Growth and Characterization of Triglycine Sulphate Single Crystal by Sankaranaryanan–Ramasamy Method

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ScienceDirect Materials Today: Proceedings 5 (2018) 18815–18822

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ICMPC_2018

Growth and Characterization of Triglycine Sulphate Single Crystal by Sankaranaryanan–Ramasamy Method V.C.Bharath Sabarish a , G.Ramesh Kumar a*, S.Gokul Raj b, A.Durairajan c, B.N.Rajashekar d b

a Departement of Physics, University College Of Engineering Arni -Thatchur 632 326 Departement Of Physics, C.Kandasamy Naidu College, Chennai 600102 c Sri Akilandeswari College for Women, Vandavasi, Tamil Nadu & Presently at the Departement Of Physics,University Of Aviero Portugal, d Indus-I beamline BL-5, Raja Ramanna Centre for Advanced Technology, Indore, Madhya Pradesh.

Abstract Transparent single crystal of dimension 10 x 1 x 1 cm3 has been successfully grown from Sankaranarayanan–Ramasamy (SR) method. The grown crystal was subjected to Optical Transmittance studies using UV-Vis-NIR spectrum. The presence of various functional groups and the vibrational structure of the compound was elucidated from Fourier transform infrared analysis. The other possible vibrations have also been identified through Raman stud

© 2018 Elsevier Ltd. All rights reserved. Selection and/or Peer-review under responsibility of Materials Processing and characterization.

Keywords: Amino acid; crystal growth ;Fourier Transform Infra Red; UV-Vis-NIR; Raman spectrum.

1. Introduction In recent years, organic – inorganic hybrid materials have attracted considerable attention. Nonlinear optical (NLO) materials play vital role in various fields of science and technological developments. They have gathered much

* Corresponding author. Cell: 94442 75758 E-mail address: [email protected]

2214-7853 © 2018 Elsevier Ltd. All rights reserved. Selection and/or Peer-review under responsibility of Materials Processing and characterization.

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attention for their high non-linear coefficient, high-laser damage threshold and high optical non-linearity [1,2]. They are also useful in optical information processing, optical communication and data storage [3].On the other hand, organic NLO materials have poor mechanical and thermal properties resulting in the damage of the crystal during processing studies. Recently this drawback has been overcome by growing semi-organic NLO crystals. The combination of organic-inorganic compounds brings the advantages such as high resistance to optical damage, multifaceted application, enhancement in the mechanical and thermal properties of the crystals etc., Researchers prefer amino acid based crystals as they are potential candidates for optical second harmonic generation (SHG). Therefore, they can be used in many electronic and optoelectronics devices. There are various techniques to grow bulk single crystals such as solution growth, Bridgman–Stockbarger method and Czochralski method, etc. [4-6]. The main advantages of solution growth method are convenience, simplicity and the use of high-purity solvent /solute and low viscosity of solution which can give controlled super saturation in growth. Sankaranarayanan–Ramasamy (SR) [7] method, a novel solution growth technique gives unidirectional crystals with good quality from solution. The entire quantity of the solute was converted into crystal and thus achieving a solute–crystal conversion efficiency of 100% Microbial contamination of the solution may also be controlled fairly from this method Triglycine sulphate (TGS) is one of the extensively studied ferroelectric materials. The ferroelectric activity of triglycine sulfate ((NH2CH2COOH)3 ·H2SO4) was discovered by Matthias et al. in 1956 [8]. It has immediately attracted the attention of many researchers because it exhibits ferroelectric properties at room temperature and it can be grown easily as large samples. Ferroelectric triglycine sulfate(TGS) and its isomorph crystals have been subjected to numerous studies in the past 30 years, especially because of its excellent ferroelectric and pyroelectric vidicon tubes, transducers and sensors [9,10]. Crystals of pure TGS with different additives have been used for the construction of the most sensitive detectors because of their high value of figure of merit [11]. In the present work Triglycine sulphate (TGS) growth conditions and its experimental details have been presented. The grown crystals were characterized by FTIR, UV-Vis-IR and Raman spectroscopy. 2. Materials And Methods 2.1. Growth of TGS crystals Triglycine sulphate (TGS) solution was prepared from glycine (E-Merck 99.99%) and sulfuric acid (EMerck 99.99%) in the molar ratio of 3:1. The scheme of equation is shown below 3(NH2CH2COOH) + H2SO4 = (NH2CH2COOH)3H2SO4 For synthesizing Triglycine sulphate (TGS) [12] room temperature solution evaporation method was adopted. The amount of raw materials required to the preparation of the saturated solution of TGS at room temperature was dissolved in deionized water. Filtration of the solution by Whatman 125mm pores filter paper ensure dust free solution. The prepared solution was then allowed for slow evaporation in a perti dish at room temperature. Fig 1. Photograph of TGS single crystals.

After one week transparent TGS crystals were grown out of which a well faceted one was selected to be used as a seed [13,14]. Transparent quality of seeds of TGS is shown in single crystal Fig 1.

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2.2 Crystal growth from Sankaranarayanan–Ramasamy (SR) method Triglycine sulphate material was fed into the SR method glass ampoule. The crystallizer was kept in a water bath to avoid the temperature fluctuations. In the freshly prepared solution, the concentration of solute is deliberately kept slightly under saturated in order to avoid any physical and chemical instability at the growth interface. After three-day’s concentration of the solution in bottom portion may set increased due to gravity. A suitable cover was placed on the top of the ampoule, the water vapor was condensed on the top cover and seeps into the solution via the wall [15]. This keeps the inner wall wet which avoids the dried solute particle from falling into the solution. With a thin plate as seed a large size crystal can be grown. A suitable temperature is provided by ring heater at the top and the bottom of the glass ampoule. The temperature around the growth region is maintained at difference of 6°C with ±0.05 °C accuracy. The temperature for the top portion of the ampoule was kept at 38°C and bottom portion temperature was made for 32 °C. In this condition, growth of highly transparent crystal was observed and it is show in Fig.2. A transparent uniaxial Triglycine Sulphate (TGS) single crystal of 1 cm diameter and 10 cm length was grown within a period of 35 days. The average growth rate was about 2 mm/day. This was found to be higher than average growth rate in conventional method under similar conditions. The shape of the crystal depends on the shape of the crucible used. By this method, desired shape and face could also be achievable.

Fig 2. A transparent uniaxial Triglycine Sulphate (TGS) single crystal grown from SR method

3. RESULTS AND DISCUSSION 3.1 Single crystal XRD Studies on TGS crystal: Single crystal Xray diffraction studies was performed on TGS crystal using ENRAF NONIUS CAD4 diffractometer using MoKα radiation (λ=0.71073 Å) and the data were obtained is tabulated in Table 1. Table 1: Lattices parameters of TGS single crystal

S.no 1. 2. 3. 4. 5. 6.

Crystal parameter

Data

Crystal System Space group

7.

Cell volume Å3

Monoclinic P21 9.167(±0.0001) 12.640(±0.0001) 5.729(±0.0001) 105.58º 638.26

a (Å) b (Å) c (Å) βº

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3.2 Fourier Transform Infrared (FTIR) analysis on TGS crystal: -

3009

3150

1737 1701

1533

1611

1372 1297 1119 1076

1051 1012

860 613

895

975

570 496

1495

1425

665 646

460

Transmittance %

415

348 355 363 367

1566

1878 1860

FTIR spectral analysis gives information on the vibrational bands present in the molecule. The FT-IR spectrum of TGS Single crystal was recorded in the frequency region 400 - 4000 cm-1 using Mattson Galaxy 7000 series FTIR Spectrometer. The sample was prepared by pressing TGS powders with KBr into pellet form. The observed spectrum is shown in Fig 3

500

1000

1500

2000

2500

3000

3500

4000

-1

Wavenumbers (cm ) Fig 3. FTIR spectrum of Triglycine sulphate (TGS)

The absorption peaks at 3150, 1701, 1495, 1119, 895 and 570 cm-1 show the presence of NH3+ group in the crystal. The peaks at 1051,1012,860 and 460 cm-1 are attributed to the C-N stretching mode vibrations. The peaks at 1860, 1611, 1425 and 613 cm-1 are due to COO- symmetric stretching mode. The absorption peak at 975, 895 cm-1 is due to the combination band of SO4- asymmetric stretching / NH3+ rocking. The peak at 1701 cm-1 is due to the NH3+ deformation/ amide. The peak at 1495 cm-1 belongs to Symmetric NH bending. The CH2 wagging appears at 1297 cm-1. The peak at 496 cm-1 represents the COO- rocking. The other vibrational band assignments for the absorption peaks of the FT-IR spectrum have been Tabulated in Table 2. The observed assignments reciprocate well with the earlier reports [13,16-19,21,22]. 3.3 Raman Studies on TGS crystal Raman analysis gives information on the Raman mode of vibration present in the molecule. Spectrum was recorded for TGS crystal in the region 90-3100 cm-1 using Jobin–Yvon Raman Spectrometer. The observed spectrum is shown in Fig 4. By using the spectral data of SO4, CH2, NH3, C-H, we assigned the observed lines to the vibrations of the characteristic groups and valence and it is listed Table 3. The observed Raman lines compared with the literature. Most of our assignments agree with previously reported values. [13,16,20-22].

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Table 2: The vibrational band assignments

Frequency (cm-1)

Band assignment

NH3+ symmetric stretching C-O stretching/ overtones NH3+ deformation/ amide COO - & NH3+– asymmetrical stretchin Symmetric NH bending COO – symmetrical stretching/ SO4- asymmetric stretching CH2 bending CH2 wagging NH3+ rocking/ SO4-out of plane stretch NH2 bending CN stretching CN stretching CH2 twisting / SO4- symmetrical stre ing NH3+ rocking/ SO4-symmetrical stre ing

3150(mb) 1860(sh) 1701(m) 1611(vs) 1495(ms) 1425(vs) 1372(s) 1297(s) 1119(m) 1076(w) 1051(vw) 1012(w) 975(w) 895(vs)

C-CN+ stretching/ NH3+ rocking SO4- bending /COO- wagging NH3+ torsion COO- rocking N-C-N stretching/ N-H torsi oscillations

860(s) 613(vs) 570(vs) 496(vs) 460 (m)

2989

vs -very strong, m-medium, w- weak, s- strong

2963

25000

3013 3023

15000

0 0

500

1000

1500

2000

2500

Raman shift (cm-1)

Fig 4. Raman spectrum of Triglycine sulphate (TGS)

2858

2740

1647 1680

1314 1379 1415 1445 1486

893

1017 1046 1087 1116 1138 1167

871

332

5000

456 503 464 585 616 630 670

3170

10000 113 131 176

intensity (a.u)

981

20000

3000

3500

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V.C.Bharath Sabarish et.al./ Materials Today: Proceedings 5 (2018) 18815–18822 Table 3: Raman Modes in TGS crystals

Wavenumber (cm-1) Assignments 176

Lattice mode vibration of Glycine

332

Lattice mode vibration of Glycine

456

SO4-

464

SO4-

503

C-CO bending

585

C-CO bending

616 630

SO4SO4-

670

O-C-O bending

871

C-C stretching

893

C-C stretching

981 1087 1116 1138 1167 1314 1379 1415 1445 1486 1647 1680 2989 3013

SO4SO4NH3+ rocking NH3+rocking NH3+ rocking CH2 wagg/twist CH2 wagg/twist CO2 sym CH2 CH2 C=O C=O CH2 stretching CH2 stretching

It is difficult to interpret the low-frequency spectrum because the character of external vibrations of TGS is determined mainly by the system of hydrogen bonds between structural elements of this crystal. The vibration with the frequency 176,332 cm-1 are Raman Modes for Lattice mode vibration of Glycine. The frequencies 456,464,616,630 cm-1 are the Raman Modes for SO4- . The frequencies 871,893 cm-1 are for the C-C stretching. The frequencies 116,1138,1167 cm-1 are for NH3 rocking and the band at 1314,1379 cm-1 CH2 wagging /twisting vibration and 1445,1486, 2989,3013 cm-1 are for CH2 stretching. The frequencies 871 ,893 cm-1 are for C-C stretching. The Raman bands at 1379 and 1415 cm-1 indicate the presence of zwitterion, which supports Hoshino's theory for the spontaneous polarization reversal in TGS [21]. 3.4 UV-Vis-NIR Studies on TGS crystal Single crystals of TGS are mainly used in optical application. Therefore, the optical properties of the grown crystals have been studied with the aid of UV-Vis NIR spectrum in the wavelength range 200-1100 nm using Perkin Elmer Lambda 35V, UV-Vis NIR spectrophotometer. Transmittance spectrum of TGS is shown in fig 5. A strong absorption peak at 234 nm corresponds to the fundamental absorption and it depicts the λ-cut off wavelength [22-26]. Crystal also shows a very good transmittance even up to NIR region

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Fig 5. UV-Vis-IR spectrum of Triglycine sulphate (TGS)

Conclusion Transparent single crystal of Triglycine sulphate of dimension 10 x 1 x 1 cm3 has been successfully grown from Sankaranarayanan–Ramasamy (SR) method. The vibrational structure of the compound was elucidated from Fourier Transform spectrum and various functional groups presented in the crystal were also identified. As the crystal belongs to non centrisymmetric space group, all vibrational modes observed in IR are also found to be Raman active. Possible Raman modes of the crystal has been highlighted. From UV-Vis-NIR study the λ-cut off wavelength was found as 234 nm and the crystal possess wide transiency even up to NIR region. Acknowledgments One of the authors Dr.G.Ramesh kumar wishes to thank CSR-DAE Indore for the financial support extended under collaborative Research scheme Grant no:(CSR-180/2016-17)28.10.2016. The authors are also thankful to senior Prof Dr. P. Ramasamy and his Research group for their valuable suggestions to grow single crystal. The authors would further thank Dr. Arindam Das, Material Science Group (MSG), IGCAR, Kalpakkam for fruitful discussions. Reference [1] Prasad P.N, Willams. D.J. Introduction to nonlinear optical effects in molecules and polymers; Washington DC,1991. [2] Marder, S.R; Sohn, J.E, Stucky, G.D., Materials for nonlinear optics, American chemical society, Washington, DC,1991. [3] Saleh B.E, Teich. A, Fundamentals of photonics, Wiley, Newyork, 1991. [4] MasahiroNakatsuk,KanaFujioka, TadashiKanabe,HisanoriFujita Journal of Crystal GrowthVolume171,Issues 3–4, 1997, Pages 531-537 [5] Benjamin G.PennBeatriz H.Cardelino Craig E.MooreAngela W.ShieldsD.O.Frazie Crystal Growth and Characterization of MaterialsnVolume 22, Issues 1–2, 1991 [6] K. Sankaranarayanan, P. Ramasamy, J. Crystal Growth 280 (2005)467. [7] K. Sankaranarayanan, J. Crystal Growth 284 (2005) 203. [8] B. T. Matthias, C. E. Millar, and J. P. Remeika, Phys. Rev. 104, 849 (1956). [9] H.V. Alexandru, C. Berbecaru, L. Ion, A. Dutu, F. Ion, L. Pintilie, R.C.Radulescu, ApplSurf.Sci.253(2006)358–362. [10] S.B. Lang, D.K. Das-Gupta, Ferroelectr.Rev.2(2000)286–292. [11] V. Lhotska, J. Fousek, N. Neumann, Phys.StatusSolidiA120(1990)273–283. [12] S. Satapathy, S. K. Sharma, A. K. Karnal, and V. K. Wadhawan, J. Cryst. Growth 240, 196(2002).

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