Skip to main content

Advertisement

SpringerLink
Log in

Studies on the growth, structural, spectral and third order nonlinear optical properties of ethylammonium hydrogen oxalate hemihydrate crystal

  • Published:
Journal of Materials Science: Materials in Electronics Aims and scope Submit manuscript

Abstract

Growth and characterization of nonlinear optical (NLO) organic crystal of ethylammonium hydrogen oxalate hemihydrate (EHOH) grown using ethylamine and oxalic acid dihydrate by slow evaporation technique is reported in this paper. The unit cell parameters and space group have been determined. The sharp Bragg’s peak in Powder X-ray diffraction (PXRD) analysis identifies the crystalline nature. Optical parameters, like lower cut off wavelength 224 nm, optical band gap Eg= 5.46 eV are calculated from the UV-Vis-NIR spectrum. The transmittance of EHOH crystal has been used to calculate the extinction coefficient (k) and refractive index (n) as functions of wavelength. FT-IR spectrum reveals the existence of the functional groups. The molecular structure has been established by nuclear magnetic resonance (NMR) spectral technique. The third order nonlinear optical parameters such as absorption coefficient (β), nonlinear refractive index (n2) are also determined using Z-scan technique. The crystal exhibits saturable absorption and self-defocusing effects. The third order NLO susceptibility (χ3) value is found to be 1.1324 × 10− 7 esu. Presence of N–H…O and O–H…O hydrogen bonds in the molecular structure is the reason for the enhanced χ3 value. The Photoluminescence (PL) spectrum shows the emission wavelengths at 229 nm, 248 and 260 nm and excitation energy values are 5.41 eV, 5 eV and 4.76 eV respectively.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

Data availability

All data are presented in the manuscript.

References

  1. D.S. Chemla, J. Zyss, Nonlinear optical properties of organic molecules and crystals (Academic press, New York, 1987)

    Google Scholar 

  2. B. Dziuk, B. Zarychta, K. Ejsmont, Allylammonium hydrogen oxalate hemihydrate. Acta Cryst. E 70, o852 (2014)

    CAS  Google Scholar 

  3. Krzysztof, Ejsmont, Diethylammonium hydrogen oxalate. Acta Cryst. E 63, o107–o109 (2007)

    Google Scholar 

  4. W. Diallo, N. Gueye, A. Crochet, L. Plasseraud, H. Cattey, Crystal structure of dimethylammonium hydrogen oxalate hemi (oxalic acid). Acta Crystall. E 71(5), 473–475 (2015)

    Article  CAS  Google Scholar 

  5. K. Ejsmont, Ethyldimethylammonium oxalate. Acta Cryst. E 62, o5852–o5854 (2006)

    Article  CAS  Google Scholar 

  6. J.C. Barnes, Benzylammonium hydrogen oxalate hemihydrate. Acta Cryst. E. 59, o931–o933 (2003)

    Article  CAS  Google Scholar 

  7. B. Blazej Dziuk, Zarychta, K. Ejsmont, Crystal structure of isobutylammonium hydrogen oxalate hemihydrate. Acta Cryst. E 70, o1175 (2014)

    Google Scholar 

  8. Krzysztof Ejsmont, J. Zaleski, Bis(tert-butylammonium) oxalate. Acta Cryst. E 62, o2512–o2513 (2006)

    Google Scholar 

  9. G. Bhagavannarayana, R.V. Ananthamurthy, G.C. Budakoti, B. Kumar, K.S. Bartwal, A study of the effect of annealing on Fe-doped LiNbO3 by HRXRD, XRT and FT-IR. J. Appl. Cryst. 38, 768–771 (2005)

    Article  CAS  Google Scholar 

  10. R.K. Choubey, P. Sen, S. Kar, G. Bhagavannarayana, K.S. Bartwal, Effect of codoping on crystalline perfection of mg:cr:LiNbO3 crystals. Solid State Commun. 140, 120–124 (2006)

    Article  CAS  Google Scholar 

  11. S. Kar, R.K. Choubey, P. Sen, G. Bhagavannarayana, K.S. Bartwal, Studies on codoping behavior of nd:mg:LiNbO3 crystals. Phys. B 393, 37–42 (2007)

    Article  CAS  Google Scholar 

  12. K. Ejsmont, J. Zaleski, Ethylammonium hydrogen oxalate hemihydrate. Acta Cryst. E 62, o3879–o3880 (2006)

    CAS  Google Scholar 

  13. A. Arunkumar, P. Ramasamy, Growth and characterization of ammonium acid phthalate single crystals. Opt. Mater. 35, 1151–1156 (2013)

    Article  CAS  Google Scholar 

  14. K. Sudhakar, P. Arulmozhichelvan, T. Arumanayagam, P. Murugakoothan, Unveiling photophysical-chemical properties of ethylenediamine ditartrate dihydrate acentric single crystal: a proficient material for nonlinear optical application. J. Mater. Sci: Mater. Electron. 30, 11257–11268 (2019)

    CAS  Google Scholar 

  15. P. Karuppasamy, T. Kamalesh, K. Anitha, S. Abdul Kalam, M.S. Pandian, P. Ramasamy, S. Varma, S. Venugopal Rao, Synthesis, crystal growth, structure and characterization of a novel third order nonlinear optical organic single crystal: 2-Amino 4,6-dimethyl pyrimidine 4-nitrophenol. Opt. Mater. 84, 475–489 (2018)

    Article  CAS  Google Scholar 

  16. P. Karuppasamy, M.S. Pandian, P. Ramasamy, S. Varma, Crystal growth, structural, optical, thermal, mechanical, laser damage threshold and electrical properties of triphenylphosphine oxide 4-nitrophenol (TP4N) single crystals for nonlinear optical applications. Opt. Mater. 79, 152–171 (2018)

    Article  CAS  Google Scholar 

  17. R. Durgadevi, A. Suvitha, T. Arumanayagam, Growth, optical, electrical properties and DFT studies on piperidinium 4-nitrophenolate NLO single crystal in acetone. J. Cryst. Growth. 582, 126512–126520 (2022)

    Article  CAS  Google Scholar 

  18. R. Durgadevi, A. Steephen, T. Arumanayagam, Growth, thermal, linear and nonlinear optical properties of a novel second order nonlinear optical crystal: urotropine p-nitrophenol. J. Mater. Sci: Mater. Electron. 31, 18683–18691 (2020)

    Google Scholar 

  19. P. Prabu, B. Vijayabhaskaran, A. Antony Joseph, R. Aarthi, R. Raja, Structural, spectral and nonlinear optical analysis of aquachloro (l-prolinato)copper(II) crystal. J. Mater. Sci: Mater. Electron. 30, 5074–5080 (2019)

    CAS  Google Scholar 

  20. M. Prakash, D. Geetha, M. Lydia Caroline, Synthesis, structural, optical, thermal and dielectric studies on new organic nonlinear optical crystal by solution growth technique. Spectrochim. Acta A 107, 16–23 (2013)

    Article  CAS  Google Scholar 

  21. R. Aarthi, C. Ramachandra Raja, Spectral and optical characterization of the new semi-organic crystal: 4-methylbenzylammonium chloride hemihydrate, to establish protonation and the effect of resultant hydrogen bonding. Bull. Mater. Sci. 42, 1–6 (2019)

    Article  CAS  Google Scholar 

  22. C. Ramachandra Raja, G. Gokila, A. Antony Joseph, Growth and spectroscopic characterization of a new organic nonlinear optical crystal: L-Alaninium succinate. Spectrochim. Acta A 72, 753–756 (2009)

    Article  Google Scholar 

  23. G. Gokila, R. Aarthi, C. Ramachandra Raja, Structural, spectral and nonlinear optical analysis of Bis(2-methyllactato)borate tetrahydrate: a new nonlinear optical crystal for laser applications. Optik. 207, 1–7 (2020)

    Google Scholar 

  24. S. Krishnan, C. Justin Raj, R. Robert, A. Ramanand, Jerome Das, Growth and characterization of succinic acid single crystals. Cryst. Res. Technol. 42, 1087–1090 (2007)

    Article  CAS  Google Scholar 

  25. N. Kalaimani, K. Ramya, R. Aarthi, C. Ramachandra Raja, Growth, structural, optical, spectral and thermal characterization of third order nonlinear optical crystal: diammonium fumarate. Chin. J. Phys. 61, 104–112 (2019)

    Article  Google Scholar 

  26. S. Manivannan, S. Dhanuskodi, Synthesis, crystal growth, structural and optical properties of an organic NLO material. J. Cryst. Growth. 262, 473–478 (2004)

    Article  CAS  Google Scholar 

  27. K. Ramya, N.T. Saraswathi, C. RamachandraRaja, Growth and characterization of an organic nonlinear optical material: L-Histidine malonate. Opt. Laser Technol. 84, 102–106 (2016)

    Article  CAS  Google Scholar 

  28. G. Gokila, R. Aarthi, C. Ramachandra Raja, Elucidation of the properties of lithium bis (2-methyllactato) borate monohydrate crystal for laser applications. J. Mater. Sci: Mater. Electron. 31, 6956–6962 (2020)

    CAS  Google Scholar 

  29. K. Ramya, N.T. Saraswathi, C. Ramachandra, Raja, Studies on the growth, spectral, thermal, and optical properties of l-arginine adipate crystal. Optik. 127, 2495–2499 (2016)

    Article  CAS  Google Scholar 

  30. N. Kalaimani, R. Aarthi, C. Ramachandra Raja, Structural, spectral, thermal and nonlinear optical analysis of potassium tartrate hemihydrate crystal. J. Mater. Sci: Mater. Electron. 30, 7974–7980 (2019)

    CAS  Google Scholar 

  31. https://sdbs.dp.aist.go.jp/sdbs/cgi-bin/directframe-top.cgi

  32. R. Aarthi, C. Ramachandra Raja, Probing the structure-property relationship of a new semiorganic nonlinear optical crystal:catena-poly[bis(4-methylbenzylammonium)[[dibromidocadmate (II)]-di-l-bromido]]. J. Mater. Sci: Mater. Electron. 30, 8698–8704 (2019)

    CAS  Google Scholar 

  33. B. Berglund, W. Robert, Vaughan, Correlations between proton chemical shift tensors, deuterium quadrupole couplings, and bond distances for hydrogen bonds in solids. J. Chem. Phys. 73, 2037–2043 (1980)

    Article  CAS  Google Scholar 

  34. D. Vojta, M. Vrankić, M. Bertmer, G.E. Schaumann, Dehydration of α-oxalic acid dihydrate: Structural, spectroscopic and thermal study with implications on the disruption of water molecular bridges in soil organic matter. Thermochim. Acta 643, 73–82 (2016)

    Article  CAS  Google Scholar 

  35. S.K. Patra, B.K. Dadhich, B. Bhushan, Ravi Kant Choubey and Amiya Priyam, nonlinear absorption and refraction of highly monodisperse and luminescent ZnTe Quantum Dots and their self-assembled nanostructures: implications for Optoelectronic Devices. ACS Omega. 6, 31375–31383 (2021)

    Article  CAS  Google Scholar 

  36. B.K. Dadhich, I. Kumar, R.K. Choubey, B. Bhushan, A. Priyam, Shape and size dependent nonlinear refraction and absorption in citrate-stabilized, near-IR plasmonic silver nanopyramids. Photochem. Photobiol. Sci. 16, 1556–1562 (2017)

    Article  CAS  Google Scholar 

  37. S. Medhekar, R. Kumar, S. Mukherjee, R.K. Choubey, Study of Nonlinear Refraction of Organic Dye by Z-scan Technique Using He–Ne Laser, AIP Conference Proceedings 1512, 470–471 (2013)

  38. R.K. Choubey, R. Trivedi, M. Das, P.K. Sen, P. Sen, S. Kar, K.S. Bartwal, R.A. Ganeev, Growth and study of nonlinear refraction and absorption in mg doped LiNbO3 single crystals. J. Cryst. Growth. 311, 2597–2601 (2009)

    Article  CAS  Google Scholar 

  39. R.K. Choubey, S. Medhekar, R. Kumar, S. Mukherjee, S. Kumar, Study of nonlinear optical properties of organic dye by Z-scan technique using He–Ne laser. J. Mater. Sci: Mater. Electron. 25, 1410–1415 (2014)

    CAS  Google Scholar 

  40. L. Chandra, J. Chandrasekaran, K. Perumal, B. Babu, Third order nonlinear optical and electrical properties of new 2-aminopyridinium 2-cholro 4-nitrobenzoate single crystals. Optik. 127, 3206–3210 (2016)

    Article  CAS  Google Scholar 

  41. P.K. Sivakumar, S. Kumar, R.M. Kumar, R. Kanagadurai, S. Sagadevan, Studies on growth, Spectral, Thermal, Mechanical and Optical Properties 4-Bromoanilinium 4-Methylbenzenesulfonate crystal: a third Order Nonlinear Optical Material. Mater. Res. 19, 937–941 (2016)

    Article  CAS  Google Scholar 

  42. B. Thirumalaiselvam, R. Kanagadurai, D. Jayaraman, V. Natarajan, X.R.D. Growth, Optical absorption spectrum, FTIR spectroscopy and Z-scan study of L-Serine. Int. J. Chem. Tech. Res. 8, 363–369 (2015)

    CAS  Google Scholar 

  43. A. Arunkumar, Ramasamy Bulk single crystals of ammonium acid phthalate grown by the Sankaranarayanan-Ramasamy method for optical limiting applications. J. Cryst. Growth 401, 195–199 (2014)

    Article  CAS  Google Scholar 

  44. M. Sukumar, R. Ramesh Babu, K. Ramamurthi, Linear and third-order nonlinear optical properties of LiKB4O7 single crystals. Appl. Phys. B 121, 369–373 (2015)

    Article  CAS  Google Scholar 

  45. M. Krishna Kumar, S. Sudhahar, P. Pandi, G. Bhagavannarayana, R. Mohan Kumar, Studies of the structural and third-order nonlinear optical properties of solution grown 4-hydroxy-3-methoxy-4′-N′-methylstilbazolium tosylate monohydrate crystals. Opt. Mater. 36, 988–995 (2014)

    Article  CAS  Google Scholar 

  46. P.S. Angel Prabha, P. Selvarajan, V. Bena Jothy, Structural, spectral and NLO studies of zinc lithium sulphate crystals. J. Inf. Comp. Sci. 10, 564–580 (2020)

    Google Scholar 

  47. F.-Q. Li, N. Zong, F.-F. Zhang, J. Yang, F. Yang, Q.-J. Peng, D.-F. Cui, J.-Y. Zhang, X.-Y. Wang, C.-T. Chen, Z.-Y. Xu, Investigation of third-order optical nonlinearity in KBe2BO3F2 crystal by Z-scan. Appl. Phys. B 108, 301–305 (2012)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The scientific supports extended by, Sophisticated Analytical Instruments Facility, Indian Institute of Technology, Chennai for SXRD, St. Joseph’s College, ACIC, Trichy for FT-IR, UV-VIS-NIR analysis and Gandhigram University, Dindigul for FT-NMR is greatly acknowledged. The authors are also grateful to Dr. D. Sastikumar, National Institute of Technology, Trichy for Z-scan analysis. Alagappa University, karaikudi for PXRD and PL analysis is greatly acknowledged.

Funding

The authors declare that no funds, grants, or other support were received during the preparation of this manuscript.

Author information

Authors and Affiliations

  1. Government Arts College (Autonomous), Kumbakonam, 612002, India

    K. Saranya, E. Muhildharani & C. Ramachandra Raja

  2. Affiliated to Bharathidasan University, Tiruchirappalli, India

    K. Saranya, E. Muhildharani & C. Ramachandra Raja

Authors
  1. K. Saranya
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. E. Muhildharani
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. C. Ramachandra Raja
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

All authors contributed to the Literature survey, Material preparation, characterization and interpretation. The first draft of the manuscript was well discussed by all and written by KS. All authors read and approved the final manuscript.

Corresponding author

Correspondence to C. Ramachandra Raja.

Ethics declarations

Conflict of interest

No Conflict of Interest exists between authors. The authors have no relevant financial or non-financial interests to disclose.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Saranya, K., Muhildharani, E. & Ramachandra Raja, C. Studies on the growth, structural, spectral and third order nonlinear optical properties of ethylammonium hydrogen oxalate hemihydrate crystal. J Mater Sci: Mater Electron 34, 1211 (2023). https://doi.org/10.1007/s10854-023-10601-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10854-023-10601-9

Search

Navigation