Applied Physics A

, 125:816 | Cite as

Synthesis and evaluation of the structural, microstructural, optical and magnetic properties of Zn1−xCoxO thin films grown onto glass substrate by ultrasonic spray pyrolysis

  • Sabrina RoguaiEmail author
  • Abdelkader Djelloul


Ultrasound pyrolysis spray technique is used to prepare single-phase thin films of Zn1−xCoxO (x = 0–22 at.%). The hexagonal wurtzite structure of the films is confirmed by X-ray diffraction with an average crystallite size estimated in the range of 18–30 nm. The compound structure and stoichiometry of the films are further characterized by energy-dispersive spectroscopy (EDAX). The spectrum analysis agreement great chords between the expected and measured Co atomic content in the films indicating an effective doping. The results also reveal a high solubility of Co into ZnO solid solution at about 14 at.%. For the optical proprieties, the bandgap energy decreases due to the presence of high concentrations of localized states in the thin films. The photoluminescence spectra of all the samples exhibited a broad emission in the visible range. In addition, the magnetic properties of Zn1−xCoxO thin films are found to be strongly influenced by Co doping.



The authors would like to thank the National Project Research (PNR) and LASPI2A Laboratory of Khenchela University (Algeria) for their financial support of this research project. The authors thank Dr. Ali Hafs for VSM measurements, Laboratoire de Physicochimie des Matériaux (LPCM), El Tarf University, 36000 El Tarf, Algeria.


  1. 1.
    S. Oktik, Low cost non-vacuum techniques for the preparation of thin/thick films for photovoltaic applications. Prog. Cryst. Growth Charact. 17, 171–240 (1988)CrossRefGoogle Scholar
  2. 2.
    K. Bouzid, A. Djelloul, N. Bouzid, J. Bougdira, Electrical resistivity and photoluminescence of zinc oxide films prepared by ultrasonic spray pyrolysis. Phys. Status Solid. A. 206, 106–115 (2009)ADSCrossRefGoogle Scholar
  3. 3.
    A. Janotti, ChG Van de Walle, Fundamentals of zinc oxide as a semiconductor. Rep. Prog. Phys. 72, 126501 (2009)ADSCrossRefGoogle Scholar
  4. 4.
    K. Ellmer, A. Klein, B. Rech (eds.), Transparent Conductive Zinc Oxide-Basics and Applications in Thin Film Solar Cells. (Series: Springer Series in Materials Science, Berlin, 2008), p. 104Google Scholar
  5. 5.
    H.M. Yang, S. Nie, Preparation and characterization of Co-doped ZnO nanomaterials. Mater. Chem. Phys. 114, 279–282 (2009)CrossRefGoogle Scholar
  6. 6.
    M. Yang, Z.X. Guo, K.H. Qiu, J.P. Long, G.F. Yin, D.G. Guan, S.T. Liu, S.J. Zhou, Synthesis and characterization of Mn-doped ZnO column arrays. Appl. Surf. Sci. 256, 4201–4205 (2010)ADSCrossRefGoogle Scholar
  7. 7.
    H. Saal, T. Bredow, M. Binnewies, Band gap engineering of ZnO via doping with manganese: effect of Mn clustering. Phys. Chem. Chem. Phys. 11, 3201–3209 (2009)CrossRefGoogle Scholar
  8. 8.
    G.M. Kumar, P. Ilanchezhiyan, J. Kawakita, M. Subramanian, R. Jayavel, Magnetic and optical property studies on controlled low-temperature fabricated one-dimensional Cr doped ZnO nanorods. Cryst. Eng. Commun. 12, 1887–1892 (2010)CrossRefGoogle Scholar
  9. 9.
    S. Fabbiyola, L.J. Kennedy, U. Aruldoss, M. Bououdina, A.A. Dakhel, J. Judith Vijaya, Synthesis of Co-doped ZnO nanoparticles via co-precipitation: structural, optical and magnetic properties. Powder Technol. 286, 757–765 (2015)CrossRefGoogle Scholar
  10. 10.
    T. Dietl, H. Ohno, F. Matsukura, J. Cibert, D. Ferrand, Zener model description of ferromagnetism in zinc-blende magnetic semiconductors. Science 287, 1019–1022 (2000)ADSCrossRefGoogle Scholar
  11. 11.
    Y.X. Wang, X. Ding, Y. Cheng, Y.J. Zhang, L.L. Yang, H.L. Liu, H.G. Fan, Y. Liu, J.H. Yang, Properties of Co-doped ZnO films prepared by electrochemical deposition. Cryst. Res. Technol. 44(5), 517–520 (2009)CrossRefGoogle Scholar
  12. 12.
    C. Song, F. Zeng, K.W. Geng, X.B. Wang, Y.X. Shen, F. Pan, The magnetic properties of Co-doped ZnO diluted magnetic insulator films prepared by direct current reactive magnetron co-sputtering. J. Magn. Magn. Mater. 309, 25–30 (2007)ADSCrossRefGoogle Scholar
  13. 13.
    A. Zukova, A. Teiserskis, S. van Dijken, Y.K. Gun’ko, V. Kazlauskiene, Giant moment and magnetic anisotropy in Co-doped ZnO films grown by pulse-injection metal organic chemical vapor deposition. Appl. Phys. Lett. 89, 232503–232505 (2006)ADSCrossRefGoogle Scholar
  14. 14.
    H. Matsui, H. Tabata, Simultaneous control of growth mode and ferromagnetic ordering in Co-doped ZnO layers with Zn polarity. Phys. Rev. B. 75, 014438–014447 (2007)ADSCrossRefGoogle Scholar
  15. 15.
    A. Sivagamasundari, R. Pugaze, S. Chandrasekar, S. Rajagopan, R. Kannan, Absence of free carrier and paramagnetism in cobalt-doped ZnO nanoparticles synthesized at low temperature using citrate sol–gel route. Appl. Nanosci. 3, 383–388 (2013)ADSCrossRefGoogle Scholar
  16. 16.
    G. Iqbal, S. Faisal, S. Khan, D.F. Shams, A. Nadhman, Photo-inactivation and efflux pump inhibition of methicillin resistant Staphylococcus aureus using thiolated cobalt doped ZnO nanoparticles. J. Photochem. Photobiol. B Biol. 192, 141–146 (2019)CrossRefGoogle Scholar
  17. 17.
    H.S. Sindhu, S. D. Kulkarni, R.J. Choudhary, P.D. Babu, B.V. Rajendra, Influence of cobalt doping on structure, optical and magnetic properties of spray pyrolysed nano structured ZnO films. Phys. B: Phys. Condens. Matter. ADSCrossRefGoogle Scholar
  18. 18.
    M. Ivill, S.J. Pearton, S. Rawal, L. Leu, P. Sadik, R. Das, A.F. Hebard, M. Chisholm, J.D. Budai, D.P. Norton, Structure and magnetism of cobalt doped ZnO thin films. New J. Phys. 10, 065002 (2008)ADSCrossRefGoogle Scholar
  19. 19.
    N.K. Tarwal, K.V. Gurav, T. PremKumar, Y.K. Jeong, H.S. Shim, I.Y. Kim, J.H. Kim, J.H. Jang, P.S. Patil, Structure, X-ray photoelectron spectroscopy, and photoluminescence investigations of the spray deposited cobalt doped ZnO thin films. J. Anal. Appl. Pyrolysis 106, 26–32 (2014)CrossRefGoogle Scholar
  20. 20.
    S. Karamat, R.S. Rawat, T.L. Tan, P. Lee, R. Chen, H.D. Sun, W. Zhou, Ferromagnetism in ZnCoO thin films deposited by PLD. Appl. Phys. A 101, 717–722 (2010)ADSCrossRefGoogle Scholar
  21. 21.
    C.B. Fitzgerald, M. Venkatesan, J.G. Lunney, L.S. Dorneles, J.M.D. Coey, Cobalt-doped ZnO—a room temperature dilute magnetic semiconductor. Appl. Surf. Sci. 247, 493–496 (2005)ADSCrossRefGoogle Scholar
  22. 22.
    A. Dinia, G. Schmerber, C. Mény, V. Pierron-Bohnes, E. Beaurepaire, Room- temperature ferromagnetism in Zn1 xCoxOZn1 xCoxO magnetic semiconductors prepared by sputtering. J. Appl. Phys. 97, 123908 (2005)ADSCrossRefGoogle Scholar
  23. 23.
    G. Lawes, A.S. Risbud, A.P. Ramirez, R. Seshadri, Absence of ferromagnetism in Co and Mn substituted polycrystalline ZnO. Phys. Rev. B. 71, 045201 (2005)ADSCrossRefGoogle Scholar
  24. 24.
    J.H. Park, M.G. Kim, H.M. Jang, S. Ryu, Y.M. Kim, Co-metal clustering as the origin of ferromagnetism in Co-doped ZnO thin films. Appl. Phys. Lett. 84, 1338 (2004)ADSCrossRefGoogle Scholar
  25. 25.
    J.H. Kim, H. Kim, D. Kim, Y.E. Ihm, W.K. Choo, Magnetic properties of epitaxially grown semiconducting Zn1 xCoxOZn1 xCoxO thin films by pulsed laser deposition. J. Appl. Phys. 92, 6066 (2002)ADSCrossRefGoogle Scholar
  26. 26.
    Y.Z. Peng, T. Liew, W.D. Song, C.W. An, K.L. Teo, T.C. Chong, Structural and optical properties of Co-doped ZnO thin films. J. Supercond. 18, 97–103 (2005)ADSCrossRefGoogle Scholar
  27. 27.
    R. Siddheswaran, R. Medlín, C.E. Jeyanthi, S.G. Raj, R.V. Mangalaraja, Structural, morphological, optical and magnetic properties of RF sputtered Co doped ZnO diluted magnetic semiconductor for spintronic applications. Appl. Phys. A 9, 125 (2019). CrossRefGoogle Scholar
  28. 28.
    A. Aravind, K. Hasna, M.K. Jayaraj, M. Kumar, R. Chandra, Magnetic and Raman scattering studies of Co-doped ZnO thin films grown by pulsed laser deposition. Appl. Phys. A 115(3), 843–849 (2014)ADSCrossRefGoogle Scholar
  29. 29.
    S. Roguai, A. Djelloul, C. Nouveau, T. Souier, A.A. Dakhel, M. Bououdina, Structure, microstructure and determination of optical constants from transmittance data of Co-doped Zn0.90 Co0.05M 0.05 O (M = Al, Cu, Cd, Na) films. J. Alloys Compd. 599, 150–158 (2014)CrossRefGoogle Scholar
  30. 30.
    M. Bouloudenine, N. Viart, S. Colis, J. Kortus, A. Dinia, Antiferromagnetism in bulk Zn1 xCoxO Zn1 xCoxO magnetic semiconductors prepared by the coprecipitation technique. Appl. Phys. Lett. 87, 052501 (2005)ADSCrossRefGoogle Scholar
  31. 31.
    X.C. Chen, J.P. Zhou, H.Y. Wang, P.S. Xu, G.Q. Pan, Chin. Phys. B. 20, 9 (2011)Google Scholar
  32. 32.
    D. Bao, H. Gu, A. Kuang, Sol-gel-derived c-axis oriented ZnO thin films. Thin Solid Films 312, 37–39 (1998)ADSCrossRefGoogle Scholar
  33. 33.
    S. Benramache, B. Benhaoua, Influence of substrate temperature and Cobalt concentration on structural and optical properties of ZnO thin films prepared by ultrasonic spray technique. Superlattices Microstruct. 52, 807–815 (2012)ADSCrossRefGoogle Scholar
  34. 34.
    G. Vijayaprasath, R. Murugan, G. Ravi, T. Mahalingam, Y. Hayakawa, Characterization of dilute magnetic semiconducting transition metal doped ZnO thin films by a sol-gel spin coating method. Appl. Surf. Sci. 313, 870–876 (2014)CrossRefGoogle Scholar
  35. 35.
    P. Lommens, P.F. Smet, C.M. Donega, A. Meijerink, L. Piraux, S. Michotte, S.M. Tempfli, D. Poelman, Z. Hens, Photoluminescence properties of Co2+-doped ZnO nanocrystals. J. Lumin. 118, 245–250 (2006)CrossRefGoogle Scholar
  36. 36.
    A.S. Pereira, A.O. Ankiewicz, W. Gehlhoff, A. Hoffmann, S. Pereira, T. Trindade, M. Jrundmann, M.C. Carmo, N.A. Sobolev, Surface modification of Co-doped ZnO nanocrystals and its effects on the magnetic properties. J. Appl. Phys. 103, 07D140 (2008). CrossRefGoogle Scholar
  37. 37.
    F. Urbach, The long-wavelength edge of photographic sensitivity and electronic absorption of solids. APS J. Phys. Rev. 92, 1324–1326 (1953)ADSCrossRefGoogle Scholar
  38. 38.
    B.J. Jin, S. Im, S.Y. Lee, Violet and UV luminescence emitted from ZnO thin films grown on sapphire by pulsed laser deposition. Thin Solid Films 366, 107–110 (2000)ADSCrossRefGoogle Scholar
  39. 39.
    D.H. Zhang, Z.Y. Xue, Q.P. Wang, The mechanisms of blue emission from ZnO films deposited on glass substrate by r.f. magnetron sputtering. J. Phys. D. 35, 2837 (2002)ADSCrossRefGoogle Scholar
  40. 40.
    A. Kaphle, P. Hari, Characterization of aluminium doped nanostructured ZnO/p-Si heterojunctions. Int. J. Eng. Sci. (IJES) 5, 41–51 (2016)Google Scholar
  41. 41.
    U. Godavarti, V.D. Mote, M.V. Ramana Reddy, P. Nagaraju, Y. VijayKumar, K. T. Dasari, M. P. Dasari, Precipitated cobalt doped ZnO nanoparticles with enhanced low temperature xylene sensing properties. Phys. B Phys. Condens. Matter. 533, 151–160 (2019). Scholar
  42. 42.
    U. Philipose, S.V. Nair, S. Trudel, C.F. Souza, S. Aouba, R.H. Hill, H.E. Ruda, High- temperature ferromagnetism in Mn-doped ZnO nanowires. Appl. Phys. Lett. 88, 263101 (2006)ADSCrossRefGoogle Scholar
  43. 43.
    L. Xu, H. Zhang, K. Shen, M. Xu, Q. Xu, Room temperature ferromagnetism in Co-doped ZnO prepared by microemulsion. J. Supercond. Nov. Magn. 25, 1951–1956 (2012)CrossRefGoogle Scholar
  44. 44.
    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. Compd. 655, 244–252 (2016)CrossRefGoogle Scholar
  45. 45.
    Z. Xiong, X.C. Liu, S.Y. Zhuo, J.H. Yang, E.W. Shi, W.S. Yan, Oxygen enhanced ferromagnetism in Cr-doped ZnO films. Appl. Phys. Lett. 99, 052513 (2011)ADSCrossRefGoogle Scholar
  46. 46.
    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
  47. 47.
    J.R. Neal, A.J. Behan, R.M. Ibrahim, H.J. Blythe, M. Ziese, A.M. Fox, G.A. Gehring, Room-temperature magneto-optics of ferromagnetic transition-metal-doped ZnO thin films. Phys. Rev. Lett. 96, 197208–197212 (2006)ADSCrossRefGoogle Scholar
  48. 48.
    M. R. Baklanov, K. P. Mogilnikov, V. G. Polovinkin, F. N. Dultsev, Determination of pore size distribution in thin films by ellipsometric porosimetry. J. Vac. Sci. Technol. B. 18, 1385–1391(2000).ADSCrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.LASPI2A Laboratoire des Structures, Propriétés et Interactions Inter AtomiquesUniversité Abbes LaghrourKhenchelaAlgeria
  2. 2.Science of MatterAbbes Laghrour UniversityKhenchelaAlgeria

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