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Triggering of ferromagnetism by amine functionalization on ZnO:Mn films grown by RF magnetron sputtering

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Abstract

The enhanced saturation magnetization in Mn-doped ZnO (ZnO:Mn) films by Amine functionalization has been reported here. First, Mn (5 mol%, 10 mol%, and 15 mol%)-doped ZnO thin films were grown by radio-frequency (RF) magnetron sputtering which are further functionalized using trioctylamine (Amine) by spin coating. XRD pattern confirms the (002) plane of hexagonal wurtzite structure and showed that there is no significant change in the peak position after Amine functionalization. The presence of green band (GB) emission at 2.4 eV and blue band (BB) at 2.8 eV by photoluminescence study confirms the existence of oxygen vacancies in the film. Further, after Amine functionalization, quenching of green band and blue band emissions were observed. The presence of elements in the films, in particular, organic ligand, N was confirmed by XPS analysis. The VSM measurement confirms that all the grown ZnO:Mn films exhibit ferromagnetic behavior. Further, the Amine functionalization enhances the saturation magnetization (Ms) due to hybridization between 4s and 2p orbital which actually makes Zn–N and N–O bonds and induces the magnetization in the system.

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References

  1. G.A. Prinz, Magnetoelectronics. Science 282(5394), 1660–1663 (1998)

    Article  CAS  Google Scholar 

  2. J. Alaria, M. Venkatesan, J.M.D. Coey, Magnetism of ZnO nanoparticles doped with 3 d cations prepared by a solvothermal method. J. Appl. Phys. 103(7), 07D123 (2008)

    Article  Google Scholar 

  3. Z. Yang, J.L. Liu, M. Biasini, W.P. Beyermann, Electron concentration dependent magnetization and magnetic anisotropy in ZnO:Mn thin films. Appl. Phys. Lett. 92(4), 042111 (2008)

    Article  Google Scholar 

  4. R. Karmakar, S.K. Neogi, N. Midya, A. Banerjee, S. Bandyopadhyay, Magnetic properties of Mn doped ZnO: the role of synthesis route. J. Mater. Sci.: Mater. Electron. 27(6), 6371–6381 (2016)

    CAS  Google Scholar 

  5. S.A. Ahmed, Structural, optical, and magnetic properties of Mn-doped ZnO samples. Results Phys. 7, 604–610 (2017)

    Article  Google Scholar 

  6. H.Y. Xu, Y.C. Liu, C.S. Xu, Y.X. Liu, C.L. Shao, R. Mu, Structural, optical, and magnetic properties of Mn-doped ZnO thin film. J. Chem. Phys. 124(7), 074707 (2006)

    Article  CAS  Google Scholar 

  7. M. Venkatesan, C.B. Fitzgerald, J.G. Lunney, J.M.D. Coey, Anisotropic ferromagnetism in substituted zinc oxide. Phys. Rev. Lett. 93(17), 177206 (2004)

    Article  CAS  Google Scholar 

  8. G.J. Huang, J.B. Wang, X.L. Zhong, G.C. Zhou, H.L. Yan, Synthesis, structure, and room-temperature ferromagnetism of Ni-doped ZnO nanoparticles. J. Mater. Sci. 42(15), 6464–6468 (2007)

    Article  CAS  Google Scholar 

  9. C. Knies, M.T. Elm, P.J. Klar, J. Stehr, D.M. Hofmann, N. Romanov, T. Kammermeier, A. Ney, Nonferromagnetic nanocrystalline ZnO:Co thin films doped with Zn interstitials. J. Appl. Phys. 105(7), 073918 (2009)

    Article  Google Scholar 

  10. T. Dietl, H. Ohno, F. Matsukura, J. Cibert, E.D. Ferrand, Zener model description of ferromagnetism in zinc-blende magnetic semiconductors. Science 287(5455), 1019–1022 (2000)

    Article  CAS  Google Scholar 

  11. Q. Wang, Q. Sun, P. Jena, Ligand induced ferromagnetism in ZnO nanostructures. J. Chem. Phys. 129(16), 164714 (2008)

    Article  Google Scholar 

  12. G. Jayalakshmi, N. Gopalakrishnan, T. Balasubramanian, Activation of room temperature ferromagnetism in ZnO films by surface functionalization with thiol and amine. J. Alloys Compd. 551, 667–671 (2013)

    Article  CAS  Google Scholar 

  13. M.B. Bouzouraa, A.E. Naciri, A. Moadhen, H. Rinnert, M. Guendouz, Y. Battie, A. Chaillou, M.A. Zaibi, M. Oueslati, Effects of silicon porosity on physical properties of ZnO films. Mater. Chem. Phys. 175, 233–240 (2016)

    Article  CAS  Google Scholar 

  14. S. Nallusamy, G. Nammalvar, Enhancement of ferromagnetism in Thiol functionalized ZnO:Mn thin films. Mater. Res. Express 5(2), 026418 (2018)

    Article  Google Scholar 

  15. S.-Z. Deng et al., Thiol-capped ZnO nanowire/nanotube arrays with tunable magnetic properties at room temperature. ACS Nano 4(1), 495–505 (2009)

    Article  Google Scholar 

  16. K.R. Kittilstved, D.R. Gamelin, Activation of High-Tc ferromagnetism in Mn2+-doped ZnO using amines. J. Am. Chem. Soc. 127(15), 5292–5293 (2005)

    Article  CAS  Google Scholar 

  17. Q.Q. Gao, Q.X. Yu, K. Yuan, X.N. Fu, B. Chen, C.X. Zhu, H. Zhu, Influence of annealing atmosphere on room temperature ferromagnetism of Mn-doped ZnO nanoparticles. Appl. Surf. Sci. 264, 7–10 (2013)

    Article  CAS  Google Scholar 

  18. S. Nallusamy, G. Nammalvar, Fabrication of thiol-functionalized Ni-doped ZnO thin films for room-temperature ferromagnetism. IEEE Magn. Lett. 8, 1–4 (2017)

    Article  Google Scholar 

  19. W. Yu, L.H. Yang, X.Y. Teng, J.C. Zhang, Z.C. Zhang, L. Zhang, G.S. Fu, Influence of structure characteristics on room temperature ferromagnetism of Ni-doped ZnO thin films. J. Appl. Phys. 103(9), 093901 (2008)

    Article  Google Scholar 

  20. Q. Shao, C. Wang, J.A. Zapien, C.W. Leung, A. Ruotolo, Ferromagnetism in Ti-doped ZnO thin films. J. Appl. Phys. 117(17), 17B908 (2015)

    Article  Google Scholar 

  21. D.R. Jung, J. Kim, B. Park, Surface-passivation effects on the photoluminescence enhancement in ZnS:Mn nanoparticles by ultraviolet irradiation with oxygen bubbling. Appl. Phys. Lett. 96(21), 211908 (2010)

    Article  Google Scholar 

  22. J. Chaboy, R. Boada, C. Piquer, M.A. Laguna-Marco, M. García-Hernández, N. Carmona, J. Llopis, M.L. Ruíz-González, J. González-Calbet, J.F. Fernández, M.A. García, Evidence of intrinsic magnetism in capped ZnO nanoparticles. Phys. Rev. B 82(6), 064411 (2010)

    Article  Google Scholar 

  23. F. Oliveira, M.F. Cerqueira, M.I. Vasilevskiy, T. Viseu, J.A. De Campos, A.G. Rolo, J.S. Martins, N.A. Sobolev, E. Alves, Room temperature paramagnetism of ZnO:Mn films grown by RF-sputtering. Thin Solid Films 518(16), 4612–4614 (2010)

    Article  CAS  Google Scholar 

  24. X.F. Liu, N. Yang, H. Li, R.H. Yu, W. Wei, Magnetism and photoluminescence of Mn:ZnO/Mn:ZnS heterostructures. Mater. Lett. 92, 405–408 (2013)

    Article  CAS  Google Scholar 

  25. N. Gopalakrishnan, L. Balakrishnan, B. Srimathy, M.S. Kumar, T. Balasubramanian, Vacancy-mediated room-temperature ferromagnetism in Zn1xMnxO thin films. Phys. Status Solidi (a) 207(9), 2180–2184 (2010)

    Article  CAS  Google Scholar 

  26. N. Gopalakrishnan, L. Balakrishnan, A. Brindha, G. Jayalakshmi, Thickness and substrate orientation dependence of ferromagnetism in ZnO:Mn thin films. Cryst. Res. Technol. 47(1), 45–52 (2012)

    Article  CAS  Google Scholar 

  27. S. Nallusamy, G. Nammalvar, Enhancing the saturation magnetization in Ni doped ZnO thin films by TOPO functionalization. J. Magn. Magn. Mater. 485, 297–303 (2019)

    Article  CAS  Google Scholar 

  28. D.L. Hou, R.B. Zhao, Y.Y. Wei, C.M. Zhen, C.F. Pan, G.D. Tang, Room temperature ferromagnetism in Ni-doped ZnO films. Curr. Appl. Phys. 10(1), 124–128 (2010)

    Article  Google Scholar 

  29. N. Gopalakrishnan, L. Balakrishnan, B. Srimathy, M.S. Kumar, T. Balasubramanian, Vacancy-mediated room-temperature ferromagnetism in Zn1−xMnxO thin films. Phys. Status Solidi (a) 207(9), 2180–2184 (2010)

    Article  CAS  Google Scholar 

  30. X. Liu, F. Lin, L. Sun, W. Cheng, X. Ma, W. Shi, Doping concentration dependence of room-temperature ferromagnetism for Ni-doped ZnO thin films prepared by pulsed-laser deposition. Appl. Phys. Lett. 88(6), 062508 (2006)

    Article  Google Scholar 

  31. R. Naeem, M.A. Ehsan, R. Yahya, M. Sohail, H. Khaledi, M. Mazhar, Fabrication of pristine Mn2O3 and Ag–Mn2O3 composite thin films by AACVD for photo electrochemical water splitting. Dalton Trans. 45(38), 14928–14939 (2016)

    Article  CAS  Google Scholar 

  32. M.R. Kesama, B.K. Yun, S.R. Dugasani, J.H. Jung, S.H. Park, Enhancing the electrical, optical, and magnetic characteristics of DNA thin films through Mn2+ fortification. Colloids Surf. B 167, 197–205 (2018)

    Article  CAS  Google Scholar 

  33. R. Wang, C. Xu, J. Sun, L. Gao, Three-dimensional Fe2O3 nanocubes/nitrogen-doped graphene aerogels: nucleation mechanism and lithium storage properties. Sci. Rep. 4(1), 1–7 (2014)

    Google Scholar 

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Acknowledgements

This work is supported by the Council of Scientific and Industrial Research (CSIR), Govt. of India, vide Project No. 03(1305)/13/EMR-II with entitle “Doping and capping in the ZnO thin films for Spintronics Applications” and is gratefully acknowledged. One of the authors, Sivanantham Nallusamy acknowledges, CSIR, Govt. of India for awarding the senior research fellowship (SRF).

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Nallusamy, S., Nammalvar, G. Triggering of ferromagnetism by amine functionalization on ZnO:Mn films grown by RF magnetron sputtering. J Mater Sci: Mater Electron 32, 1623–1630 (2021). https://doi.org/10.1007/s10854-020-04931-1

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