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 M. Vallikkodi and  S. Sudhahar/ BIBECHANA 16 (2019) 15-22: RCOST  p.15 (Online Publication: Dec., 2018)   BIBECHANA A Multidisciplinary Journal of Science, Technology and Mathematics      ISSN 2091-0762 (Print), 2382-5340 (0nline) Journal homepage: http://nepjol.info/index.php/BIBECHANA Publisher: Research Council of Science and Technology, Biratnagar, Nepal 
    The non-linear optical crystal growth and characterization of piperizantum p- aminobentzone   M. Vallikkodi*, S. Sudhahar Department of Physics, Alagappa University, Karaikudi- 630 004, India. *Email: vallikkodi.10@gmail.com  Article history: Received 09 February, 2018; Accepted 3  August,  2018 DOI: http://dx.doi.org/10.3126/bibechana.v16i0.20875 This work is licensed under the Creative Commons CC BY-NC License. https://creativecommons.org/licenses/by-nc/4.0/  Abstract The nonlinear optical properties of piperizanium p – aminobenzoate (PZPAB) crystal were successfully grown with the help of temperature gradient (Slow evaporation) method. The good quality of PZPAB single crystal is formed. The PZPAB is characterized with the help of X-ray diffraction (XRD), Fourier transform infrared (FTIR) measurement, photoluminescence (PL), Raman spectroscopy, ultra violet visible spectroscopy (UV) and finally etching analysis was done.   Keywords: Piperizanium p – aminobenzoate; nonlinear optical crystal; slow evaporation                        method. .   1. Introduction   A material that has good crystalline nature is also having good optical and electrical properties [1-3]. Many organic and inorganic crystal materials had high polarization ability and are good candidates for nonlinear optical (NLO) studies [4]. However, the net polarization depends on the material symmetry properties, with respect to the impinging fields. So far, there are many organic crystals which is used for NLO yet, piperizanium p- aminobenzoate having the adorable nature of nonlinear properties. In the present article, gives the advancement of new NLO material (piperizanium p- aminobenzoate); which is being characterized with the help of XRD, FTIR, UV, Raman and PL.   2. Materials and Methods  Piperazinium p-aminobenzoate crystal was prepared in the room temperature by slow evaporation growth method [5] by using as a methanol solvent. The precursor’s materials of Piperazine (98%) and p-aminobenzoic acid (99%) were taken in the equimolar ratio of 1:1 for the synthesis process is shown in figure 1.  The  p-Aminobenzoic acid was first dissolved in the solvent of methonal, after  



M. Vallikkodi and  S. Sudhahar/ BIBECHANA 16 (2019) 15-22: RCOST  p.16 (Online Publication: Dec., 2018) complete dissolved acid material and then the base compound of Piperazine was added little by little with the acid solution. The solution is allowed to get a homogenous mixture by continuously stirring for 8 hours using the temperature control magnetic stirrer in the room temperature circumstances [5]. After attaining the homogenous saturated state the solution was filtered using the whatman filter paper which is having the fine holes in the range of 110 µm and the filtered solution was covered with the perforated sheet having the fine holes for the evaporation and it was kept at the room temperature without disturbance. After 2 successive recrystallization process the good quality PZPAB crystal was harvested with in the span of 60 days. The figure 2 shows the crystal of PZPAB.  NHHNPIPERAZINE OHO NH2P AMINOBENZOIC ACID NH2+HN PIPERAZINIUM P AMINOBENZOATEO-O NH2   Fig. 1: Synthesis scheme of Piperazinium P-Aminobenzoate.     Fig. 2: Grown crystal of Piperazinium P-Aminobenzoate.    3. Results and Discussion XRD Analysis    (i) The single crystal X-ray diffraction analysis is the powerful tool for determination of the structure of the crystal.  The Piperazinium P-Aminobenzoate crystal belongs to orthorhombic crystal system with noncentrosymmetric space group Pna21. This space group satisfies one of the basic essential requirements of NLO material. The lattice parameters of the Piperazinium P-Aminobenzoate is found   



M. Vallikkodi and  S. Sudhahar/ BIBECHANA 16 (2019) 15-22: RCOST  p.17 (Online Publication: Dec., 2018)  to be a = 18.2964 Å, b = 7.1388 Å, c = 10.3574 Å, α = 90°, β = 90°, γ = 90° and volume V = 1352.83 Å3. The structural parameters of the Piperazinium P-Aminobenzoate crystal were listed in the table 1.  Table 1: PZPAB crystal. Crystal property Piperazinium P-Aminobenzoate Empirical formula C4H11N2+•C7H6NO2−•H2O  Crystal system Orthorhombic Spacegroup Pna21  Unit cell parameters a = 18.2964 Å, b =7.1388 Å,                     c =10.3574 Å, α = 90°, β = 90°, γ = 90° Volume of the unit cell V = 1352.83 Å3 Radiation wavelength λ = 0.71073 Å   The crystalline nature of the Piperazinium p-aminobenzoic crystal was characterized by Powder x-ray diffraction analysis to reveal crystalline perfection of the compound. The x-ray diffraction spectrum of PZPAB was recorded using the X’pert PRO powder diffractometer with CuKα radiation having the wavelength of λ = 1.5406 Å. The sample was scanned from the range of 10° to 80° at the rate of 2°/minute. The recorded powder x-ray diffraction spectrum is shown in Figure 3. The presence of sharp and well defined peaks confirms the good crystalline nature of piperazinium p-aminobenzoate crystal and the corresponding peaks were indexed. The sharp intense peaks are shown in the table 2.  FTIR Analysis The FTIR spectrum was recorded to understand the chemical bonding and it provides useful information regarding the molecular structure of the compound. The KBr pellet technique was used to analyze the sample. FTIR spectrum was taken for the powdered sample in the wavelength range 4000-400 cm-1 using 380 FTIR Spectrophotometer having the resolution of  0.5 cm-1 and the spectrum of FTIR is shown in Figure 4.The observed FTIR is summarized in table 3.  Raman Analysis Laser Raman spectrum was taken for the powdered sample in the wavelength range 4000-400 cm-1 using STR 500 mm focal length laser Raman spectrometer and the Raman spectrum is shown in the figure 5. Raman bands along with their vibrational assignments are summarized in table 4.  UV-Visible optical Absorption spectral analysis The optical absorption spectral analysis of the grown PZPAB crystal was carried out using Perkin Elmer Lambda35 spectrometer between 250 and 800 nm. The absorption & transmittance spectrum of the as grown PZPAB crystal is shown in the Figure 6. The UV cut off wavelength of the crystal was found to be at 317 nm. The absence of absorption in the visible region suggests that the crystal possess the good nonlinear optical property.  



M. Vallikkodi and  S. Sudhahar/ BIBECHANA 16 (2019) 15-22: RCOST  p.18 (Online Publication: Dec., 2018)  Table 2: Peaks of XRD. Pos. [°2Th.] Height [cts] FWHM Left [°2Th.] d-spacing [Å] Rel. Int. [%] 10.4002 121.43 0.1476 8.50603 3.53 13.5267 439.65 0.1476 6.54617 12.78 14.1626 173.47 0.1476 6.25365 5.04 15.1903 641.65 0.1476 5.83283 18.65 15.5192 252.21 0.0984 5.70992 7.33 17.0567 1184.78 0.1476 5.19854 34.44 19.5580 551.63 0.1476 4.53897 16.04 21.0129 470.57 0.1476 4.22787 13.68 21.5337 3439.78 0.1476 4.12679 100.00 23.8882 2086.44 0.1476 3.72510 60.66 24.8055 1168.61 0.1476 3.58939 33.97 26.3194 821.87 0.1476 3.38626 23.89 26.8804 317.96 0.1476 3.31685 9.24 27.4870 740.96 0.1476 3.24502 21.54 28.3924 145.42 0.1476 3.14356 4.23 29.4507 256.36 0.1476 3.03297 7.45 30.5232 719.77 0.1968 2.92879 20.92 31.3467 721.21 0.1476 2.85371 20.97 31.9957 276.41 0.1476 2.79729 8.04 32.4648 201.46 0.1968 2.75793 5.86 33.7596 164.56 0.1476 2.65506 4.78 34.3585 209.28 0.2952 2.61014 6.08 35.1350 131.82 0.1968 2.55421 3.83 35.6070 134.51 0.1476 2.52143 3.91 36.3967 554.72 0.1968 2.46852 16.13 37.9391 177.68 0.1476 2.37163 5.17 39.0984 130.54 0.2460 2.30395 3.80 39.5630 76.17 0.1476 2.27795 2.21 41.2584 89.98 0.3936 2.18818 2.62 41.8669 81.48 0.1476 2.15778 2.37 43.3737 77.32 0.1476 2.08624 2.25 43.8176 84.64 0.1476 2.06613 2.46 44.3690 117.18 0.1476 2.04173 3.41 45.0060 82.97 0.1968 2.01430 2.41 46.4121 73.75 0.1476 1.95650 2.14 48.0597 46.94 0.1968 1.89320 1.36 49.2598 48.17 0.1968 1.84985 1.40 50.7274 282.97 0.2460 1.79973 8.23 51.2972 67.33 0.1476 1.78107 1.96 52.5555 50.83 0.2460 1.74135 1.48 53.4279 22.86 0.2952 1.71496 0.66 54.1358 19.44 0.2952 1.69420 0.57 55.2169 25.97 0.3936 1.66356 0.76 56.6958 36.33 0.2952 1.62363 1.06 57.8343 32.12 0.5904 1.59435 0.93 60.7458 28.30 0.5904 1.52472 0.82        



M. Vallikkodi and  S. Sudhahar/ BIBECHANA 16 (2019) 15-22: RCOST  p.19 (Online Publication: Dec., 2018)    Fig. 3: Powder XRD pattern of PZPAB crystal.  Table 3: FTIR frequency assignments of PZPAB compound. Functional groups Theoretical value FTIR Experimental value Assignments Amine  1200 – 1025 1089 C-N stretching alkyl Amine  3500 – 3300 3327 N-H stretching Alcohols  1200 – 1000 1123 C-O stretching Carboxyl  1320 – 1210 1224 C-O stretching Aromatics  3020 – 3000 3009 CH stretching Aromatics  ~1600 1609 C=C stretching  Fig. 4: FTIR spectrum of PZPAB.  



M. Vallikkodi and  S. Sudhahar/ BIBECHANA 16 (2019) 15-22: RCOST  p.20 (Online Publication: Dec., 2018)  Table 4: Raman frequency assignments of PZPAB compound.  Functional groups Theoretical value Laser Raman Experimental values Assignments Amine  1200 – 1025 1150 C-N stretching alkyl Amine  3500 – 3300 3331 N-H stretching Alcohols  1200 – 1000 1150 C-O stretching Carboxyl  1320 – 1210   ----- C-O stretching Aromatics  3020 – 3000 3077 CH stretching Aromatics  ~1600 1605 C=C stretching    Fig. 5: Laser Raman spectrum of PZPAB. UV-Visible optical Absorption spectral analysis The optical absorption spectral analysis of the grown PZPAB crystal was carried out using Perkin Elmer Lambda35 spectrometer between 250 and 800 nm. The absorption & transmittance spectrum of the as grown PZPAB crystal is shown in the Figure 6. The UV cut off wavelength of the crystal was found to be at 317 nm. The absence of absorption in the visible region suggests that the crystal possess the good nonlinear optical property.  Photoluminescence studies Photo luminescence spectroscopy is a non -destructive method for finding out the electronic structure and optical behavior. The Photoluminescence spectrum of the grown PZPAB was recorded in the wavelength region between 300 nm and 550 nm using RF-5301 spectrophotometer. The PL spectrum (Figure 7) of PZPAB grown crystal is excited at 350 nm. From the PL spectrum, one high intensity blue emission peak and one medium intensity violet emission peak was observed at 455 nm, 384 nm  



M. Vallikkodi and  S. Sudhahar/ BIBECHANA 16 (2019) 15-22: RCOST  p.21 (Online Publication: Dec., 2018)  respectively, and it attributes to shallow defects in the band gap and more ordered structure. The sharp high intensity caused because of the similar transition occurring at the various energy levels within the band gap.   Fig. 6: UV-Visible absorption & transmittance spectrum of PZPAB.   Fig. 7: Photoluminescence spectrum of PZPAB.  4. Conclusion The piperazinium p-aminobenzoate crystal was successfully grown and characterized. The XRD pattern confirms the properties of NLO and the Raman and FTIR confirm all the functional groups. The UV and PL show the Optical properties. Thus, a good NLO crystal was successfully formed for LASER applications.  



M. Vallikkodi and  S. Sudhahar/ BIBECHANA 16 (2019) 15-22: RCOST  p.22 (Online Publication: Dec., 2018)  References [1]  G. U.  Sankar,  A Survey on Wavelength Based Application of  Ultraviolet LED  Computing, 2007. [2]  C. G. Moorthy,  G. U. Sankar, and G.  Raj Kumar, A Design for Charging Section of Electrostatic Precipitators by Applying a Law for Electric Field Waves. Imperial Journal of Interdisciplinary Research 3(6) (2017) 842. [3]  G. U.  Sankar, Climate change challenge – photosynthesis vs. hydro-electrolysis principle. Climate Change 3 (2016) 128-131. [4]  Y.R. Shen, The principles of nonlinear optics,  New York, Wiley-Inter-science, 1984, p.575. [5]  H. G. Bhamidi, S. R. Wilson, R.B. Tan, P.J. Kenis, and C. F.  Zukoski, Direct growth of γ-glycine from neutral aqueous solutions by slow, evaporation-driven crystallization, Crystal growth & design 6(8) (2006) 1746-1749.