Journal of Materials Science: Materials in Electronics

, Volume 29, Issue 17, pp 14387–14395 | Cite as

Room temperature ferromagnetism in Ni, Fe and Ag co-doped Cu–ZnO nanoparticles: an experimental and first-principles DFT study

  • O. M. LemineEmail author
  • A. Modwi
  • A. Houas
  • J. H. Dai
  • Y. Song
  • M. Alshammari
  • A. Alanzi
  • R. Alhathlool
  • M. Bououdina


We report an experimental and theoretical investigation on the room temperature ferromagnetism of Zn0.95Cu0.05O and Zn0.94Cu0.05M0.01O (M=Ni, Fe and Ag)Ni nanoparticles synthesized by sol–gel method. X-ray diffraction analysis reveals single hexagonal wurtzite; meanwhile the lattice parameters are found to be sensitive to the ionic radius of the doping elements and the crystallite size varies in the range 22–47 nm. Field emission scanning electron microscopy observations show particles with spherical shape for ZnO and semi-spherical shape for co-doped nanopowders. Magnetic measurements using SQUID reveal room temperature ferromagnetic ordering for doped and co-doped nanopowders with a lower saturation magnetization compared to Cu-doped ZnO. It is found that the co-doping has resulted in weakening the ferromagnetic phase at the expense of the paramagnetic. First-principles calculations indicate that only Cu and Fe codoped ZnO systems own ferromagnetism, which originated from the interaction between Fe-d and O-p electrons. However, all doped systems show positive formation energies indicating they are less stable than undoped ZnO.


  1. 1.
    P. Sharma, A. Gupta, K.V. Rao, F.J. Owens, R. Sharma, R. Ahuja, J.M.O. Guillen, B. Johansson, G.A. Gehring, Ferromagnetism above room temperature in bulk and transparent thin films of Mn-doped ZnO. Nat. Mater. 2, 673 (2003)CrossRefGoogle Scholar
  2. 2.
    T.L. Phan, P. Zhang, D.S. Yang, N.X. Nghia, S.C. Yu, Local structure and paramagnetic properties of Zn1-xMnxO. J. Appl. Phys. 110, 063912 (2011)CrossRefGoogle Scholar
  3. 3.
    M.A. Garcia, M.L. Ruiz Gonzalez, A. Quesada, J.L. Costa-Kramer, J.F. Fernandez, S.J. Khatib, A. Wennberg, A.C. Caballero, M.S. Martın, M. Gonzalez, F. Villegas, J.M. Briones, Gonzalez-Calbet, A. Hernando, Magnetic properties of ZnO nanoparticles. Nano Lett. 7(6), 1489–1494 (2007)CrossRefGoogle Scholar
  4. 4.
    T. Dietl, A ten-year perspective on dilute magnetic semiconductors and oxides. Nat. Mater. 9, 965–974 (2010)CrossRefGoogle Scholar
  5. 5.
    R. Saleh, N.F. Djaja, S.P. Prakoso, The correlation between magnetic and structural properties of nanocrystalline transition metal-doped ZnO particles prepared by the co-precipitation method. J. Alloy. Compd. 546, 48–56 (2013)CrossRefGoogle Scholar
  6. 6.
    M. Bououdina, N. Mamouni, O.M. Lemine, A. Al-Saie, A. Jaafar, B. Ouladdiaf, A. El Kenz, A. Benyoussef, E.K. Hlil, Neutron diffraction study and ab-initio calculations of nanostructured doped ZnO. J. Alloys Compds. 536, 66–72 (2012)CrossRefGoogle Scholar
  7. 7.
    K. Omri, J.El Ghoul, O.M. Lemine, M. Bououdina, B. Zhang, L. ElMir, Magnetic and optical properties of manganese doped ZnO nanoparticles synthesized by sol–gel technique. Superlattices Microstruct. 60, 139–147 (2013)CrossRefGoogle Scholar
  8. 8.
    M. Bououdina, K. Omri, M. El-Hilo, A. El Amiri, O.M. Lemine, A. Alyamani, E.K. Hlil, H. Lassri, L. El Mir, Structural and magnetic properties of Mn-doped ZnO nanocrystals. Physica E 56, 107–112 (2014)CrossRefGoogle Scholar
  9. 9.
    S. Fabbiyola, L.J. Kennedy, J. Judith Vijaya, M. Bououdina, S. Dunn, Structural, optical and magnetic properties of Cu-doped ZnO nanoparticles by co-precipitation method. J. Nanosci. Nanotechnol. 16(9), 9722–9730 (2016)CrossRefGoogle Scholar
  10. 10.
    M. Zhu, Z. Zhang, M. Zhong, M. Tariq, Y. Li, W. Li, H. Jin, K. Skotnicova, Y. Li, Oxygen vacancy induced ferromagnetism in Cu-doped ZnO. Ceram. Int. 43(4), 3166–3170 (2017)CrossRefGoogle Scholar
  11. 11.
    K. Omri, A. Bettaibi, K. Khirouni, L. El Mir, The optoelectronic properties and role of Cu concentration on the structural and electrical properties of Cu doped ZnO nanoparticles. Physica B, 537 (2018) 167–175CrossRefGoogle Scholar
  12. 12.
    A. Modwi, O.M. Lemine, M. Alshammari, A. Houas, Ferromagnetism at room temperature in Zn 0.95 Cu 0.05 O nanoparticles synthesized by sol-gel method. Mater. Lett. 194, 98–101 (2017)CrossRefGoogle Scholar
  13. 13.
    J. Shim, T. Hwang, J. Park, S.J. Han, Y. Jeong, Origin of ferromagnetism in Fe- and Cu-codoped ZnO. Appl. Phys. Lett. 86(8), 082503 (2005)CrossRefGoogle Scholar
  14. 14.
    H.-W. Zhang, Z.-R. Wei, Z.-Q. Li, G.-Y. Dong, Room-temperature ferromagnetism in Fe-doped, Fe- and Cu-codoped ZnO diluted magnetic semiconductor. Mater. Lett. 61, 3605–3607 (2007)CrossRefGoogle Scholar
  15. 15.
    L.B. Duan, G.H. Rao, Y.C. Wang, J. Yu, T. Wang, Ferromagnetism of lightly Co-doped … and magnetic properties of Mn-doped ZnO nanoparticles. J. Appl. Phys. 104(1), 013909 (2008)CrossRefGoogle Scholar
  16. 16.
    H. Liu, J. Yang, Z. Hua, Y. Liu, L. Yang, Y. Zhang, J. Cao, Ferromagnetism in Cu-Doped ZnO nanoparticles at room temperature. Mater. Chem. Phys. 125(3), 656–659 (2011)CrossRefGoogle Scholar
  17. 17.
    J.A. Wibowo, N.F. Djaja, R. Saleh, Cu- and Ni-doping effect on structure and magnetic properties of Fe-doped ZnO nanoparticles. Adv. Mater. Phys. Chem. 3, 48–57 (2013)CrossRefGoogle Scholar
  18. 18.
    A. Modwi, M.A. Abbo, E.A. Hassan, A. Houas, Effect of annealing on physicochemical and photocatalytic activity of Cu5% loading on ZnO synthesized by sol–gel method. J. Mater. Sci. 27(12), 12974–12984 (2016)Google Scholar
  19. 19.
    M. Bououdina, A.A. Dakhel, M. El-Hilo, D.H. Anjum, M. Benali Kanoun, S. Goumri-Said, Revealing a room temperature ferromagnetism in cadmium oxide nanoparticles: an experimental and first-principles study. RSC Adv. 5, 33233–33238 (2015)CrossRefGoogle Scholar
  20. 20.
    S. Azzaza, M. El-Hilo, S. Narayanan, J. Judith Vijaya, N. Mamouni, A. Benyoussef, A. ElKenz, M. Bououdina, Structural, optical and magnetic characterizations of Mn-doped MgO nanoparticles. Mater. Chem. Phys. 143(3), 1500–1507 (2014)CrossRefGoogle Scholar
  21. 21.
    H.L. Liu, J.H. Yang, Y.J. .Zhang, Y.X. Wang, M.B. Wei, D.D. Wang, L.Y. Zhao, J.H. Lang, M. Gao, Ferromagnetism in Cu-doped ZnO nanoparticles at room temperature. J. Mater. Sci. 20, 628–631 (2009)Google Scholar
  22. 22.
    M. Zhu, Z. Zhang, M. Zhong, M. Tariq, Y. Li, W. Li, H. Jin, K. Skotnicova, Y. Li, Oxygen vacancy induced ferromagnetism in Cu-doped ZnO. Ceram. Int. 43(3), 3166–3170 (2016)CrossRefGoogle Scholar
  23. 23.
    W. Liu, X. Tang, Z. Tang, F. Chu, T. Zeng, N. Tang, Role of oxygen defects in magnetic property of Cu doped ZnO. J. Alloy. Compd. 615, 740–744 (2014)CrossRefGoogle Scholar
  24. 24.
    G.H. Mhlongo, K. Shingange, Z.P. Tshabalala, B.P. Dhonge, F.A. Mahmoud, B.W. Mwakikunga, D.E. Motaung, Room temperature ferromagnetism and gas sensing in ZnO nanostructures: influence of intrinsic defects and Mn, Co, Cu doping. Appl. Surf. Sci. 390, 804–815 (2016)CrossRefGoogle Scholar
  25. 25.
    M. Fang, C.M. Tang, Z.W. Liu, Microwave-assisted hydrothermal synthesis of Cu-Doped ZnO single crystal nanoparticles with modified photoluminescence and confirmed ferromagnetism. J. Electron. Mater. 47(2), 1390–1396 (2018)CrossRefGoogle Scholar
  26. 26.
    M. Shatnawi, A.M. Alsmadi, I. Bsoul, B. Salameh, G.A. Alna’washi, F. Al-Dweri, F. El Akkad, Magnetic and optical properties of Co-doped ZnO nanocrystalline particles. J. Alloys Compds. 655, 244–252 (2016)CrossRefGoogle Scholar
  27. 27.
    S. Karamat, R.S. Rawat, P. Lee, T.L. Tan, R.V. Ramanujan, Structural, elemental, optical and magnetic study of Fe doped ZnO and impurity phase formation. Prog. Nat. Sci. 24(2), 142–149 (2014)CrossRefGoogle Scholar
  28. 28.
    M. He, Y.F. Tian, D. Springer, I.A. Putra, G.Z. Xing, E.E.M. Chia, S.A. Cheong, T. Wu, Polaronic transport and magnetism in Ag-doped ZnO. Appl. Phys. Lett. 99, 222511–222513 (2011)CrossRefGoogle Scholar
  29. 29.
    A.K. Rana, Y. Kumar, P. Rajput, S.N. Jha, D. Bhattacharyya, P.M. Shirage, Search for origin of room temperature ferromagnetism properties in Ni-doped ZnO nanostructure. ACS Appl. Mater. Interfaces 9(8), 7691–7700 (2017)CrossRefGoogle Scholar
  30. 30.
    S. Fabbiyola, V. Sailaja, L. John Kennedy, M. Bououdina, J. Judith Vijaya, Optical and magnetic properties of Ni-doped ZnO nanoparticles. J. Alloys Compds. 694, 522–531 (2016)CrossRefGoogle Scholar
  31. 31.
    D.Y. Darshana, A.K. Inamdar, I. Dubenko, N. Ali, S. Mahamuni, Room temperature ferromagnetism and photoluminescence of Fe doped ZnO nanocrystals. J. Phys. Chem. C115(48), 23671–23676 (2011)Google Scholar
  32. 32.
    S. Fabbiyola, L.J. Kennedy, T. Ratnaji, J. Judith Vijaya, M. Bououdina, Effect of Fe-doping on the structural, optical and magnetic properties of ZnO nanostructures synthesised by co-precipitation method. Ceram. Int. 42(1), 1588–1596 (2016)CrossRefGoogle Scholar
  33. 33.
    B.D. Cullity, C.D. Graham, Introduction to Magnetic Materials (Hoboken, Wiley, 2011), pp. 125–127Google Scholar
  34. 34.
    R.N. Bhatt, X. Wan, M.P. Kennett, M. Berciu, Numerical simulations of random spin (and fermionic) models with a wide distribution of energy scales. Comput. Phys. Commun. 147, 684 (2002)CrossRefGoogle Scholar
  35. 35.
    C.-Y. Yang, Y.-H. Lu, W.-H. Lin, M.-H. Lee, Y.-J. Hsu, Y.-C. Tseng, Structural imperfections and attendant localized/itinerant ferromagnetism in ZnO nanoparticles. J. Phys. D 47, 345003 (2014)CrossRefGoogle Scholar
  36. 36.
    P. Ordejón, E. Artacho, J.M. Soler, Self-consistent order-N density-functional calculations for very large systems. Phys. Rev. B 53, R10441 (1996)CrossRefGoogle Scholar
  37. 37.
    N. Troullier, J.L. Martins, Efficient pseudopotentials for plane-wave calculations. II. Operators for fast iterative diagonalization. Phys. Rev. B 43, 1993–2005 (1991)CrossRefGoogle Scholar
  38. 38.
    J.A. Mary, J. Judith Vijaya, J.H. Dai, M. Bououdina, L.J. Kennedy, Y. Song, Experimental and DFT studies of structure, optical and magnetic properties of (Zn 1 – 2xCexCox) O nanopowders. J. Mol. Struct. 1084, 155–164 (2015)CrossRefGoogle Scholar
  39. 39.
    J. Mary, J. Judith Vijaya, M. Bououdina, L.J. Kennedy, J.H. Dai, Y. Song, Effect of Ce and Cu co-doping on the structural, morphological, and optical properties of ZnO nanocrystals and first principle investigation of their stability and magnetic properties. Physica E 66, 209–220 (2015)CrossRefGoogle Scholar

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Authors and Affiliations

  • O. M. Lemine
    • 1
    Email author
  • A. Modwi
    • 2
  • A. Houas
    • 2
  • J. H. Dai
    • 3
  • Y. Song
    • 3
  • M. Alshammari
    • 4
  • A. Alanzi
    • 4
  • R. Alhathlool
    • 1
  • M. Bououdina
    • 5
  1. 1.Department of Physics, College of SciencesAl Imam Mohammad Ibn Saud Islamic University (IMISU)RiyadhSaudi Arabia
  2. 2.Department of Chemistry, College of SciencesAl Imam Mohammad Ibn Saud Islamic University (IMISU)RiyadhSaudi Arabia
  3. 3.School of Materials Science and EngineeringHarbin Institute of Technology at WeihaiWeihaiChina
  4. 4.National Nanotechnology CenterKACSTRiyadhSaudi Arabia
  5. 5.Department of Physics, College of ScienceUniversity of BahrainManamaBahrain

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