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Growth, optical, dielectrical, thermal and mechanical behavior of organic nonlinear optical Nicotinium p-toluenesulfonate monohydrate single crystal
Optik - International Journal for Light and Electron Optics 194 (2019) 163048
Contents lists available at ScienceDirect
Optik journal homepage: www.elsevier.com/locate/ijleo
Original research article
Growth, optical, dielectrical, thermal and mechanical behavior of organic nonlinear optical Nicotinium p-toluenesulfonate monohydrate single crystal V. Thayanithia, B. Gunasekaranb, P. Praveen Kumara, a b
T
⁎
Department of Physics, Presidency college, Chennai, 600005, Tamilnadu, India Department of Physics & Nano Technology, SRM University, SRM Nagar, Kattankulathur, Kancheepuram Dist., Chennai, 603 203, India
A R T IC LE I N F O
ABS TRA CT
Keywords: Organic compounds Crystal growth Laser damage threshold Differential scanning calorimetric Nonlinear optical properties
Noncentrosymmetric crystal of Nicotinium p-Toluenesulfonate (NPT) was grown by slow evaporation growth method. The crystal structure was determined by Single crystal X-ray diffraction and it confirms that the grown NPT crystal belong to orthorhombic crystal system with noncentrosymmetric space group Pmn21. The vibrations of the functional groups and chemical bonds were analyzed by FTIR spectrum. The grown NPT compound is thermally stable upto 60 °C and its decomposition was elucidated by Thermal analysis. The grown NPT crystal posses wide optical transmittance in the visible region and lower cut-off wavelength is found to be 335 nm. The emission region of grown NPT crystal was identified by photoluminescence emission spectrum. The surface with stand stability from damage induced by high power laser beam for grown NPT crystal was studied. The dielectric parameters of the grown NPT crystal are inversely proportional to the applied frequency. The grown NPT crystals belong to hard material category. The SHG efficiency of the grown NPT crystal is 0.75 times than that of KDP.
1. Introduction In recent years, organic molecule based nonlinear optical materials surpasses the inorganic nonlinear optical materials because of their large nonlinear optical susceptibilities (χ), high power of laser withstand stability, short lower cut-off wavelength with good transparency and inherent ultrafast response time [1,2]. The organic crystals have received greater attention among recent investigators due to high second order nonlinearity and its potential optical applications, such as optical storage devices, frequency doubling, optoelectronics, terahertz generation and detection [3–5]. Nonlinear optical response of organic molecules is caused by intramolecular charged transfer of donor/acceptor through π-space and delocalized electrons. Increasing of π-conjugated bond length and positioning of donor/acceptor moieties help to enhance nonlinear activity in organic materials. Polar π-conjugated forms the push-pull conjugated structure by one end of electron donor group with another end as an electron acceptor group. The polar πconjugated molecule increases the electronic distribution asymmetrically by electron donor and acceptor group [6–8]. p-Toluenesulfonic acid is an organic acid with strong sulfonic acid and also easily obtainable in salt form. It can be mixed with organic base compounds to form organic salts [9,10]. The compound has electron donor group (methyl) and electron acceptor group (sulfonate) [11]. The present investigation deals with structure, growth and characterization of Nicotiniump-Toluenesulfonate monohydrate (NPT)
⁎
Corresponding author. E-mail address: [email protected] (P.P. Kumar).
https://doi.org/10.1016/j.ijleo.2019.163048 Received 26 March 2019; Received in revised form 23 June 2019; Accepted 2 July 2019 0030-4026/ © 2019 Elsevier GmbH. All rights reserved.
Optik - International Journal for Light and Electron Optics 194 (2019) 163048
V. Thayanithi, et al.
Fig. 1. Synthesis scheme of the grown NPT crystal.
crystal. Defect free crystal of NPT crystal was grown by slow evaporation method. Structure of NPT crystal was solved by SHELXS97. The grown NPT crystal belongs to orthorhombic crystal system with noncentrosymmetric space group Pmn21. The grown crystal is subjected to different characterization such as FTIR spectroscopy, Thermal analysis, UV–vis-NIR spectroscopy, Laser damage threshold, Micro hardness and Second harmonic generation (SHG) to confirm their suitability for desirable device applications.
2. Experimental procedure and crystal growth The crystal compound of NPT was synthesized by dissolving equimolar ratio of Nicotinic acid and p-toluene sulfonic acid monohydrate in de-ionized water at room temperature. The saturated solution was filtered into a beaker and it was kept in dust free place. The reaction scheme of the grown NPT crystal is shown in Fig. 1. Transparent and well grown crystal with size of 20 × 8 × 3 mm3 was harvested from the solution in 20 days of time period. The photograph of the as grown NPT crystal by conventional method is shown in Fig. 2.
3. Result and disscussion 3.1. Single crystal X-ray diffraction Single crystal X-ray diffraction was analyzed at room temperature using Bruker Kappa diffractometer with Mo Kα radiation using ω/2θ scan mode. The grown NPT compound crystallizes in Orthorhombic crystal system with noncentrosymmetric space group Pmn21 and cell parameters are a = 6.7368(12) Å, b = 7.4199(7) Å, c = 14.3455(6) Å. The structure of compound was resolved by direct method procedure as implemented in SHELXS97 program. The Oak Ridge Thermal-Ellipsoid Plot (ORTEP) plot of the grown NPT compound is shown in Fig. 3. Table 1 summarizes the crystallographic data of the grown NPT compound. Morphology of the grown crystal was determined by X-ray goniometry and it was drawn. The drawn morphology of the grown crystal is shown in Fig. 4. The grown crystal face planes are (001), (010), (0–10), (100), (−100), (01–1) and (0–1–1). The predominant axis of the grown NPT crystal isc-axis and it determines length of the crystal. The b-axis and a-axis determines the width of the grown NPT crystal.
3.2. FTIR spectroscopy FTIR spectrum was recorded using Perkin elmer spectrometer in range of 450–4000 cm–1 by KBr pellet at room temperature and it is shown in Fig. 5. The peak at 3300 cm–1 is indicates the NeH stretching. The peak at 2948 cm–1 shows that presence of OeH stretching. The presence of carboxylic acid group of C]O stretching was indicated by the peak at 1708 cm–1. The peak at 2219 cm–1 indicates the presence of CeN stretching and the peak at 1632 cm–1 shows that the NeH bending. The peak at 1494 cm–1 shows that presence of C]N stretching vibration. The peak at 1545 cm–1 is due to C]C stretching. The peak at 1474 cm–1 is due to aromatic ring stretching of CeC. The peak at 1320 cm–1 is due to presence of CeS stretching vibration. The presence of SO3 asymmetric stretching is confirmed by the peak at 1225 cm–1 and the presence of SO3 symmetric stretching is confirmed by the peaks at 1011 cm–1 and 566 cm–1.
Fig. 2. The Photograph of as grown NPT crystals. 2
Optik - International Journal for Light and Electron Optics 194 (2019) 163048
V. Thayanithi, et al.
Fig. 3. ORTEP plot of the grown NPT compound. Table 1 Crystal data, data collection and structure refinement of grown NPT crystal. Formula
C13H15NO6S
Formula weight Crystal system, Space group T (K) Unit cell parameters
313.32 Orthorhombic, Pmn21 295(2) a = 6.7368(12) Å b = 7.4199(7) Å c = 14.3455(6) Å α = 90º β = 90º γ = 90º 717.08(15) 2 1.451 328 0.253 0.30 0.25 0.20 2.75–26.97 −8 ≤ h ≤ 8 −9 ≤ k ≤ 9 −18 ≤ l ≤ 18 8283 1698 (0.0307) 1562 131 0.0307 0.0830 0.0351 0.0795 1.049 0.211/−0.188 1528873
V (Å3) Z Dx (g cm−3) F(000) μ (mm−1) Crystal size (mm) Θ range (º) hkl range
Reflections Collected Unique (Rint) With [I > 2σ(I)] Number of parameters R(F) [I > 2σ(I)] wR(F2) [I > 2σ(I)] R(F) [all data] wR(F2) [all data] Goodness of fit Max/min Δρ (e Å−3) CCDC No
3.3. Thermal analysis Thermal stability and decomposition of the grown NPT compound are analysed by Thermogravimetric analysis (TGA) and Differential scanning calorimetric (DSC) and its were measured in presence of nitrogen gas. Three stages thermal decomposition of the grown NPT compound is shown in Fig. 6. First stage of decomposition (70 °C to 80 °C) is due to the loss of H2O (water) molecule in the grown NPT compound. Second decomposition (180 °C and 300 °C) may due to the release of Nicotinate, 3CH = CH and SO3 [12,13]. Third weight loss of the grown compound occurs at 360 °C with 5.72% and it may be due to the liberation of hydrocarbons 3
Optik - International Journal for Light and Electron Optics 194 (2019) 163048
V. Thayanithi, et al.
Fig. 4. External morphology of the grown NPT crystal.
Fig. 5. FTIR spectrum of the grown NPT compound.
Fig. 6. Thermogravimetric analysis (TGA) of the grown NPT compound.
gases [9] molecule. DSC curve of the NPT crystal is shown in Fig. 7 and it shows that the sharp endothermic peak starts from 57 °C to 70 °C. The DSC curve clearly indicates that the melting point of the grown NPT crystal compound is 61.06 °C and it is thermally stable up to 60 °C. 3.4. UV–vis-NIR spectroscopy In nonlinear optics, single crystal of good optical transmittance is a desirable one for various applications [14]. UV–vis-NIR spectra were recorded for the grown NPT crystal (thickness ˜2 mm) using Shimadzu spectrometer in range between 200–800 nm. Transmittance spectra of the grown NPT crystalis shown in Fig. 8. From UV–vis graph, it is observed that the lower cut-off wavelength of the grown NPT crystals is 335 nm. Optical band gap of the grown NPT crystal was identified by Tauc’s relation [15]. The graph (Fig.9) was drawn between (αhν)2 and hν. The optical band gap of the grown NPT crystal is found to be 3.63 eV. The grown NPT crystals have wide transparency window without absorption in the entire visible region and it is more suitable for optoelectronic applications. 4
Optik - International Journal for Light and Electron Optics 194 (2019) 163048
V. Thayanithi, et al.
Fig. 7. Differential scanning calorimetric (DSC) curve of the grown NPT compound.
Fig. 8. Transmittance spectra of the grown NPT crystals.
Fig. 9. Plot of (αhυ)2vshυ.
3.5. Photoluminescence Photoluminescence on solid state organic molecule has attracted much attention in the field of basic photochemistry and material chemistry [16]. Emission spectra of the grown crystals (thickness ˜2 mm) were measured in the range 350–600 nm by using Bruker S4 pioneer. Emission spectrum of the grown NPT crystals is shown in Fig.10 and the excited wavelength of the grown NPT crystal is 340 nm. From the spectrum, emission wavelength of grown NPT crystals is observed at 664 nm, which indicates the red emission [17].
5
Optik - International Journal for Light and Electron Optics 194 (2019) 163048
V. Thayanithi, et al.
Fig. 10. Emission spectrum of the grown NPT crystal.
3.6. Laser damage threshold Laser damage threshold is a catastrophic complex phenomenon and it involves interaction of high power laser with physical, chemical, optical and thermal process in the crystal [18]. Surface withstand stability of the grown NPT crystals was determined by Qswitched high energy Nd:YAG laser (Quanta ray model lab – 170–10) with wavelength of 1064 nm and pulse width of 10 ns. The laser damage energy density of the grown crystals was calculated [19]. The calculated energy density of the grown NPT crystal is 1.9 GW/ cm–1. The optical photograph of damaged NPT crystal by high intensity laser is shown in Fig. 11. The damage of the NPT is due to the thermal effects of melting point and molecular decomposing.
3.7. Dielectric properties The prominent plane (001) of grown NPT crystal (thickness ˜1 mm) was subjected to measure the capacitance (C) and dissipation factor (D) and it was made to act as parallel plate capacitor by coating air-dying sliver paste on opposite side. The dielectric measurements were carried out at room temperature from 50 Hz to 5 MHz. The dielectric constant (εr) of grown NPT crystal was found [20] and graph was plotted for (εr) against log f and it is shown in Fig. 12. The dielectric constant of the grown NPT crystal is inversely proportional to the applied frequency which means dielectric constant decreases with increasing frequency. The dielectric loss (tan δ) of the grown crystal also decreases by increasing frequency and shown in Fig. 13. The grown NPT crystal possesses higher value of dielectric constant at low frequency. It may be due to space charge polarization. The low dielectric loss shows that the grown crystal has good optical quality and lesser defects [20].
3.8. Vickers micro hardness test Micro hardness load indentations were made on cut and polished without crack surface crystals of NPT, load increases slowly in the ranging from 10 g to 60 g with constant indentation time of 5 s. The micro hardness (Hv) was determined [13] and the graph (Fig. 14) was drawn for micro hardness (Hv) values as a function of applied loads (p). Micro hardness (Hv) values of grown NPT crystal decrease with increasing applied load (p) and it clearly indicates normal indentation size effect [21]. Indentation of load (p) is stopped at 70 g due to cracks were occurred on surface of the grown NPT crystal. Work hardening co-efficient for the grown crystal was identified by Mayer’s relation [12] and the graph (Fig. 15) is plotted between log p and log d. The value of work hardening coefficient n of the grown NPT crystals is found to be 1.44 and it indicates that the grown crystals belong to hard material category [22,23]. According to Sangwal, the grown NPT crystals obey normal ISE [24].
Fig. 11. The optical photograph of the damaged by laser beam. 6
Optik - International Journal for Light and Electron Optics 194 (2019) 163048
V. Thayanithi, et al.
Fig. 12. Dielectric constant of the grown NPT crystal.
Fig. 13. The dielectric loss of the grown NPT crystal.
Fig. 14. Hardness (Hv) vs Load P.
3.9. Second harmonic generation (SHG) test Kurtz Perry technique determines the SHG efficiency. Efficiency is compared with reference material Potassium dihydrogen phosphate (KDP). A Q-switched high-energy Nd:YAG laser (Quanta ray model lab–170–10) with wavelength of 1064 nm was used to measure SHG outputs. The input energy is 0.701 J/pulse with pulse duration of 6 ns and repetition rate of 10 Hz. was passed through pellet samples. The emission of green radiation (λ = 532 nm) was measured by the photomultiplier tube and it confirms the generation of second harmonic. The output of the grown NPT compound is found to be 6.77 mJ and KDP is found to be 8.91 mJ. The SHG 7
Optik - International Journal for Light and Electron Optics 194 (2019) 163048
V. Thayanithi, et al.
Fig. 15. log P Vslog d.
efficiency of the grown NPT crystal is 0.75 times that of KDP. 4. Conclusion Synthesis compound of NPT single crystals were successfully grown by conventional method. Single crystal XRD confirms the crystalline nature and the grown crystal belongs to orthorhombic crystal system with noncentrosymmetric space group Pmn21. The vibrations of the functional group in the grown NPT compound are identified by the FTIR spectroscopy. Thermal stability of the grown crystal compound is found to be 60 °C. The grown NPT crystal shows higher transmittance in visible region and it slower cutoff wavelength is found to be 335 nm. The emission wavelength of grown NPT crystals is observed at 664 nm and it is in red emission region. The calculated LDT value of the grown NPT crystal is 1.9 GW/cm–2. The dielectric parameters of the grown NPT crystal are inversely proportional to the applied frequency. Work hardening coefficient indicates the grown crystal belongs to hard material category. The SHG efficiency of the grown NPT crystal is 0.75 times that of KDP. The grown NPT crystal is considerable one in field of optoelectronic applications. Acknowledgement The authors acknowledge the SAIF, IIT Madras for characterization studies. References [1] G. Liu, J. Liu, X. Zheng, Y. Liu, D. Yuan, X. Zhang, Z. Gao, X. Tao, Bulk crystal growth and characterization of semiorganic nonlinear optical crystal tridiethylammonium hexachlorobismuthate (TDCB), CrystEngComm 17 (2015) 2569–2574. [2] T. Pal, T. Kar, G. Bocelli, L. Rigi, Synthesis, growth, and characterization of l-arginine acetate crystal: a potential nlo material, Cryst. Grow. Design 3 (2003) 13–16. [3] D.S. Chemla, J. Zyss (Eds.), Nonlinear Optical Properties of Organic Molecules and Crystals, Vol. I Academic press, New York, 1987. [4] K. Rajesh, A. Mani, K. Anandan, P. Praveen Kumar, Crystal and optical perfection, linear and nonlinear optical qualities of β alanine β alaninium picrate (βAβAP) single crystal: a promising NLO crystal for optics and photonics applications, J Mater Sci: Mater Electron 28 (2014) 11446–11454. [5] K. Rajesh, A. Mani, V. Thayanithi, P. Praveen Kumar, Optical, thermal, and mechanical properties of L-Serine phosphate, a semiorganic enhanced NLO single crystal, Int. J. Opt., Int. J. Opt. 2016 (2016) 5. [6] M.S. Ahmad, M. Khalid, M.A. Shaheen, M.N. Tahir, M.U. Khan, A.A.C. Braga, H.A. Shad, Synthesis and XRD, FT-IR vibrational, UV–vis, and nonlinear optical exploration of novel tetra substituted imidazole derivatives: a synergistic experimental-computational analysis, J. Phys. Chem. Solids 115 (2018) 265–276. [7] E. Selvakumar, G. Anandha babu, P. Ramasamy, T. Rajnikant, R. Uma Devi, A. Meenakshi, Chandramohan, Synthesis, growth, structure and spectroscopic characterization of a new organic nonlinear optical hydrogen bonding complex crystal: 3-Carboxyl anilinium p-toluene sulfonate, Spectrochim. Acta A: Mol. Biomol. Spectrosc. 125 (2014) 114–119. [8] M. Suresh, S. Asath Bahadur, S. Athimoolam, Crystal growth and characterization of a new NLO material: p-Toluidine p-Toluenesulfonate, Indian J. Mater. Sci. 2013 (2013) 1–4. [9] M. Suresh, S. Asath Bahadur, S. Athimoolam, Synthesis, growth and characterization of a new hydrogen bonded organic tosylate crystal: L-alaninium ptoluenesulfonate for second order nonlinear optical applications, J. Mater Sci. Mater Electron 27 (2016) 4578–4589. [10] M. Suresh, S. Asath Bahadur, S. Athimoolam, Synthesis, growth, structural, spectral, thermal and microhardness studies of a new hydrogen bonded organic nonlinear optical material: l–valinium p–toluenesulfonate monohydrate (LVPT), J. Mol. struct. 1112 (2016) 71–80. [11] G. Vadivelan, M. Saravanabhavan, V. Murugesan, M. Sekar, Synthesis, characterization and biological studies of a charge transfer complex: 2-Aminopyridinium4-methylbenzenesulfonate, Spectrochim. Acta A. Mol. Biomol. Spectrosc. 145 (2015) 461–466. [12] V. Thayanithi, P. Praveen Kumar, Growth, optical, mechanical and thermal behavior of unidirectionally grown L-Glutaminium p-Toluenesulfonate crystal, Mater. Res. Express 6 (2019) 046207. [13] Z. Vargová, V. Zeleòák, I. C´ısaøová, K. Györyová, Correlation of thermal and spectral properties of zinc(II) complexes of pyridinecarboxylic acids with their crystal structures, Thermochim. Acta 423 (2004) 149–157. [14] P. Urit Charoen-In, P. Ramasamy, Manyum Unidirectional growth, improved structural perfection and physical properties of a semi-organic nonlinear optical dichlorobis(L-proline)zinc(II) single crystal, J. Cryst. Growth 362 (2013) 220–226. [15] N. Rani, N. Vijayan, B. Riscob, S.K. Jat, A. Krishna, S. Das, G. Bhagavannarayana, B. Rathi, M.A. Wahab, Single crystal growth of ninhydrin by unidirectional Sankaranarayanan–Ramasamy (SR) method by using a glass ampoule for nonlinear optical applications, CrystEngComm. 15 (2013) 2127–2132.
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[16] Y. Sonoda, M. Goto, Y. Norikane, R. Azumi, Crystal structures and fluorescence spectroscopic properties of Cyano-Substituted Diphenylhexatrienes, Cryst. Growth Des. 14 (2014) 4781–4789. [17] J. Reichman, Handbook of Optical Filters for Fluorescence Microscopy, Chroma Technol Corp, Brattleboro, 2000. [18] N.L. Boling, M.D. Crisp, G. Dubé, Laser induced surface damage, Appl. Opt. 12 (1973) 650–660. [19] H.E. Bennett, H.A. Guenther, D. Milam, B.E. Newnam, Laser Induced Damage in Optical Materials, U.S Department of Commerce, National Bureau of Standards, Boulder, Colorado, 1986. [20] R. Uthrakumar, C. Vesta, C. Justin Raj, S. Krishnan, S. Jerome Das, Bulk crystal growth and characterization of non-linear optical bisthiourea zinc chloride single crystal by unidirectional growth method, Curr. Appl. Phys. 10 (2010) 548–552. [21] G. Peramaiyan, P. Pandia, N. Vijayan, R. Bhagavannarayana, Mohan Kumar, Studies on growth, structural, optical and mechanical properties of xylenol orange dye admixtured l-arginine phosphate single crystal, Optik 124 (2013) 4058–4063. [22] E.M. Onitsch, Microscopia 2 (1947) 131. [23] M. Hanneman, Metall. Manch. 23 (1941) 135. [24] K. Sangwal, On the reverse indentation size effect and microhardness measurement of solids, Mater. Chem. Phys. 63 (2000) 145–152.
9
Contents lists available at ScienceDirect
Optik journal homepage: www.elsevier.com/locate/ijleo
Original research article
Growth, optical, dielectrical, thermal and mechanical behavior of organic nonlinear optical Nicotinium p-toluenesulfonate monohydrate single crystal V. Thayanithia, B. Gunasekaranb, P. Praveen Kumara, a b
T
⁎
Department of Physics, Presidency college, Chennai, 600005, Tamilnadu, India Department of Physics & Nano Technology, SRM University, SRM Nagar, Kattankulathur, Kancheepuram Dist., Chennai, 603 203, India
A R T IC LE I N F O
ABS TRA CT
Keywords: Organic compounds Crystal growth Laser damage threshold Differential scanning calorimetric Nonlinear optical properties
Noncentrosymmetric crystal of Nicotinium p-Toluenesulfonate (NPT) was grown by slow evaporation growth method. The crystal structure was determined by Single crystal X-ray diffraction and it confirms that the grown NPT crystal belong to orthorhombic crystal system with noncentrosymmetric space group Pmn21. The vibrations of the functional groups and chemical bonds were analyzed by FTIR spectrum. The grown NPT compound is thermally stable upto 60 °C and its decomposition was elucidated by Thermal analysis. The grown NPT crystal posses wide optical transmittance in the visible region and lower cut-off wavelength is found to be 335 nm. The emission region of grown NPT crystal was identified by photoluminescence emission spectrum. The surface with stand stability from damage induced by high power laser beam for grown NPT crystal was studied. The dielectric parameters of the grown NPT crystal are inversely proportional to the applied frequency. The grown NPT crystals belong to hard material category. The SHG efficiency of the grown NPT crystal is 0.75 times than that of KDP.
1. Introduction In recent years, organic molecule based nonlinear optical materials surpasses the inorganic nonlinear optical materials because of their large nonlinear optical susceptibilities (χ), high power of laser withstand stability, short lower cut-off wavelength with good transparency and inherent ultrafast response time [1,2]. The organic crystals have received greater attention among recent investigators due to high second order nonlinearity and its potential optical applications, such as optical storage devices, frequency doubling, optoelectronics, terahertz generation and detection [3–5]. Nonlinear optical response of organic molecules is caused by intramolecular charged transfer of donor/acceptor through π-space and delocalized electrons. Increasing of π-conjugated bond length and positioning of donor/acceptor moieties help to enhance nonlinear activity in organic materials. Polar π-conjugated forms the push-pull conjugated structure by one end of electron donor group with another end as an electron acceptor group. The polar πconjugated molecule increases the electronic distribution asymmetrically by electron donor and acceptor group [6–8]. p-Toluenesulfonic acid is an organic acid with strong sulfonic acid and also easily obtainable in salt form. It can be mixed with organic base compounds to form organic salts [9,10]. The compound has electron donor group (methyl) and electron acceptor group (sulfonate) [11]. The present investigation deals with structure, growth and characterization of Nicotiniump-Toluenesulfonate monohydrate (NPT)
⁎
Corresponding author. E-mail address: [email protected] (P.P. Kumar).
https://doi.org/10.1016/j.ijleo.2019.163048 Received 26 March 2019; Received in revised form 23 June 2019; Accepted 2 July 2019 0030-4026/ © 2019 Elsevier GmbH. All rights reserved.
Optik - International Journal for Light and Electron Optics 194 (2019) 163048
V. Thayanithi, et al.
Fig. 1. Synthesis scheme of the grown NPT crystal.
crystal. Defect free crystal of NPT crystal was grown by slow evaporation method. Structure of NPT crystal was solved by SHELXS97. The grown NPT crystal belongs to orthorhombic crystal system with noncentrosymmetric space group Pmn21. The grown crystal is subjected to different characterization such as FTIR spectroscopy, Thermal analysis, UV–vis-NIR spectroscopy, Laser damage threshold, Micro hardness and Second harmonic generation (SHG) to confirm their suitability for desirable device applications.
2. Experimental procedure and crystal growth The crystal compound of NPT was synthesized by dissolving equimolar ratio of Nicotinic acid and p-toluene sulfonic acid monohydrate in de-ionized water at room temperature. The saturated solution was filtered into a beaker and it was kept in dust free place. The reaction scheme of the grown NPT crystal is shown in Fig. 1. Transparent and well grown crystal with size of 20 × 8 × 3 mm3 was harvested from the solution in 20 days of time period. The photograph of the as grown NPT crystal by conventional method is shown in Fig. 2.
3. Result and disscussion 3.1. Single crystal X-ray diffraction Single crystal X-ray diffraction was analyzed at room temperature using Bruker Kappa diffractometer with Mo Kα radiation using ω/2θ scan mode. The grown NPT compound crystallizes in Orthorhombic crystal system with noncentrosymmetric space group Pmn21 and cell parameters are a = 6.7368(12) Å, b = 7.4199(7) Å, c = 14.3455(6) Å. The structure of compound was resolved by direct method procedure as implemented in SHELXS97 program. The Oak Ridge Thermal-Ellipsoid Plot (ORTEP) plot of the grown NPT compound is shown in Fig. 3. Table 1 summarizes the crystallographic data of the grown NPT compound. Morphology of the grown crystal was determined by X-ray goniometry and it was drawn. The drawn morphology of the grown crystal is shown in Fig. 4. The grown crystal face planes are (001), (010), (0–10), (100), (−100), (01–1) and (0–1–1). The predominant axis of the grown NPT crystal isc-axis and it determines length of the crystal. The b-axis and a-axis determines the width of the grown NPT crystal.
3.2. FTIR spectroscopy FTIR spectrum was recorded using Perkin elmer spectrometer in range of 450–4000 cm–1 by KBr pellet at room temperature and it is shown in Fig. 5. The peak at 3300 cm–1 is indicates the NeH stretching. The peak at 2948 cm–1 shows that presence of OeH stretching. The presence of carboxylic acid group of C]O stretching was indicated by the peak at 1708 cm–1. The peak at 2219 cm–1 indicates the presence of CeN stretching and the peak at 1632 cm–1 shows that the NeH bending. The peak at 1494 cm–1 shows that presence of C]N stretching vibration. The peak at 1545 cm–1 is due to C]C stretching. The peak at 1474 cm–1 is due to aromatic ring stretching of CeC. The peak at 1320 cm–1 is due to presence of CeS stretching vibration. The presence of SO3 asymmetric stretching is confirmed by the peak at 1225 cm–1 and the presence of SO3 symmetric stretching is confirmed by the peaks at 1011 cm–1 and 566 cm–1.
Fig. 2. The Photograph of as grown NPT crystals. 2
Optik - International Journal for Light and Electron Optics 194 (2019) 163048
V. Thayanithi, et al.
Fig. 3. ORTEP plot of the grown NPT compound. Table 1 Crystal data, data collection and structure refinement of grown NPT crystal. Formula
C13H15NO6S
Formula weight Crystal system, Space group T (K) Unit cell parameters
313.32 Orthorhombic, Pmn21 295(2) a = 6.7368(12) Å b = 7.4199(7) Å c = 14.3455(6) Å α = 90º β = 90º γ = 90º 717.08(15) 2 1.451 328 0.253 0.30 0.25 0.20 2.75–26.97 −8 ≤ h ≤ 8 −9 ≤ k ≤ 9 −18 ≤ l ≤ 18 8283 1698 (0.0307) 1562 131 0.0307 0.0830 0.0351 0.0795 1.049 0.211/−0.188 1528873
V (Å3) Z Dx (g cm−3) F(000) μ (mm−1) Crystal size (mm) Θ range (º) hkl range
Reflections Collected Unique (Rint) With [I > 2σ(I)] Number of parameters R(F) [I > 2σ(I)] wR(F2) [I > 2σ(I)] R(F) [all data] wR(F2) [all data] Goodness of fit Max/min Δρ (e Å−3) CCDC No
3.3. Thermal analysis Thermal stability and decomposition of the grown NPT compound are analysed by Thermogravimetric analysis (TGA) and Differential scanning calorimetric (DSC) and its were measured in presence of nitrogen gas. Three stages thermal decomposition of the grown NPT compound is shown in Fig. 6. First stage of decomposition (70 °C to 80 °C) is due to the loss of H2O (water) molecule in the grown NPT compound. Second decomposition (180 °C and 300 °C) may due to the release of Nicotinate, 3CH = CH and SO3 [12,13]. Third weight loss of the grown compound occurs at 360 °C with 5.72% and it may be due to the liberation of hydrocarbons 3
Optik - International Journal for Light and Electron Optics 194 (2019) 163048
V. Thayanithi, et al.
Fig. 4. External morphology of the grown NPT crystal.
Fig. 5. FTIR spectrum of the grown NPT compound.
Fig. 6. Thermogravimetric analysis (TGA) of the grown NPT compound.
gases [9] molecule. DSC curve of the NPT crystal is shown in Fig. 7 and it shows that the sharp endothermic peak starts from 57 °C to 70 °C. The DSC curve clearly indicates that the melting point of the grown NPT crystal compound is 61.06 °C and it is thermally stable up to 60 °C. 3.4. UV–vis-NIR spectroscopy In nonlinear optics, single crystal of good optical transmittance is a desirable one for various applications [14]. UV–vis-NIR spectra were recorded for the grown NPT crystal (thickness ˜2 mm) using Shimadzu spectrometer in range between 200–800 nm. Transmittance spectra of the grown NPT crystalis shown in Fig. 8. From UV–vis graph, it is observed that the lower cut-off wavelength of the grown NPT crystals is 335 nm. Optical band gap of the grown NPT crystal was identified by Tauc’s relation [15]. The graph (Fig.9) was drawn between (αhν)2 and hν. The optical band gap of the grown NPT crystal is found to be 3.63 eV. The grown NPT crystals have wide transparency window without absorption in the entire visible region and it is more suitable for optoelectronic applications. 4
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Fig. 7. Differential scanning calorimetric (DSC) curve of the grown NPT compound.
Fig. 8. Transmittance spectra of the grown NPT crystals.
Fig. 9. Plot of (αhυ)2vshυ.
3.5. Photoluminescence Photoluminescence on solid state organic molecule has attracted much attention in the field of basic photochemistry and material chemistry [16]. Emission spectra of the grown crystals (thickness ˜2 mm) were measured in the range 350–600 nm by using Bruker S4 pioneer. Emission spectrum of the grown NPT crystals is shown in Fig.10 and the excited wavelength of the grown NPT crystal is 340 nm. From the spectrum, emission wavelength of grown NPT crystals is observed at 664 nm, which indicates the red emission [17].
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Fig. 10. Emission spectrum of the grown NPT crystal.
3.6. Laser damage threshold Laser damage threshold is a catastrophic complex phenomenon and it involves interaction of high power laser with physical, chemical, optical and thermal process in the crystal [18]. Surface withstand stability of the grown NPT crystals was determined by Qswitched high energy Nd:YAG laser (Quanta ray model lab – 170–10) with wavelength of 1064 nm and pulse width of 10 ns. The laser damage energy density of the grown crystals was calculated [19]. The calculated energy density of the grown NPT crystal is 1.9 GW/ cm–1. The optical photograph of damaged NPT crystal by high intensity laser is shown in Fig. 11. The damage of the NPT is due to the thermal effects of melting point and molecular decomposing.
3.7. Dielectric properties The prominent plane (001) of grown NPT crystal (thickness ˜1 mm) was subjected to measure the capacitance (C) and dissipation factor (D) and it was made to act as parallel plate capacitor by coating air-dying sliver paste on opposite side. The dielectric measurements were carried out at room temperature from 50 Hz to 5 MHz. The dielectric constant (εr) of grown NPT crystal was found [20] and graph was plotted for (εr) against log f and it is shown in Fig. 12. The dielectric constant of the grown NPT crystal is inversely proportional to the applied frequency which means dielectric constant decreases with increasing frequency. The dielectric loss (tan δ) of the grown crystal also decreases by increasing frequency and shown in Fig. 13. The grown NPT crystal possesses higher value of dielectric constant at low frequency. It may be due to space charge polarization. The low dielectric loss shows that the grown crystal has good optical quality and lesser defects [20].
3.8. Vickers micro hardness test Micro hardness load indentations were made on cut and polished without crack surface crystals of NPT, load increases slowly in the ranging from 10 g to 60 g with constant indentation time of 5 s. The micro hardness (Hv) was determined [13] and the graph (Fig. 14) was drawn for micro hardness (Hv) values as a function of applied loads (p). Micro hardness (Hv) values of grown NPT crystal decrease with increasing applied load (p) and it clearly indicates normal indentation size effect [21]. Indentation of load (p) is stopped at 70 g due to cracks were occurred on surface of the grown NPT crystal. Work hardening co-efficient for the grown crystal was identified by Mayer’s relation [12] and the graph (Fig. 15) is plotted between log p and log d. The value of work hardening coefficient n of the grown NPT crystals is found to be 1.44 and it indicates that the grown crystals belong to hard material category [22,23]. According to Sangwal, the grown NPT crystals obey normal ISE [24].
Fig. 11. The optical photograph of the damaged by laser beam. 6
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Fig. 12. Dielectric constant of the grown NPT crystal.
Fig. 13. The dielectric loss of the grown NPT crystal.
Fig. 14. Hardness (Hv) vs Load P.
3.9. Second harmonic generation (SHG) test Kurtz Perry technique determines the SHG efficiency. Efficiency is compared with reference material Potassium dihydrogen phosphate (KDP). A Q-switched high-energy Nd:YAG laser (Quanta ray model lab–170–10) with wavelength of 1064 nm was used to measure SHG outputs. The input energy is 0.701 J/pulse with pulse duration of 6 ns and repetition rate of 10 Hz. was passed through pellet samples. The emission of green radiation (λ = 532 nm) was measured by the photomultiplier tube and it confirms the generation of second harmonic. The output of the grown NPT compound is found to be 6.77 mJ and KDP is found to be 8.91 mJ. The SHG 7
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Fig. 15. log P Vslog d.
efficiency of the grown NPT crystal is 0.75 times that of KDP. 4. Conclusion Synthesis compound of NPT single crystals were successfully grown by conventional method. Single crystal XRD confirms the crystalline nature and the grown crystal belongs to orthorhombic crystal system with noncentrosymmetric space group Pmn21. The vibrations of the functional group in the grown NPT compound are identified by the FTIR spectroscopy. Thermal stability of the grown crystal compound is found to be 60 °C. The grown NPT crystal shows higher transmittance in visible region and it slower cutoff wavelength is found to be 335 nm. The emission wavelength of grown NPT crystals is observed at 664 nm and it is in red emission region. The calculated LDT value of the grown NPT crystal is 1.9 GW/cm–2. The dielectric parameters of the grown NPT crystal are inversely proportional to the applied frequency. Work hardening coefficient indicates the grown crystal belongs to hard material category. The SHG efficiency of the grown NPT crystal is 0.75 times that of KDP. The grown NPT crystal is considerable one in field of optoelectronic applications. Acknowledgement The authors acknowledge the SAIF, IIT Madras for characterization studies. References [1] G. Liu, J. Liu, X. Zheng, Y. Liu, D. Yuan, X. Zhang, Z. Gao, X. Tao, Bulk crystal growth and characterization of semiorganic nonlinear optical crystal tridiethylammonium hexachlorobismuthate (TDCB), CrystEngComm 17 (2015) 2569–2574. [2] T. Pal, T. Kar, G. Bocelli, L. Rigi, Synthesis, growth, and characterization of l-arginine acetate crystal: a potential nlo material, Cryst. Grow. Design 3 (2003) 13–16. [3] D.S. Chemla, J. Zyss (Eds.), Nonlinear Optical Properties of Organic Molecules and Crystals, Vol. I Academic press, New York, 1987. [4] K. Rajesh, A. Mani, K. Anandan, P. Praveen Kumar, Crystal and optical perfection, linear and nonlinear optical qualities of β alanine β alaninium picrate (βAβAP) single crystal: a promising NLO crystal for optics and photonics applications, J Mater Sci: Mater Electron 28 (2014) 11446–11454. [5] K. Rajesh, A. Mani, V. Thayanithi, P. Praveen Kumar, Optical, thermal, and mechanical properties of L-Serine phosphate, a semiorganic enhanced NLO single crystal, Int. J. Opt., Int. J. Opt. 2016 (2016) 5. [6] M.S. Ahmad, M. Khalid, M.A. Shaheen, M.N. Tahir, M.U. Khan, A.A.C. Braga, H.A. Shad, Synthesis and XRD, FT-IR vibrational, UV–vis, and nonlinear optical exploration of novel tetra substituted imidazole derivatives: a synergistic experimental-computational analysis, J. Phys. Chem. Solids 115 (2018) 265–276. [7] E. Selvakumar, G. Anandha babu, P. Ramasamy, T. Rajnikant, R. Uma Devi, A. Meenakshi, Chandramohan, Synthesis, growth, structure and spectroscopic characterization of a new organic nonlinear optical hydrogen bonding complex crystal: 3-Carboxyl anilinium p-toluene sulfonate, Spectrochim. Acta A: Mol. Biomol. Spectrosc. 125 (2014) 114–119. [8] M. Suresh, S. Asath Bahadur, S. Athimoolam, Crystal growth and characterization of a new NLO material: p-Toluidine p-Toluenesulfonate, Indian J. Mater. Sci. 2013 (2013) 1–4. [9] M. Suresh, S. Asath Bahadur, S. Athimoolam, Synthesis, growth and characterization of a new hydrogen bonded organic tosylate crystal: L-alaninium ptoluenesulfonate for second order nonlinear optical applications, J. Mater Sci. Mater Electron 27 (2016) 4578–4589. [10] M. Suresh, S. Asath Bahadur, S. Athimoolam, Synthesis, growth, structural, spectral, thermal and microhardness studies of a new hydrogen bonded organic nonlinear optical material: l–valinium p–toluenesulfonate monohydrate (LVPT), J. Mol. struct. 1112 (2016) 71–80. [11] G. Vadivelan, M. Saravanabhavan, V. Murugesan, M. Sekar, Synthesis, characterization and biological studies of a charge transfer complex: 2-Aminopyridinium4-methylbenzenesulfonate, Spectrochim. Acta A. Mol. Biomol. Spectrosc. 145 (2015) 461–466. [12] V. Thayanithi, P. Praveen Kumar, Growth, optical, mechanical and thermal behavior of unidirectionally grown L-Glutaminium p-Toluenesulfonate crystal, Mater. Res. Express 6 (2019) 046207. [13] Z. Vargová, V. Zeleòák, I. C´ısaøová, K. Györyová, Correlation of thermal and spectral properties of zinc(II) complexes of pyridinecarboxylic acids with their crystal structures, Thermochim. Acta 423 (2004) 149–157. [14] P. Urit Charoen-In, P. Ramasamy, Manyum Unidirectional growth, improved structural perfection and physical properties of a semi-organic nonlinear optical dichlorobis(L-proline)zinc(II) single crystal, J. Cryst. Growth 362 (2013) 220–226. [15] N. Rani, N. Vijayan, B. Riscob, S.K. Jat, A. Krishna, S. Das, G. Bhagavannarayana, B. Rathi, M.A. Wahab, Single crystal growth of ninhydrin by unidirectional Sankaranarayanan–Ramasamy (SR) method by using a glass ampoule for nonlinear optical applications, CrystEngComm. 15 (2013) 2127–2132.
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