- Email: [email protected]
Growth, structural, optical, spectral and thermal characterization of third order nonlinear optical crystal: Diammonium fumarate
Chinese Journal of Physics 61 (2019) 104–112
Contents lists available at ScienceDirect
Chinese Journal of Physics journal homepage: www.elsevier.com/locate/cjph
Growth, structural, optical, spectral and thermal characterization of third order nonlinear optical crystal: Diammonium fumarate N. Kalaimania, K. Ramyab, R. Aarthic, C. Ramachandra Rajac, a b c
T
⁎
Department of Physics, Thiru.Vi.Ka Government Arts College, Thiruvarur 610 003, Tamilnadu, India Department of Physics, TUK Arts College, Thanjavur 613 002, Tamilnadu, India Department of Physics, Government Arts College (Autonomous), Kumbakonam 612 002, Tamilnadu, India
A R T IC LE I N F O
ABS TRA CT
Keywords: Diammonium fumarate Single crystal X-ray analysis Thermal analysis Z-scan technique
Single crystals of diammonium fumarate were grown from aqueous solution by slow evaporation method. The lattice parameters and the crystal system are estimated from single crystal X-ray diffraction analysis. The transmission range of the crystal was revealed from UV-Vis-NIR analysis. The vibrational modes of different molecular groups present in the crystal was identified from IR and Raman spectroscopy. The NMR analysis confirms the molecular structure of the grown crystal. The thermal properties were analyzed from TG/DTA thermograms. The nonlinear refractive index and third order nonlinear optical susceptibility were determined from Z-scan technique.
1. Introduction In the present scenario, nonlinear optics and photonic fields are important in the development of applications in many disciplines of research and in industries. A variety of nonlinear optical materials can serve as radiation detectors, solid state lasers, harmonic generators, transducers and crystalline thin films for microelectronics and computer industries. Organic materials are prominent owing to its good nonlinear optical response, but they suffer from low mechanical and thermal stability. The inorganic materials exhibit good mechanical, thermal and deep UV transmission properties, but have low nonlinear efficiency. The combination of organic and inorganic materials with large nonlinear optical characteristics, leads to the investigation of semi organic materials [1–3]. The semi organic crystals are grown due to their stable physiochemical properties, that are essential for fabrication of devices and in applied research [4,5]. The hydrogen bonding interaction between cations and anions in organic and inorganic compounds, produces high second and third harmonic generation efficiency, good transmittance in UV-Vis region and better chemical, mechanical and thermal stability [6–9]. Semiorganic crystals with centrosymmetric space group produce third harmonic generation that are used in information processing and optoelectronic devices [10]. The nonlinear optical properties of many crystal derivatives of ammonium are already reported [11,12]. Here in this report, the crystals of diammonium fumarate have been grown using solvent evaporation solution growth method. The structure of diammonium fumarate has already been reported [13]. Apart from the description of crystal structure, the studies on the growth and characterization have not been carried out. Hence the grown crystal were characterized by single crystal X-ray diffraction analysis, UV-Vis-NIR spectroscopy, FTIR spectroscopy, Raman spectroscopy, NMR spectroscopy, and Thermal analysis. The third order nonlinear optical susceptibility was measured from Z-scan technique.
⁎
Corresponding author. E-mail address: [email protected] (C. Ramachandra Raja).
https://doi.org/10.1016/j.cjph.2019.08.007 Received 27 October 2018; Received in revised form 21 August 2019; Accepted 27 August 2019 Available online 02 September 2019 0577-9073/ © 2019 The Physical Society of the Republic of China (Taiwan). Published by Elsevier B.V. All rights reserved.
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Fig. 1. Photograph of diammonium fumarate crystals.
2. Materials and methods Diammonium fumarate crystal was obtained from slow evaporation method. Ammonium carbonate and fumaric acid were mixed in an equimolar ratio of 1:1 in double distilled water and the solution was stirred well using magnetic stirrer for about 3 h to obtain a homogeneous saturated solution. This saturated solution was filtered using Whatmann filter paper. Then the filtered solution was covered using polythene paper and few holes were made for solvent evaporation. After 40 days colorless crystals were harvested. Fig. 1, shows the photograph of grown diammonium fumarate crystals. The reaction scheme of the grown crystal is given below.
3. Results and discussion 3.1. Single crystal XRD analysis Nonius CAD4/MACH 3 single crystal X-ray diffractometer with MoKα (λ = 0.71069 Å) radiation was used to analyses the grown crystal. This analysis reveals the lattice parameters of the grown crystal. The grown crystal belongs to monoclinic system with centrosymmetric space group P21/c. The comparison of lattice parameters obtained from single crystal XRD with reported values [13] are given in Table 1. 3.2. Optical analysis λ35 model Perkin Elmer double beam UV-Vis-NIR spectrometer in the range from 190 nm to 1100 nm was employed to study the transparency range of grown crystal. The transmission spectrum of the grown crystal is shown in Fig. 2. As seen from the transmittance spectrum, the lower cut off wavelength occurs at 300 m, and there is no absorption of light seen in the visible and near infra red regions. This good transmittance from 300 nm to 1100 nm makes the crystal suitable for NLO and optoelectronic applications. 3.3. Vibrational spectral analyses The KBr pellet technique is employed to record FTIR spectrum using a SPECTROMRX1 FTIR spectrometer and the BRUKER RFS 27 spectrometer was employed to record FT Raman spectrum of the grown crystal. The FTIR and FT Raman spectra of diammonium Table 1 Lattice parameters of diammonium fumarate crystal. Lattice parameters
Observed values
Reported values [13]
a(Å) b(Å) c(Å) α (°) β(°) γ(°)
3.773(1) 8.10(3) 11.65(5) 90 92.57(9) 90
3.733(3) 8.009(2) 11.508(2) 90 92.46(3) 90
105
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Fig. 2. UV-Vis-NIR spectrum of diammonium fumarate crystal.
fumarate crystal are shown in Figs. 3 and 4 respectively. The absorption band in the region from 3300-3000 cm−1 attributed to the stretching vibration of NH4+ group [14]. The absorption band at 3174 cm−1 in IR is assigned to NH4+asymmetric stretching vibration. The NH4+ group symmetric stretching was observed at 3084 cm−1 in IR and 3029 cm−1 in Raman spectra. The asymmetric deformation of NH4+ group was observed at 1699 cm−1 in IR and 1655 cm−1 in Raman spectra respectively. The IR peaks at 1577 cm−1 and 1424 cm−1 are due to asymmetric and symmetric vibration of caboxylate group. Its corresponding Raman peak are observed at 1555cm−1 and 1408 cm−1. The ammonium cations (NH4+) are linked to the carboxylate group of fumarate anion forming bidentate bond. The bidentate bond was formed when the difference between the wavenumbers is ΔV<200 cm−1 (asymmetric and symmetric vibration of COO¯ group) [15–17]. The bidentate bond formed between ammonium and fumaric acid confirms the formation of diammonium fumarate crystal. The asymmetric and symmetric stretching of CeC vibrations are observed at 1201 cm−1 and 977 cm−1 in IR and 1274 cm−1 and 979 cm−1 in Raman respectively. The vibrational assignments based on the spectra are given in Table 2.
Fig. 3. FTIR spectrum of diammonium fumarate crystal. 106
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Fig. 4. FT Raman spectrum of diammonium fumarate crystal.
Table 2 Observed vibrational wavenumbers and their assignments. Wavenumber cm−1
Assignments
FTIR
FT Raman
3174 3084 2858 1699 1577 1424 1201 977 887
– 3029 – 1655 1555 1408 1274 979 865
NH4+ asymmetric stretching NH4+ symmetric stretching CH stretching NH4+ asymmetric deformation COO¯ asymmetric stretching COO¯ symmetric stretching C-C asymmetric stretching CeC symmetric stretching C = C stretching
3.4. NMR studies The presence of carbon and proton signals were recorded using 1H NMR and 13C NMR spectroscopy. The solvent used here is D2O at room temperature and the instrument model is Bruker 300 MHz (ultrasheild)™ (operated at 300 MHz for 1H NMR and 75 MHz for 13 C NMR). Fig. 5 shows the 1H NMR spectrum of diammonium fumarate crystal. The peak values for 1H NMR and 13C NMR spectra are given in Table 3. The peak observed at δ = 4.686 ppm was due to the solvent D2O. The signal observed at δ = 6.335 ppm was attributed to the CH proton of fumaric acid in diammonium fumarate crystal. In pure fumaric acid (Table 3) the proton signal for CH group was observed at δ = 6.647 ppm. The peak values are shifted towards the upfield. The upfield shift in the value of CH proton was due to the intermolecular interaction between ammonium and fumaric acid. Thus, the absence of COOH proton of fumaric acid, indicates the formation of bond between the fumarate anion and ammonium cation, with the result in formation of diammonium fumarate crystal. The 13C NMR spectrum of diammonium fumarate crystal given in Fig. 6, produces two signals with respect to two carbon atoms present in the crystal. The presence of peak at δ = 173.42 ppm was due to the carbonyl carbon (COOH) and the peak at δ = 134.19 ppm was due to methylidene carbon (CH) of diammonium fumarate crystal. Table 3 gives the value of carbonyl and methylidene carbon of pure fumaric acid. Here also the values are shifted towards the upfield in diammonium fumarate crystal. This upfield shift was due to the bond, formed between ammonium and fumaric acid. 3.5. Thermal analysis Thermal studies were carried out using the instrument NETZSCH SDT Q600 V 8.3 build 101 in nitrogen atmosphere at a heating rate of 20 °C/min in the temperature 30–1000 °C. The TG/DTA curves of diammonium fumarate crystal are given in Fig. 7. The TGA curve reveals that the crystal is stable upto 225 °C. After this temperature, the crystal undergoes complete decomposition. The 107
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Fig. 5. 1H NMR spectrum of diammonium fumarate crystal. Table 3 Chemical shifts in 1H and Spectra
1
H NMR
13
C NMR
13
C NMR spectra of diammonium fumarate crystal. Chemical shift δ (ppm) diammonium fumarate crystal
Fumaric acid
Group Identification
6.335 4.686 173.42 134.19
6.647 177.23 137.95
–CH= D2O –COOH –CH=
endothermic peak at 257 °C in DTA curve represents the melting and decomposition of the compound. This endothermic peak also coincides with the weight loss in the TGA curve. 3.6. Third order nonlinear optical analysis Nd:YAG laser of intensity 5 mW (λ = 532 nm) focussed by a lens of 3.5 cm focal length was employed to record the Z-scan traces of the grown crystal. The Z-scan technique is used to determine the nonlinear optical parameters such as refractive index (n2), absorption co-efficient (β) and third order nonlinear optical susceptibility (χ3). These parameters are calculated from standard formulas available in the literature [18–21] and the results are given in Table 4. When intense laser beam propagates in a crystal, a nonlinear polarization is produced in the crystal which changes the propagation characteristics of the laser beam. The modification in the refractive index of the crystal in response to the applied intense light is known as Kerr effect and is a nonlinear optical effect. The magnitude of nonlinear refractive index (n2) can be measured with closed aperture Z-scan measurement. A positive n2 value is revealed as a pre-focal valley followed by post-focal peak curve and a negative n2 as a pre-focal peak followed by post-focal valley curve. The Kerr induced self-focussing effect gives a positive n2. The self-defocussing effect gives a negative n2. It arises due to the localized absorption of a focussed beam propagating through a crystal. This beam produces a spatial variation of refractive index due to spatial distribution of temperature in the crystal [22,23]. Consequently, it results in phase distortion of the propagating laser beam due to thermal effects. The closed aperture curve of diammonium fumarate crystal is given in Fig. 8. The observed n2 value of diammonium fumarate crystal is −10.31 × 10−8 cm2/W. It reveals the self-defocusing nature of diammonium fumarate crystal. This property makes the crystal to find applications like optical sensors, night vision devices [24]. The nonlinear absorption of the crystal can be found by recording open aperture curve through Z-scan technique. In case of positive nonlinear absorption (reverse saturable absorption), minimum transmittance is observed near the focus (Z = 0) and for 108
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Fig. 6.
13
C NMR spectrum of diammonium fumarate crystal.
Fig. 7. TG/DTA curve of diammonium fumarate crystal.
109
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Table 4 Third order nonlinear optical parameters of diammonium fumarate crystal. Parameters
Values
Nonlinear refractive index (n2) Nonlinear absorption co-efficient (β) Real part of susceptibility (Re χ3) Imaginary part of susceptibility (Im χ3) Third order susceptibility (χ3)
−10.31 × 10−8 cm2/W −0.02 × 10−4 cm/W 9.33 × 10−6 esu 0.12 × 10−6 esu 9.33 × 10−6 esu
Fig. 8. Closed aperture curve of diammonium fumarate crystal.
negative nonlinear absorption (saturable absorption), maximum transmittance is observed near the focus (Z = 0) [25]. Saturable absorption means the absorption of light decreases with increasing intensity. At high intensity, atoms in the ground level become excited into an upper energy level at such a rate that there is not enough time for the atoms to come back to the ground level before it gets depleted and the absorption subsequently saturates. The open aperture curve of diammonium fumarate crystal (Fig. 9) shows
Fig. 9. Open aperture curve of diammonium fumarate crystal. 110
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Table 5 (χ3) values of diammonium fumarate with some third order nonlinear optical crystal. Crystal name
Third order susceptibility (χ3) esu
References
Diammonium fumarate 4BPTS LiRbB4O7 LiKB4O7 2APTC KDP
9.33 × 10−6 4.162 × 10−8 2.719 × 10−7 4.85 × 10−9 9.6963 × 10−12 1.5 × 10−14
Present work [27] [28] [29] [30] [31]
saturable absorption property. This is an important optical property and it can be employed in Q switching to generate short optical pulses [26]. The third order susceptibility value depends on the hydrogen bonding interaction between the cations and anions present in the crystal. In the title crystal structure, the ammonium cations and fumarate anions are connected by (NeH…O) hydrogen bond. This hydrogen bonding interaction is responsible for the molecular polarization resulting in higher third order nonlinear susceptibility value. The susceptibility value of diammonium fumarate crystal is compared with the susceptibility values of some reported nonlinear optical crystals and are presented in Table 5. 4. Conclusion Diammonium fumarate crystals have been grown using an aqueous solution by solvent evaporation solution growth method. The single crystal X-ray diffraction analysis determines the lattice parameter and confirms that the crystal system is monoclinic. The lower cut off wavelength was observed at 300 nm. The presence of various functional groups were identified from FTIR and FTRaman spectral analyses. The 1H and 13C NMR reveals the molecular structure of grown crystal. The thermal behavior was investigated by TG/DTA experiment, which indicated that the crystal is thermally stable upto 225 °C. The values such as χ3 = 9.33 × 10−6esu and n2 = −10.31 × 10−8 cm2/W were calculated from Z-scan technique and reveals that the crystal is suitable for third harmonic generation. Conflicts of interest None. Acknowledgment The authors thank the sophisticated analytical instruments facility (SAIF), Indian Institute of Technology (IITM), Chennai for providing single crystal XRD and FT Raman spectrum and gratefully acknowledge the Instrumentation centre of St. Joseph's College, Trichy for recording FTIR and UV-Vis-NIR spectra. The authors wish to thank CECRI, Karaikudi, for TG/DTA studies and SASTRA university, Thanjavur for NMR studies. The authors are also grateful to Dr. G. Vinitha, VIT, Chennai for recording the Z-scan curves. References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23]
P.R. Newman, L.F. Warren, P. Cunningham, T.Y. Chang, D.E. Cooper, G.L. Burdge, Mater. Res. Soc. Symp. Proc. 173 (1990) 557–561. H.O. Marcy, L.F. Warren, M.S. Webb, C.A. Ebbers, S.P. Velsko, G.C. Kennedy, Appl. Opt. 31 (1992) 5051–5060. U. Ramabadran, D.E. Zelmon, G.C. Kennedy, Appl. Phys. Lett. 60 (1992) 2589–2592. R.A. Laudise (Ed.), The Growth of Single Crystals, Prentice Hall, Eagle wood Cliffs New Jersy, 1970. R.A. Laudise, R. Ueda, J.B. Mullin (Eds.), Crystal Growth an Characterization, North–Holland publishing Co., 1975. G. Xing, M. Jiang, Z. Shao, D. Xu, Chin. J. Lasers 14 (1987) 357–360. R. Mohan Kumar, D. Rajan Babu, D. Jayaraman, R. Jayavel, K. Kitamura, J. Cryst. Growth 275 (2005) 1935–1939. H.Q. Sun, D.R. Yuan, X.Q. Wang, X.F. Cheng, C.R. Gong, M. Zhou, H.Y. Xu, X.C. We, C.N. Luan, D.Y. Pan, Z.F. Li, X.Z. Shi, Cryst. Res. Technol. 40 (2005) 882–886. N. Karthick, R. Sankar, R. Jayavel, S. Pandi, J. Cryst. Growth 312 (2009) 114–119. R. Aarthi, P. Umarani, C. Ramachandra Raja, Appl. Phys. A. 124 (2018) 498–504. Redrothu Hanumantharao, S. Kalainathan, G. Bhagavannarayana, U. Madhusoodanan, Spectrochim. Acta Part A. 103 (2013) 388–399. D. Joseph Daniel, P. Ramasamy, Mater. Res. Bull. 47 (2012) 708–713. Hiroyuki Hosomi, Yoshikatsu Ito, Shigeru Ohba, Acta Cryst. C 54 (1998) 142–145. G. Socrates, Infrared, Raman Characteristic Group Frequencies, Tables and Charts, 3rd edn, Wiley, Chichester, 2001. K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, th ed, Wiley, New York, 1997, p. 60. E.Y. Ionashiro, F.J. Caires, A.B. Siqueira, L.S. Lima, C.T. Carvalho, J. Therm. Anal. Calorim. 108 (2012) 1183–1188. W. Lewandowski, H. Baranska, J. Raman Spectrosc. 17 (1986) 17–22. P. Karuppasamy, V. Sivasubramani, M. Senthil Pandian, P. Ramasamy, RSC Adv. 6 (2016) 33159–33169. T.C.S. Girisun, S. Dhanuskodi and G. Vinitha, Mater. Chem. Phys., 129(2011) 9–14. T. Thilak, M.B. Ahamed, G. Vinitha, Int. J. Light Electron Opt. 124 (2013) 4716–4720. A.N. Vigneshwaran, P. Umarani, C. Ramachandra Raja, J. Mater. Sci. Mater. Electron. 28 (2017) 11430–11438. E.L. Buckland, R.W. Boyd, Opt. Lett. 21 (15) (1996) 1117–1121. N. Sivakumar, G. Anbalagan, Opt. Mater. 60 (2016) 533–540.
111
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
[24] [25] [26] [27] [28] [29] [30] [31]
T.H. Wei, D.J. Hagan, M.J. Sence, E.W. Van Stryland, J.W. Perry, D.R. Coulter, Appl. Phys. B 54 (1992) 46–51. S. Dhanuskodi, T.C. Sabari Girisun, S. Vinitha Curr, Appl. Phys. 11 (2011) 860–864. Sze Y. Set, Hiroshi Yaguchi, Yuichi Tanaka, Mark Jablonski, J. Lightwave Technol. 22 (1) (2004) 51. K. Sivakumar, Saravana Kumar, R. Mohan Kumar, R. Kanagadurai, S. Sagadevan, Mat. Res. 19 (2016) 937–941. M. Sukumar, R. Ramesh Babu, K. Ramamurthi, Solid State Sci. 51 (2016) 8–12. M. Sukumar, K. Ramamurthi and, R. Ramesh Babu, Appl. Phys. B. 121 (2015) 369–373. M.K. Kumar, S. Sudhahar, A. Silambarasan, B.M. Sornamurthy, R.M. Kumar, Int. J. Light Electron Opt. 125 (2014) 751–755. A.N. Vigneshwaran, P. Paramasivam, C. Ramachandra Raja, Mater Lett. 178 (2016) 100–103.
112
Contents lists available at ScienceDirect
Chinese Journal of Physics journal homepage: www.elsevier.com/locate/cjph
Growth, structural, optical, spectral and thermal characterization of third order nonlinear optical crystal: Diammonium fumarate N. Kalaimania, K. Ramyab, R. Aarthic, C. Ramachandra Rajac, a b c
T
⁎
Department of Physics, Thiru.Vi.Ka Government Arts College, Thiruvarur 610 003, Tamilnadu, India Department of Physics, TUK Arts College, Thanjavur 613 002, Tamilnadu, India Department of Physics, Government Arts College (Autonomous), Kumbakonam 612 002, Tamilnadu, India
A R T IC LE I N F O
ABS TRA CT
Keywords: Diammonium fumarate Single crystal X-ray analysis Thermal analysis Z-scan technique
Single crystals of diammonium fumarate were grown from aqueous solution by slow evaporation method. The lattice parameters and the crystal system are estimated from single crystal X-ray diffraction analysis. The transmission range of the crystal was revealed from UV-Vis-NIR analysis. The vibrational modes of different molecular groups present in the crystal was identified from IR and Raman spectroscopy. The NMR analysis confirms the molecular structure of the grown crystal. The thermal properties were analyzed from TG/DTA thermograms. The nonlinear refractive index and third order nonlinear optical susceptibility were determined from Z-scan technique.
1. Introduction In the present scenario, nonlinear optics and photonic fields are important in the development of applications in many disciplines of research and in industries. A variety of nonlinear optical materials can serve as radiation detectors, solid state lasers, harmonic generators, transducers and crystalline thin films for microelectronics and computer industries. Organic materials are prominent owing to its good nonlinear optical response, but they suffer from low mechanical and thermal stability. The inorganic materials exhibit good mechanical, thermal and deep UV transmission properties, but have low nonlinear efficiency. The combination of organic and inorganic materials with large nonlinear optical characteristics, leads to the investigation of semi organic materials [1–3]. The semi organic crystals are grown due to their stable physiochemical properties, that are essential for fabrication of devices and in applied research [4,5]. The hydrogen bonding interaction between cations and anions in organic and inorganic compounds, produces high second and third harmonic generation efficiency, good transmittance in UV-Vis region and better chemical, mechanical and thermal stability [6–9]. Semiorganic crystals with centrosymmetric space group produce third harmonic generation that are used in information processing and optoelectronic devices [10]. The nonlinear optical properties of many crystal derivatives of ammonium are already reported [11,12]. Here in this report, the crystals of diammonium fumarate have been grown using solvent evaporation solution growth method. The structure of diammonium fumarate has already been reported [13]. Apart from the description of crystal structure, the studies on the growth and characterization have not been carried out. Hence the grown crystal were characterized by single crystal X-ray diffraction analysis, UV-Vis-NIR spectroscopy, FTIR spectroscopy, Raman spectroscopy, NMR spectroscopy, and Thermal analysis. The third order nonlinear optical susceptibility was measured from Z-scan technique.
⁎
Corresponding author. E-mail address: [email protected] (C. Ramachandra Raja).
https://doi.org/10.1016/j.cjph.2019.08.007 Received 27 October 2018; Received in revised form 21 August 2019; Accepted 27 August 2019 Available online 02 September 2019 0577-9073/ © 2019 The Physical Society of the Republic of China (Taiwan). Published by Elsevier B.V. All rights reserved.
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Fig. 1. Photograph of diammonium fumarate crystals.
2. Materials and methods Diammonium fumarate crystal was obtained from slow evaporation method. Ammonium carbonate and fumaric acid were mixed in an equimolar ratio of 1:1 in double distilled water and the solution was stirred well using magnetic stirrer for about 3 h to obtain a homogeneous saturated solution. This saturated solution was filtered using Whatmann filter paper. Then the filtered solution was covered using polythene paper and few holes were made for solvent evaporation. After 40 days colorless crystals were harvested. Fig. 1, shows the photograph of grown diammonium fumarate crystals. The reaction scheme of the grown crystal is given below.
3. Results and discussion 3.1. Single crystal XRD analysis Nonius CAD4/MACH 3 single crystal X-ray diffractometer with MoKα (λ = 0.71069 Å) radiation was used to analyses the grown crystal. This analysis reveals the lattice parameters of the grown crystal. The grown crystal belongs to monoclinic system with centrosymmetric space group P21/c. The comparison of lattice parameters obtained from single crystal XRD with reported values [13] are given in Table 1. 3.2. Optical analysis λ35 model Perkin Elmer double beam UV-Vis-NIR spectrometer in the range from 190 nm to 1100 nm was employed to study the transparency range of grown crystal. The transmission spectrum of the grown crystal is shown in Fig. 2. As seen from the transmittance spectrum, the lower cut off wavelength occurs at 300 m, and there is no absorption of light seen in the visible and near infra red regions. This good transmittance from 300 nm to 1100 nm makes the crystal suitable for NLO and optoelectronic applications. 3.3. Vibrational spectral analyses The KBr pellet technique is employed to record FTIR spectrum using a SPECTROMRX1 FTIR spectrometer and the BRUKER RFS 27 spectrometer was employed to record FT Raman spectrum of the grown crystal. The FTIR and FT Raman spectra of diammonium Table 1 Lattice parameters of diammonium fumarate crystal. Lattice parameters
Observed values
Reported values [13]
a(Å) b(Å) c(Å) α (°) β(°) γ(°)
3.773(1) 8.10(3) 11.65(5) 90 92.57(9) 90
3.733(3) 8.009(2) 11.508(2) 90 92.46(3) 90
105
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Fig. 2. UV-Vis-NIR spectrum of diammonium fumarate crystal.
fumarate crystal are shown in Figs. 3 and 4 respectively. The absorption band in the region from 3300-3000 cm−1 attributed to the stretching vibration of NH4+ group [14]. The absorption band at 3174 cm−1 in IR is assigned to NH4+asymmetric stretching vibration. The NH4+ group symmetric stretching was observed at 3084 cm−1 in IR and 3029 cm−1 in Raman spectra. The asymmetric deformation of NH4+ group was observed at 1699 cm−1 in IR and 1655 cm−1 in Raman spectra respectively. The IR peaks at 1577 cm−1 and 1424 cm−1 are due to asymmetric and symmetric vibration of caboxylate group. Its corresponding Raman peak are observed at 1555cm−1 and 1408 cm−1. The ammonium cations (NH4+) are linked to the carboxylate group of fumarate anion forming bidentate bond. The bidentate bond was formed when the difference between the wavenumbers is ΔV<200 cm−1 (asymmetric and symmetric vibration of COO¯ group) [15–17]. The bidentate bond formed between ammonium and fumaric acid confirms the formation of diammonium fumarate crystal. The asymmetric and symmetric stretching of CeC vibrations are observed at 1201 cm−1 and 977 cm−1 in IR and 1274 cm−1 and 979 cm−1 in Raman respectively. The vibrational assignments based on the spectra are given in Table 2.
Fig. 3. FTIR spectrum of diammonium fumarate crystal. 106
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Fig. 4. FT Raman spectrum of diammonium fumarate crystal.
Table 2 Observed vibrational wavenumbers and their assignments. Wavenumber cm−1
Assignments
FTIR
FT Raman
3174 3084 2858 1699 1577 1424 1201 977 887
– 3029 – 1655 1555 1408 1274 979 865
NH4+ asymmetric stretching NH4+ symmetric stretching CH stretching NH4+ asymmetric deformation COO¯ asymmetric stretching COO¯ symmetric stretching C-C asymmetric stretching CeC symmetric stretching C = C stretching
3.4. NMR studies The presence of carbon and proton signals were recorded using 1H NMR and 13C NMR spectroscopy. The solvent used here is D2O at room temperature and the instrument model is Bruker 300 MHz (ultrasheild)™ (operated at 300 MHz for 1H NMR and 75 MHz for 13 C NMR). Fig. 5 shows the 1H NMR spectrum of diammonium fumarate crystal. The peak values for 1H NMR and 13C NMR spectra are given in Table 3. The peak observed at δ = 4.686 ppm was due to the solvent D2O. The signal observed at δ = 6.335 ppm was attributed to the CH proton of fumaric acid in diammonium fumarate crystal. In pure fumaric acid (Table 3) the proton signal for CH group was observed at δ = 6.647 ppm. The peak values are shifted towards the upfield. The upfield shift in the value of CH proton was due to the intermolecular interaction between ammonium and fumaric acid. Thus, the absence of COOH proton of fumaric acid, indicates the formation of bond between the fumarate anion and ammonium cation, with the result in formation of diammonium fumarate crystal. The 13C NMR spectrum of diammonium fumarate crystal given in Fig. 6, produces two signals with respect to two carbon atoms present in the crystal. The presence of peak at δ = 173.42 ppm was due to the carbonyl carbon (COOH) and the peak at δ = 134.19 ppm was due to methylidene carbon (CH) of diammonium fumarate crystal. Table 3 gives the value of carbonyl and methylidene carbon of pure fumaric acid. Here also the values are shifted towards the upfield in diammonium fumarate crystal. This upfield shift was due to the bond, formed between ammonium and fumaric acid. 3.5. Thermal analysis Thermal studies were carried out using the instrument NETZSCH SDT Q600 V 8.3 build 101 in nitrogen atmosphere at a heating rate of 20 °C/min in the temperature 30–1000 °C. The TG/DTA curves of diammonium fumarate crystal are given in Fig. 7. The TGA curve reveals that the crystal is stable upto 225 °C. After this temperature, the crystal undergoes complete decomposition. The 107
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Fig. 5. 1H NMR spectrum of diammonium fumarate crystal. Table 3 Chemical shifts in 1H and Spectra
1
H NMR
13
C NMR
13
C NMR spectra of diammonium fumarate crystal. Chemical shift δ (ppm) diammonium fumarate crystal
Fumaric acid
Group Identification
6.335 4.686 173.42 134.19
6.647 177.23 137.95
–CH= D2O –COOH –CH=
endothermic peak at 257 °C in DTA curve represents the melting and decomposition of the compound. This endothermic peak also coincides with the weight loss in the TGA curve. 3.6. Third order nonlinear optical analysis Nd:YAG laser of intensity 5 mW (λ = 532 nm) focussed by a lens of 3.5 cm focal length was employed to record the Z-scan traces of the grown crystal. The Z-scan technique is used to determine the nonlinear optical parameters such as refractive index (n2), absorption co-efficient (β) and third order nonlinear optical susceptibility (χ3). These parameters are calculated from standard formulas available in the literature [18–21] and the results are given in Table 4. When intense laser beam propagates in a crystal, a nonlinear polarization is produced in the crystal which changes the propagation characteristics of the laser beam. The modification in the refractive index of the crystal in response to the applied intense light is known as Kerr effect and is a nonlinear optical effect. The magnitude of nonlinear refractive index (n2) can be measured with closed aperture Z-scan measurement. A positive n2 value is revealed as a pre-focal valley followed by post-focal peak curve and a negative n2 as a pre-focal peak followed by post-focal valley curve. The Kerr induced self-focussing effect gives a positive n2. The self-defocussing effect gives a negative n2. It arises due to the localized absorption of a focussed beam propagating through a crystal. This beam produces a spatial variation of refractive index due to spatial distribution of temperature in the crystal [22,23]. Consequently, it results in phase distortion of the propagating laser beam due to thermal effects. The closed aperture curve of diammonium fumarate crystal is given in Fig. 8. The observed n2 value of diammonium fumarate crystal is −10.31 × 10−8 cm2/W. It reveals the self-defocusing nature of diammonium fumarate crystal. This property makes the crystal to find applications like optical sensors, night vision devices [24]. The nonlinear absorption of the crystal can be found by recording open aperture curve through Z-scan technique. In case of positive nonlinear absorption (reverse saturable absorption), minimum transmittance is observed near the focus (Z = 0) and for 108
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Fig. 6.
13
C NMR spectrum of diammonium fumarate crystal.
Fig. 7. TG/DTA curve of diammonium fumarate crystal.
109
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Table 4 Third order nonlinear optical parameters of diammonium fumarate crystal. Parameters
Values
Nonlinear refractive index (n2) Nonlinear absorption co-efficient (β) Real part of susceptibility (Re χ3) Imaginary part of susceptibility (Im χ3) Third order susceptibility (χ3)
−10.31 × 10−8 cm2/W −0.02 × 10−4 cm/W 9.33 × 10−6 esu 0.12 × 10−6 esu 9.33 × 10−6 esu
Fig. 8. Closed aperture curve of diammonium fumarate crystal.
negative nonlinear absorption (saturable absorption), maximum transmittance is observed near the focus (Z = 0) [25]. Saturable absorption means the absorption of light decreases with increasing intensity. At high intensity, atoms in the ground level become excited into an upper energy level at such a rate that there is not enough time for the atoms to come back to the ground level before it gets depleted and the absorption subsequently saturates. The open aperture curve of diammonium fumarate crystal (Fig. 9) shows
Fig. 9. Open aperture curve of diammonium fumarate crystal. 110
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
Table 5 (χ3) values of diammonium fumarate with some third order nonlinear optical crystal. Crystal name
Third order susceptibility (χ3) esu
References
Diammonium fumarate 4BPTS LiRbB4O7 LiKB4O7 2APTC KDP
9.33 × 10−6 4.162 × 10−8 2.719 × 10−7 4.85 × 10−9 9.6963 × 10−12 1.5 × 10−14
Present work [27] [28] [29] [30] [31]
saturable absorption property. This is an important optical property and it can be employed in Q switching to generate short optical pulses [26]. The third order susceptibility value depends on the hydrogen bonding interaction between the cations and anions present in the crystal. In the title crystal structure, the ammonium cations and fumarate anions are connected by (NeH…O) hydrogen bond. This hydrogen bonding interaction is responsible for the molecular polarization resulting in higher third order nonlinear susceptibility value. The susceptibility value of diammonium fumarate crystal is compared with the susceptibility values of some reported nonlinear optical crystals and are presented in Table 5. 4. Conclusion Diammonium fumarate crystals have been grown using an aqueous solution by solvent evaporation solution growth method. The single crystal X-ray diffraction analysis determines the lattice parameter and confirms that the crystal system is monoclinic. The lower cut off wavelength was observed at 300 nm. The presence of various functional groups were identified from FTIR and FTRaman spectral analyses. The 1H and 13C NMR reveals the molecular structure of grown crystal. The thermal behavior was investigated by TG/DTA experiment, which indicated that the crystal is thermally stable upto 225 °C. The values such as χ3 = 9.33 × 10−6esu and n2 = −10.31 × 10−8 cm2/W were calculated from Z-scan technique and reveals that the crystal is suitable for third harmonic generation. Conflicts of interest None. Acknowledgment The authors thank the sophisticated analytical instruments facility (SAIF), Indian Institute of Technology (IITM), Chennai for providing single crystal XRD and FT Raman spectrum and gratefully acknowledge the Instrumentation centre of St. Joseph's College, Trichy for recording FTIR and UV-Vis-NIR spectra. The authors wish to thank CECRI, Karaikudi, for TG/DTA studies and SASTRA university, Thanjavur for NMR studies. The authors are also grateful to Dr. G. Vinitha, VIT, Chennai for recording the Z-scan curves. References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23]
P.R. Newman, L.F. Warren, P. Cunningham, T.Y. Chang, D.E. Cooper, G.L. Burdge, Mater. Res. Soc. Symp. Proc. 173 (1990) 557–561. H.O. Marcy, L.F. Warren, M.S. Webb, C.A. Ebbers, S.P. Velsko, G.C. Kennedy, Appl. Opt. 31 (1992) 5051–5060. U. Ramabadran, D.E. Zelmon, G.C. Kennedy, Appl. Phys. Lett. 60 (1992) 2589–2592. R.A. Laudise (Ed.), The Growth of Single Crystals, Prentice Hall, Eagle wood Cliffs New Jersy, 1970. R.A. Laudise, R. Ueda, J.B. Mullin (Eds.), Crystal Growth an Characterization, North–Holland publishing Co., 1975. G. Xing, M. Jiang, Z. Shao, D. Xu, Chin. J. Lasers 14 (1987) 357–360. R. Mohan Kumar, D. Rajan Babu, D. Jayaraman, R. Jayavel, K. Kitamura, J. Cryst. Growth 275 (2005) 1935–1939. H.Q. Sun, D.R. Yuan, X.Q. Wang, X.F. Cheng, C.R. Gong, M. Zhou, H.Y. Xu, X.C. We, C.N. Luan, D.Y. Pan, Z.F. Li, X.Z. Shi, Cryst. Res. Technol. 40 (2005) 882–886. N. Karthick, R. Sankar, R. Jayavel, S. Pandi, J. Cryst. Growth 312 (2009) 114–119. R. Aarthi, P. Umarani, C. Ramachandra Raja, Appl. Phys. A. 124 (2018) 498–504. Redrothu Hanumantharao, S. Kalainathan, G. Bhagavannarayana, U. Madhusoodanan, Spectrochim. Acta Part A. 103 (2013) 388–399. D. Joseph Daniel, P. Ramasamy, Mater. Res. Bull. 47 (2012) 708–713. Hiroyuki Hosomi, Yoshikatsu Ito, Shigeru Ohba, Acta Cryst. C 54 (1998) 142–145. G. Socrates, Infrared, Raman Characteristic Group Frequencies, Tables and Charts, 3rd edn, Wiley, Chichester, 2001. K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, th ed, Wiley, New York, 1997, p. 60. E.Y. Ionashiro, F.J. Caires, A.B. Siqueira, L.S. Lima, C.T. Carvalho, J. Therm. Anal. Calorim. 108 (2012) 1183–1188. W. Lewandowski, H. Baranska, J. Raman Spectrosc. 17 (1986) 17–22. P. Karuppasamy, V. Sivasubramani, M. Senthil Pandian, P. Ramasamy, RSC Adv. 6 (2016) 33159–33169. T.C.S. Girisun, S. Dhanuskodi and G. Vinitha, Mater. Chem. Phys., 129(2011) 9–14. T. Thilak, M.B. Ahamed, G. Vinitha, Int. J. Light Electron Opt. 124 (2013) 4716–4720. A.N. Vigneshwaran, P. Umarani, C. Ramachandra Raja, J. Mater. Sci. Mater. Electron. 28 (2017) 11430–11438. E.L. Buckland, R.W. Boyd, Opt. Lett. 21 (15) (1996) 1117–1121. N. Sivakumar, G. Anbalagan, Opt. Mater. 60 (2016) 533–540.
111
Chinese Journal of Physics 61 (2019) 104–112
N. Kalaimani, et al.
[24] [25] [26] [27] [28] [29] [30] [31]
T.H. Wei, D.J. Hagan, M.J. Sence, E.W. Van Stryland, J.W. Perry, D.R. Coulter, Appl. Phys. B 54 (1992) 46–51. S. Dhanuskodi, T.C. Sabari Girisun, S. Vinitha Curr, Appl. Phys. 11 (2011) 860–864. Sze Y. Set, Hiroshi Yaguchi, Yuichi Tanaka, Mark Jablonski, J. Lightwave Technol. 22 (1) (2004) 51. K. Sivakumar, Saravana Kumar, R. Mohan Kumar, R. Kanagadurai, S. Sagadevan, Mat. Res. 19 (2016) 937–941. M. Sukumar, R. Ramesh Babu, K. Ramamurthi, Solid State Sci. 51 (2016) 8–12. M. Sukumar, K. Ramamurthi and, R. Ramesh Babu, Appl. Phys. B. 121 (2015) 369–373. M.K. Kumar, S. Sudhahar, A. Silambarasan, B.M. Sornamurthy, R.M. Kumar, Int. J. Light Electron Opt. 125 (2014) 751–755. A.N. Vigneshwaran, P. Paramasivam, C. Ramachandra Raja, Mater Lett. 178 (2016) 100–103.
112