Research Article
392
*Corresponding author:M. Anitha
GROWTH AND CHARACTERIZATION OF L-ARGININE DOPED
SUCCINIC ACID SINGLE CRYSTAL (LASA)
M. Anitha
1, B.Ravindran
2*M. Vijayalakshmi
3*1,3* Assistant Professor of Physics, Rabiammal Ahamed Maideen College for Women, Tiruvarur. (Affiliated to
Bharathidasan University)
2,*PG and Research Dept of physics, Thiru Vi Ka Govt Arts and College, Thiruvarur *Corresponding author (Affiliated to Bharathidasan University)
Article History:Received:11 november 2020; Accepted: 27 December 2020; Published online: 05 April 2021 ABSTRACT : Under room temperature condition semi-organic crystals of L-Arginine mixed with succinic acid were grown from a solution maintained in aqueous from by slow evaporation solution growth method. Spectral analysis Fourier transform infrared and power diffraction by X-rays was used to determine the structural behavior of the grown LASA crystals. The lower cut off wavelength values 240 nm and efficiency transparency was confirmed using ultraviolet-Vis-NIR spectrum. The efficiency of second harmonic generation has been carried out for the grown LASA crystals and the detailed discussion about the results obtained was recorded. The thermal stability and melting range of the grown mixed crystal was carried out using thermogravimetric and Differential Scanning Calorimeter analysis.
Keywords: L-Arginine, succinic acid, XRD, FTIR, UV- Visible, TGA/DSC, NLO. 1. INTRODUCTION
L- Arginine emotes itself as a basic amino acid it tries to combine with several salts with various inorganic and organic materials to form a new semi organic one due to its basic nature. Mast of the newly generated compounds arises due to the inclusion shows very fair NLO properties [1]. Semi organic material possess excellent non-linearly and fluorescent behavior and due to the significance the grown materials are used in optical computing, telecommunication, optical data storage, optical processing of information and light emitting diodes etc [2-3]. NLO organic materials will have high non-linearly on compound to inorganic one and used to possess with third orders second order co-efficient. Even through being a poor transparent nature laser damage threshold and short optical band gab inorganic materials produce excellent NLO materials while included with organic [4-7]. The peculiar chemical and physical properties of amino acids are due to the occurrence of accept on (NH2) amino group and donor carboxyl (-COO) acid group. Existence of dipolar
molecules became of its non-Centro symmetric nature amino acids shows vital importance in the non-linearly field [8]. The scopes of the current work focus on the characterization and growth of LASA. Characterization studies such as UV-Vis-NIR, TGA/DSC, FTIR, XRD and NLO studies were used to confirm the grown crystals.
2. EXPERIMENTAL PROCEDURE:
A mixer of L-Arginine and succinic acid with equimolar quantity was taken in beaker dissolved using doubly deionized water. The propose reaction in shown below fig (1). Amino acid (L-Arginine) mixed with succinic acid were grown into crystals, by the adoption of solution slow evaporation growth technique under room temperature. By attaining saturation due to dissolving the solute mixture of L-Arginine doped succinic acid into the solvent. The obtained mixtures are made to form itself as a homogeneous mixture by proper stirring for about one hour using magnetic stirrer. Finally the solution was filtered using filter paper (Whattman) [9-11]. Then the filtered solution collected in a crystal-clear beaker was kept in a undisturbed position covered with a micro hole perforated plastic paper. The mixture solution was allowed to evaporate up to the dry level maintained under room temperature and the induction period was recorded before harvesting the grown crystal.Fig.1 confirms the morphology of the grown crystal with a perion of 20 days. After harvesting the crystals the material was subjected to various characterization mechanisms to prove the grown one. Fig.1 gives the photograph of the grown crystal.
Fig.1. Morphology of LASA 3. RESULTS AND DISCUSSION
3.1 X-ray Diffraction Studies
Fine powders of grown LASA crystals were subjected to X-ray powder diffraction to identify the crystal lattice parameter and reflection planes. The X-ray powder diffraction pattern of LASA crystal in shown in fig.2.The powder diffraction reflections from the X-rays are all indexed using an indexing package software table.1.given the obtained 2ϴ, d-spacing and hkl values. Software package named as UNITCELL is used to determine the lattice parameters from the X-ray powder diffraction data and are recorded as a=5.06Aͦ , b=8.83 Aͦ, c=5.46 Aͦ and volume= 245Aͦ. The observed values are found to be in good agreement with the experimental results.
Fig.2.Powder XRD graph of LASA Crystal
Table.1. Powder XRD Analysis
2Ө h k l values 24 020 27 021 39 21-1 42 212 46 512 49 252
Sample Crystal Axial length Interfacial angles Structure LASA a = 5.06 b = 8.83 c =5.46 α =β=γ=900 Monoclinic
3.2. UV- Visible Spectral analysis:
Lambda 35 spectrometer is used to record the optical transmission spectra operating under a range of 200-1100nm and plotted in the fig (3a). For the entire visible region the grown crystal seems to be highly transparent and has a cut off wavelength at 240nm. Materials considered for optical applications must satisfy the optical transparency in the entire region of wavelength. Hence it was proposed that the L-Arginine will have a good optical behavior became of its non-centro symmetric nature. The major transmittance reveals that the mixed crystal of LASA will play vital enrolment in the list of optical materials. As the entire region beams no absorption then it was confirmed that the transmission is 100% high which suits for NLO applications fig (3a) exposes the resultant spectrum and the transmittance (T) measured was used to predict the absorption co-efficient (α) unity the formula given below [12-14].
α=2.303 log(
1 T ) t
Where sample thickness is mentioned as ‘t’. The following with photon energy relation is used to study the co-efficient of absorption (α)
(α h ѵ) = A (Eg – hѵ) 1/2
Taking Eg as the optical band gap, A as constant, Plank’s constant as h and υ the incident photon
frequency. From the UV-Vis-NIR date the optical band gap of the plotted profile between (αhυ) 2 and (hυ). E g
value is calculated from the slope drawn and was found to the noted of 5.5eV. It was confirmed that the internal efficiency is proportional to the co-efficient of a absorption. Hence band upon the necessity on device fabrications using and can be properly. The energy of forbidden gap was calculated from the high transmittance edge of energy utilizing the given formula.
E = hc / λ
From the slope obtained the forbidden energy gap value was found to be noted a 5.5eV which reveals that the grown material suit for the fabrication of devices utilizes in the field of photo electronics [15-16].
The following equation is used to device the K (extinction co-efficient) K= λa
4𝜋 Given transmittance (T) is noted from
T= (1−R)2exp(−at) 1−R2exp(−2at)
And from the above equation ‘R’ (Reflectance) can be obtained in term of co-efficient absorption. R=exp(−at)±√exp(−at)T−exp(−3at)T+exp−(2at)T2
exp(−at)T+exp−(2at)T
Using the following equation the determination of Reflection index (n) from the reflectance can be recovered. n = - (R+1)±2 √R
(R−1)
Fig.3 (b) plot of (h ʋ) versus photon energy K
Fig. 3(c) plot of (α h ʋ) 2 versus photon energy hʋ
3.3. Fourier-Transform Infrared Spectroscopy Studies:
The FTIR spectrum of LASA crystal was shown in the fig 4.The broad high energy region envelope between 3958.75cm-1 and 2535.72 cm-1 were formed due to the O-H and N-H stretching vibration. The
frequency range between 1829.77 cm-1 and 1694.49 cm-1 attributed to C=O stretching. Asymmetric stretching of
carboxyl group was assigned at 1416.44 cm-1 where as the bending in plane C-H is occurred at 1309.37 cm-1.
The asymmetric and stretching of carbonyl groups were displayed at 1201.47 cm-1 and 911.32 cm-1.
Simultaneously the vibration due to C-H outing plane bending, CH2 rocking, C-H bending out of plane COO
-wagging and NH2 rock were characterized at 801.80 cm-1, 692.89 cm-1, 636.18 cm-1 582.84 cm-1 and 443.20 cm -1 respectively. Frequency assignments of the absorption peaks are given in table.2.
Table.3. Fundamental Frequencies of vibrations LASA Wave number (cm-1) Assignments
3958.75 O-H Stretching 3048.02 N-H stretching 2931.35 N-H Stretching 2742.46 O-H Stretching 2649.04 O-H Stretching 2535.72 O-H Stretching 1829.77 C=O Stretching 1729.07 C=O Stretching
1694.41 C=O Stretching of COOH
1416.44 Asymmetric stretching of COO-
1309.37 C-H bending in plane
1201.47 C-O Asymmetric Stretching
692.89 CH2 rocking
636.18 C-H bending out of phase
582.84 COO- wagging
443.20 NH2 rock
Fig.4. FTIR spectrum of LASA 3.4. TGA\DSC Analysis
SDT Q600 V20.9 Build 20 was used to analyses the thermal behavior of the grown LASA crystal heated under a range of 30˚C to 1000˚C maintaining a scanning rate of 20˚C/min with nitrogen as its surrounding atmosphere [17]. Shown in the Fig (5) occurred endothermic and exothermic peaks of the grown LASA crystal three endothermic peaks were recorded at 187.89˚C, 243.06˚C and 715.05˚C respectively. Weight loss starts at first endothermic peak at 187.89˚C and a major loss was observed at 243.06˚C. Completed decomposition takes place at 940˚C and in between another endothermic was observed at 715.05˚C. 65% weight loss was calculated between ranges of temperature 187.89˚C to 243.06˚C. From the profile it was confirmed that the weight loss was mainly due to evaporation of carboxylic acids and nitrate.
Fig.5. TG/ DSC of LASA crystal 3.5 Second Harmonic Generation
High energy Q-switched laser emitted out from a solid state Nd-YAG source was used to test the Second Harmonic Generation efficiency of the grown LASA crystal. The non linear optical behavior of the crystal was confirmed due to the emission of 532nm output ray emerged out from the crystal with respect to the incident beam of wavelength 1064nm[18]. The measured output was 4mV which reads to a suggestion that it may be used for the device fabrication with a controlled output.
The slow evaporation method was adopted to slow the LASA crystal from the solution growth technique. Determinations of incorporations were done using the powder diffractions by X-ray and the nature of good crystalline. Conformations of the presence of functional groups were analyzed by Fourier Transformation IR- spectroscopy. Grown LASA crystals thermal stability was sharply predicted using the analysis from TGA/DSC studies. Enhancement of SHG efficiency of the LASA crystal was concluded using NLO (Non Linear Optical) studies. The emerge output of 4mV confirmed the NLO behavior and leads to make a proposal that the grown crystal may be utilized for device fabrications in the field of Non linear optics.
References
Monaco, S. B., Devis, L. E., Velsko, S.P., Wang, F.T., Eimerl, D. and Zalkin, A., J. Cryst. Growth, 1987, 85, 252.
Williams J (edn) (1983) Nonlinear Optical Properties Organic and Polymeric Materials. American Chemical Society Symposium Series 233. American Chemical Society, Washington DC.
Chemla DS, Zuss J (edn) (1987) Nonlinear Optical Properties of Organic molecule and Crystals, vol 1 and 2, Academic press, New York.
LedouxSmZyss J, Nonlinear Organic Molecules and Materials for Optoelectronic Devices. Int J Nonlinear Opt Phys 3: (1994) 287-316.
Mostad A. Natarajan S, Crystal and molecular structure of DL-methionine nitrate Z Kristallogr 210(1995) 114-117.
Shen YR The principles of nonlinear optics, Wiley, New York. (1984)
Marcy HO, Warren LF, Webb MS, Ebbers CA, Velsko SP, Catella GC (1992) Second-harmonic generation in zinc tris (thiourea) sulfate. Appl Opt 31:5051-5060.
Fuchs, B. A., Ksyn, C. and Veisko, S.P., Appl. Opt., 1989, 28, 4465
B.Anitha, S.Rathakrishnan,r. Umamaheshwari and Josesh Arul Pragasam studies on the Growth and characterization of organic L-Arginine SemicarbazoneDihydrate NLO single crystal,vol7(7)1014-1017 July 2014
Saravanan M, Senthil A, Abraham Rajasekar S. Growth and Characterisation of non Centro symmetric single crystals of L-Argininium-4-nitro Phenolate Monohydrate, A Potential second order nonlinear optical material. Optical materials.2015; 48: 226-232.
Joseph ArulPragasam A, Anitha B and Sagayaraj P. Growth, thermal and mechanical characterizations of Non linear optical L-arginine benzohydrazide single crystal. Journal of Chemical and Pharmaceutical research. 2014; 6(11):739-743.
S. Umavenkateshwari and M. Alagar Crystal Growth and Characterization of L-Arginine doped UREA ANJAC J. Sci., Vol. 12, No.2, 2013
Joseph Arul Pragasam, A., Madhavan, J., Gulam Mohammed, M., Selvakumar, S., Ambujam, K. and Sagayaraj, P., Opt. Mat., 2006, 29, 173.
P.V.Dhanaraj, T.Suthan,N.P.Rajesh , Synthesis, crystal growth and characterization of a semiorganic material: Calcium dibromidebis (glycine) tetrahydrate Current Applied Physics10 (2010)1349e1353
Anbu Chudar Azhagan, S., Ganesan, S. Effect of zinc acetate addition on crystal growth, structural, optical, thermal properties of glycine single crystals. Arabian Journal of Chemistry (2013
James EFranke Thomas MNiemczyk-Department of Chemistry, University of NeMexico, Albuquerque, NM 87131, U.S.A.
Baraniraj, P.Philominathan, Spectrochimica acta Part A: Molecular and Biomolecular Spectroscopy, 75(2010)74-76.
P.Praveen kumat,V.Manivannan, S.Tsmilselvan, S.Senthil, Antony Raj victor, P.Sagayaraj and J.Madhavan, Optics communication 2008,281:2989-2995
