the crystal

3

7x9x2 mm3

3.0 Results and Discussion 3.1. Single crystal X-Ray Diffraction (XRD) Analysis Single Crystal X-ray diffraction analysis of pure and L-lysine doped TGBC was recorded using ENRAF NONIUS CAD-4 automatic X-ray diffractometer. This analysis reveals that the pure and doped TGBC crystallizes in orthorhombic system with space group pbcn. The calculated lattice 3

3

.

The lattice parameters are well agreed with reported value [24]. Thus, the XRD results confirm that MMSE Journal. Open Access www.mmse.xyz

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Mechanics, Materials Science & Engineering, March 2017

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there is no change in crystals structure, but there is a small changes in the lattice parameters. The change in the lattice parameter may due to incorporation of L-lysine with TGBC. 3.2. Powder X-Ray Diffraction Analysis Powder XRD diffraction analysis was carried out using BRUCKER, Germany (model D8 Advance) X-ray diffractometer with CuKalpha to 80o at a scanned rate of 1o per minute to study the crystalinity of the grown crystal. The diffracted peaks are varying for pure and doped a TGBC crystal, which is shown in figure 2. The well-defined sharp peaks signify the good crystalline nature of the pure and doped TGBC crystal.

Fig. 2. Powder XRD pattern of pure and L-lysine doped TGBC crystal.

3.3. Fourier Transform Infrared (FTIR) spectroscopy study The infrared spectral analysis is fruitfully used to understand the chemical bonding and provides information about molecular structure of the synthesized compound. Crushed powder of pure and Llysine doped (tri) glycine barium chloride was pelletized using KBr. The spectrum was recorded using a Thermo Nicolet V-200 FTIR Spectrometer in the range 4000 - 400 cm-1 wavenumber region. The FTIR spectra of powdered TGBC with and without L-lysine are shown in Figure 3. The observed wavenumbers and their corresponding assignments for the title compound were found and listed in the table 2. The peaks around 3432 cm-1 is attributed to NH asymmetric stretching whereas in Llysine doped TGBC crystal this mode was found at 3437 cm-1. The drift in wavenumber of the doped crystal is due to the participation of amino groups in the hydrogen bonding formation. The peaks obtained at 3062, 3059 and 2981 cm-1 for pure and doped crystals, respectively were assigned to CH stretching. The peaks of IR spectrum at 2589, 2590 cm-1 for pure and doped crystal ascribed to NH3+ stretching vibration. The NH3+ deformation of pure and doped TGBC was observed as sharp peak at 1571 cm-1. A very strong peak is observed at 1478 cm-1 may due to vibration of NH2 deformation for pure TGBC whereas this peak is shifted to 1480 cm-1 in L-lysine doped crystal. The COO- symmetric stretching is observed as a sharp peak at 1404 and 1406 cm-1 for pure and doped TGBC respectively . The pure and doped TGBC crystal, the peak at 1330 and 1336 cm-1 are due to C-N-H symmetric bending. The peak around 1116 cm-1 , 896 and 668 cm-1 attributed to CH2 rocking, CCN stretching and C-Cl stretching respectively. A peak at 1031 and 1035 cm-1 for C-C-N-C symmetric stretching for pure and doped TGBC respectively.

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Fig. 3. The FTIR spectrum of pure and doped TGBC. Table 2. Band assignments of FTIR spectrum of doped TGBC. Wavenumber cm-1 Doped TGBC Pure TGBC 3432 3437 3062 3059 2984 2589 2590 1571 1574 1478 1480 1404 1406 1330 1336 1116 1118 1031 1030 896 898 668 669

Assignments NH asymmetric stretching C-H stretching C-H stretching NH3+ stretching NH+3 deformation NH2 deformation COO- symmetric stretching C-N-H symmetric stretching CH2 rocking C-C-N C symmetric stretching CCN stretching C-Cl stretching

3.4. Optical Transmission Study Crystal plates of pure TGBC and doped TGBC with a thickness of 2mm were cut and polished without any coating for optical measurements optical transmission spectra were recorded for the grown crystals in the wavelength region from 200 to 1000 nm using double beam UV visible spectra of pure and doped TGBC crystals is shown in figure 4. From the transmission spectra, it is noticed that pure and L-lysine doped TGBC crystal has high transmittance in the entire visible NIR region of the spectra, and this property enables the materials for the NLO application. A UV cut off wavelength MMSE Journal. Open Access www.mmse.xyz

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for pure TGBC and doped TGBC is observed at 234 nm and 251 nm respectively. This is an augmented characteristic for the fabrication of optoelectronic devices [25].

Fig. 4. Optical transmission of pure and doped TGBC. 3.5 Nonlinear optical study SHG conversion efficiency measurements has been carried out using Kurtz and Perry technique [26].

A Q-switched Nd:YAG laser beam of wavelength 1064 nm with input beam energy of 1.5 mJ/pulse and pulse width 10 ns with a repetition rate of 10 Hz was used. The grown crystals of pure and Llysine doped TGBC crystal was powdered with uniform particle size and tightly packed in a microcapillary of uniform bore and exposed to the laser radiation. emission has been observed which indicates that the SHG behaviour of the grown crystals. The relative SHG efficiency of pure TGBC (10.84 mJ) and L-lysine doped TGBC (14.56 mJ) are nearly 1.33 and 1.86 times that of KDP (7.80 mJ) respectively.

3.6 TG - DTA analysis Thermal properties of the material was studied by Thermogravimetric (TGA) and Differential Thermal Analysis (DTA) using STA 409 C instrument between the temperature 50 and 800 heating rate of 20 the TGDTA curve of pure and L-lysine doped TGBC crystals respectively.

The absence of water molecule in pure and L-lysine doped TGBC crystal was observed by absence e and 174.4 -lysine doped TGBC, which corresponds to the melting point of the compound. Hence the thermal stability of pure and doped tri-glycine barium chloride to the addition of L-lysine with TGBC the thermal the sudden loss of mass due to the glycine. From the TG curve, the mass loss is take place after the tempe loss of 7% occuring in the temperature limit of 321h confirms the L-lysine doping into the TGBC crystal. The actual residual amount of mass is 50% which may be considered to be the compound of barium. From the above analysis, the melting point of the pure and doped (tri) glycine barium chloride -glycine sulpho-nitrate -18].

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45.00 5.3%

100.0

40.00 90.0 35.00 43.0%

80.0

30.00 70.0 25.00 60.0 20.00 50.0 15.00 40.0 10.00 30.0 5.00

169.3Cel 5.36uV

321.8Cel 4.33uV

20.0

0.00 10.0 -5.00 0.0 -10.00 100.0

200.0

300.0

400.0 Temp Cel

500.0

600.0

700.0

800.0

Fig. 5. TG and DTA curve of pure TGBC crystal.

5.1%

0.00

100.0

90.0

-5.00

80.0

41.2%

-10.00

-15.00

70.0

-20.00

60.0

50.0

-25.00 525.1Cel -29.46uV

40.0

-30.00

30.0

-35.00

174.4Cel -34.88uV 20.0

-40.00

10.0

-45.00

-50.00 100.0

200.0

322.0Cel -49.24uV 300.0 400.0 Temp Cel

0.0 500.0

600.0

700.0

800.0

Fig. 6. TG and DTA curve of L-lysine doped TGBC crystal.

Summary. Well-developed good quality transparent crystals of pure and L-lysine doped TGBC was grown successfully by slow evaporation technique. Unit cell parameters and crystal system were determined by single crystal X -ray diffraction technique. Powder XRD shows good crystalline of the grown pure and doped crystal. The various functional groups presence in the grown crystal of pure and doped was identified by FTIR study. The UV cut off wavelength of pure and L-lysine doped TGBC crystal was found to be 234 nm and 251 nm respectively, which reveals grown crystals are potential candidate for NLO applications. The second harmonic generation (SHG) efficiency of pure and L-lysine doped TGBC crystal is about 1.33 and 1.86 times that of KDP respectively and the addition of L-lysine with TGBC the SHG efficiency has increased. Thermal properties of the material was studied by Thermogravimetric (TGA) and Differential Thermal Analysis (DTA), the melting point of the pure and doped tri- glycine barium chloride Acknowledgement Acknowledgments The Corresponding author sincerely thankful to UGC for funding minor research project, (MRP06288/15 (SERO/UGC) and also acknowledge Dr. M. Basheer Ahamed, Head, Dept.

Of Physics, B. S. Abdur Rahman University, Chennai for carryout the NLO test.

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Cite the paper S. Chennakrishnan, S.M. Ravikumar, D. Sivavishnu, M. Packiya Raj, S.Varalakshmi (2017). Investigation on Pure and L-lysine Doped (Tri) Glycine Barium Chloride (TGBC) Single Crystal for Nonlinear Optical Applications. Mechanics, Materials Science & Engineering, Vol 8. doi:10.2412/mmse.05.501.447

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