Magnetic Oxide Semiconductors

  • Nguyen Hoa HongEmail author


In 2000, it was theoretically predicted that ferromagnetism (FM) at high temperature could be obtained in many semiconductors such as ZnO, GaAs, GaN, etc., if we dope Mn plus a certain concentration of holes into these systems. The magnetic ordering in those compounds was suggested to originate from the Ruderman–Kittel–Kasuya–Yoshida interaction of localized moments of dopants via 2p holes or 4s electrons. Inspired by this idea, many experimentalists have tried to dope transition metals (TM) into many oxides such as ZnO, TiO2, SnO2, In2O3, etc., with the hope to obtain room temperature FM in semiconductors, in order to be able to exploit both charge and spin in the same devices. Actually, room temperature FM was observed; however, the phenomenon is not exactly as what theorists have proposed. The finding of FM in undoped HfO2 thin films in 2004 has first given some alert to the magnetism community to rejudge the real role that a dopant indeed plays. More recently, experimental observations of FM for various oxides such as TiO2, HfO2, In2O3, ZnO, CeO2, Al2O3, and MgO in low-dimensional structures have confirmed that FM is certainly possible for undoped oxide semiconductors. It was suggested that FM might stem from oxygen vacancies and/or defects that were formed at the surface and interfaces.

Research on very thin films and nanoparticles of Diluted Magnetic Oxide semiconductors (DMSO) has pointed out that downscaling magnetic oxide semiconductors to nanometer scale should be an important step, in order to make them ferromagnetic. It opens a door to exploit the bright side of nano-world in this field of spintronics.

The domain of DMSO research still requires a lot of efforts of the world wide research groups toward higher levels with the hope to bring it closer to a realization of spintronic devices based on DMSO materials.


Oxygen Vacancy TiO2 Film Impurity Band Magnetic Force Microscopy SnO2 Film 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

List of Abbreviations


Charge transfer ferromagnetism


Diluted magnetic semiconductors


Diluted magnetic semiconducting oxides


Density of states


Fermi level






Magnetization versus magnetic field


Magnetization versus temperature


Magnetic force microscopy


Saturated magnetization


Rutherford backscattering spectroscopy






Curie temperature


Transition metal




X-ray absorption spectroscopy


X-ray magnetic circular dichroism


X-ray diffraction



The author would like to thank J. Sakai, A. Hassini, A. Ruyter, N. Poirot, V. Brize, N. Q. Huong, A. Barla, C-K. Park, and J-H. Song for their co-work and then contributions in experiments that lead to our results in the DMSO field. The work on ZrO2 and writing of this Chapter were supported by project 3348–20100041 of the National Research Foundation of Korea. The work on C-doped SnO2 was supported by project 3348–20100016 of SNU R&D Foundation.


  1. 1.
    Dietl T, Ohno H, Matsukura F, Cibert J, Ferrand D (2000) Zener Model Description of Ferromagnetism in Zinc-Blende Magnetic Semiconductors. Science 287:1019CrossRefADSGoogle Scholar
  2. 2.
    Sato K, Katayama-Yoshida H (2000) Material design for transparent ferromagnets with ZnO-based magnetic semiconductors. Jpn J Appl Phys Part 2 39:L555CrossRefGoogle Scholar
  3. 3.
    Matsumoto Y, Murakami M, Shono T, Hasegawa T, Fukumura T, Kawasaki M, Ahmet P, Chikyow T, Koshihara S, Koinuma H (2001) Room-temperature ferromagnetism in transparent transition metal-doped titanium dioxide. Science 291:854CrossRefADSGoogle Scholar
  4. 4.
    Prellier W, Fouchet A, Mercey B (2003) Oxide-diluted magnetic semiconductors: a review of the experimental status. J Phys Condens Matter 15:R 1583CrossRefADSGoogle Scholar
  5. 5.
    Ranish R, Gopal P, Spaldin NA (2005) Transition metal-doped TiO2 and ZnO – present status of the field. J Phys Condens Matter 17:R657CrossRefGoogle Scholar
  6. 6.
    Venkatesan M, Fitzgerald CB, Coey JMD (2004) Thin films: Unexpected magnetism in a dielectric oxide. Nature 430:630CrossRefADSGoogle Scholar
  7. 7.
    Schwartz DA, Gamelin DR (2004) Reversible 300K Ferromagnetic Ordering in a Diluted Magnetic Semiconductor. Adv Mater 16:2115CrossRefGoogle Scholar
  8. 8.
    Hong NH, Sakai J, Huong NT, Poirot N, Ruyter A (2005) Role of defects in tuning ferromagnetism in diluted magnetic oxide thin films. Phys Rev B 72:45336CrossRefADSGoogle Scholar
  9. 9.
    Hong NH, Sakai J, Poirot N, Brizé V (2006) Room-temperature ferromagnetism observed in undoped semiconducting and insulating oxide thin films. Phys Rev B 73:132404CrossRefADSGoogle Scholar
  10. 10.
    Hong NH, Sakai J, Huong NT, Ruyter A, Brizé V (2006) Magnetism in transition-metal-doped In2O3 thin films. J Phys Condens Matter 18:6897CrossRefADSGoogle Scholar
  11. 11.
    Hong NH, Poirot N, Sakai J (2008) Ferromagnetism observed in pristine SnO2 thin films. Phys Rev B 77:33205; Chang GS, Forrest J, Kurmaev EZ, Morozovska AN, Glinchuk MD, McLeod JA, Moewes A, Surkova TP, Hong NH (2012) Oxygen-vacancy-induced ferromagnetism in undoped SnO2 thin films. Phys Rev B 85:165319Google Scholar
  12. 12.
    Sundaresan A, Bhagravi B, Rangarajan N, Siddesh U, Rao CNR (2006) Ferromagnetism as a universal feature of nanoparticles of the otherwise nonmagnetic oxides. Phys Rev B 74:161306 (R)Google Scholar
  13. 13.
    Martínez-Boubeta C, Beltrán JI, Balcells L, Konstantinović Z, Valencia S, Schmitz D, Arbiol J, Estrade S, Cornil J, Martínez B (2010) Ferromagnetism in transparent thin films of MgO. Phys Rev B 82:024405CrossRefADSGoogle Scholar
  14. 14.
    Sato K et al (2007) Computational materials design of ZnO-based semiconductor spintronics. In: Hong NH (ed) Magnetism in semiconducting oxides. Transworld Research Network, TrivandrumGoogle Scholar
  15. 15.
    Sato K, Dederichs PH, Katayama-Yoshida H, Kudrnovsky J (2004) Exchange interactions in diluted magnetic semiconductors. J Phys Condens Matter 16:S5491CrossRefADSGoogle Scholar
  16. 16.
    Sato K, Dederichs PH, Katayama-Yoshida H (2003) Curie temperatures of III–V diluted magnetic semiconductors calculated from first principles. Europhys Lett 61:403CrossRefADSGoogle Scholar
  17. 17.
    Zunger A, in Solid State Physics, edited by H. Ehren- reich and D. Turnbull (Academic, New York, 1986) 39:276Google Scholar
  18. 18.
    Hong NH, Sakai J, Prellier W, Hassini A, Ruyter A, Gervais F (2004) Ferromagnetism in transition-metal-doped TiO2 thin films. Phys Rev B 70:195204CrossRefADSGoogle Scholar
  19. 19.
    Kimura H, Fukumura T, Kawasaki M, Inaba K, Hasegawa T, Koinuma H (2002) Rutile-type oxide-diluted magnetic semiconductor: Mn-doped SnO2. Appl Phys Lett 80:94CrossRefADSGoogle Scholar
  20. 20.
    Ogale SB, Choudhary RJ, Buban JP, Lofland SE, Shinde SR, Kale SN, Kulkarni VN, Higgins J, Lanci C, Simpson JR, Browning ND, Das SS, Drew HD, Greene RL, Venkatesan T (2003) High temperature ferromagnetism with a giant magnetic moment in transparent Co-doped SnO2-δ. Phys Rev Lett 91:77205CrossRefADSGoogle Scholar
  21. 21.
    Coey JMD, Douvalis AP, Fitzgerald CB, Venkatesan M (2004) Ferromagnetism in Fe-doped SnO2 thin films. Appl Phys Lett 84:1332CrossRefADSGoogle Scholar
  22. 22.
    Hong NH, Sakai J, Prellier W, Hassini A (2005) Transparent Cr-doped SnO2 thin films: ferromagnetism beyond room temperature with a giant magnetic moment. J Phys Condens Matter 17:1697CrossRefADSGoogle Scholar
  23. 23.
    Hong NH, Ruyter A, Prellier W, Sakai J, Huong NT (2005) Magnetism in Ni-doped SnO2 thin films. J Phys: Condens Matter 17:6533ADSGoogle Scholar
  24. 24.
    Hong NH, Sakai J (2005) Ferromagnetic V-doped SnO2 thin films. Physica B 358:265CrossRefADSGoogle Scholar
  25. 25.
    Kittel C (1996) Introduction to solid state physics, 7th edn. Wiley, New YorkGoogle Scholar
  26. 26.
    Hong NH, Sakai J, Huong NT, Ruyter A, Brizé V (2006) Magnetism in transition-metal-doped In2O3 thin films. J Phys: Condens Matter 18:6897ADSGoogle Scholar
  27. 27.
    Hong NH, Sakai J, Hassini A (2005) Magnetism in V-doped ZnO thin films. J Phys: Condens Matter 17:199ADSGoogle Scholar
  28. 28.
    Wang Q, Sun Q, Rao BK, Sena P (2004) Magnetism and energetics of Mn-Doped ZnO (1010) thin films. Phys Rev B 69:233310CrossRefADSGoogle Scholar
  29. 29.
    Spaldin NA (2004) Search for ferromagnetism in transition-metal-doped piezoelectric ZnO. Phys Rev B 69:125201CrossRefADSGoogle Scholar
  30. 30.
    Hong NH, Brizé V, Sakai J (2005) Mn-doped ZnO and .Mn, Cu.-doped ZnO thin films: Does the Cu doping indeed play a key role in tuning the ferromagnetism?. Appl Phys Lett 86:82505CrossRefGoogle Scholar
  31. 31.
    Pemmaraju CD, Sanvito S (2005) Ferromagnetism Driven by Intrinsic Point Defects in HfO2. Phys Rev Lett 94:217205CrossRefADSGoogle Scholar
  32. 32.
    Hong NH, Barla A, Sakai J, Huong NQ (2007) Can undoped semiconducting oxides be ferromagnetic?. Phys Status Solid (c) 4:4461CrossRefADSGoogle Scholar
  33. 33.
    Barla A, Schmerber G, Beaurepaire E, Dinia A, Bieber H, Colis S, Scheurer F, Kappler J-P, Imperia P, Nolting F, Wilhelm F, Rogalev A, Muller D, Grob J-J (2007) Paramagnetism of the Co sublattice in ferromagnetic Zn1–xCoxO films. Phys Rev B 76:125201CrossRefADSGoogle Scholar
  34. 34.
    Coey JMD, Venkatesan M, Stamenov P, Fitzgerald CB, Dorneles LS (2005) Magnetism in hafnium dioxide. Phys Rev B 72:24450CrossRefADSGoogle Scholar
  35. 35.
    Bouzerar G, Ziman T (2006) Model for Vacancy-Induced d0 Ferromagnetism in Oxide Compounds. Phys Rev Lett 96:207602CrossRefADSGoogle Scholar
  36. 36.
    Yoon SD, Chen Y, Yang A, Goodrich TL, Zuo X, Arena DA, Ziemer K, Vittoria C, Harris VG (2006) Oxygen-defect-induced magnetism to 880 K in semiconducting anatase TiO2–δ films. J Phys Condens Matter 18:L355–L361CrossRefADSGoogle Scholar
  37. 37.
    Hassini A, Sakai J, Lopez JS, Hong NH (2008) Magnetism in spin-coated pristine TiO2 thin films. Phys Lett A 372:3299CrossRefADSGoogle Scholar
  38. 38.
    Hartnagel HL, Dawar AL, Jain AK, Jagadish C (1995) Semiconducting transparent thin films. IOP Publishing, Bristol/PhiladelphiaGoogle Scholar
  39. 39.
    Hays J, Punnoose A, Baldner R, Engelhard MH, Peloquin J, Reddy KM (2005) Relationship between the structural and magnetic properties of Co-doped SnO2 nanoparticles. Phys Rev B 72:075203CrossRefADSGoogle Scholar
  40. 40.
    Hong NH, Song J-H, Raghavender AT, Asaeda T, Kurisu M (2011) Ferromagnetism in C-doped SnO2 thin films. Appl Phys Lett 99:052505CrossRefADSGoogle Scholar
  41. 41.
    Barla A, Hong NH et al (2007–2012) Unpublished XMCD results on TiO2 systemGoogle Scholar
  42. 42.
    Huong NQ (2007) Magnetism due to oxygen vacancies in undoped oxide thin films. In: Hong NH (ed) Magnetism in semiconducting oxides. Transworld Research Network, KeralaGoogle Scholar
  43. 43.
    Hong NH, Park C-K, Raghavender AT, Ruyter A, Chikoidze E, Dumont Y (2012) High temperatureferromagnetism in cubic Mn-doped ZrO2 thin films. J Mag Mag Mater 324:3013CrossRefADSGoogle Scholar
  44. 44.
    Coey JMD, Venkatesan M, Fitzgerald CB (2005) Donor impurity band exchange in dilute ferromagnetic oxides. Nat Mater 4:173–179CrossRefADSGoogle Scholar
  45. 45.
    Elfimov IS, Yunoki S, Sawatzky GA (2002) Possible Path to a New Class of Ferromagnetic and Half-Metallic Ferromagnetic Materials. Phys Rev Lett 89:216403CrossRefADSGoogle Scholar
  46. 46.
    Coey JMD, Magnetism and Magnetic Materials. Cambridge Univ. Press, 2010CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  1. 1.Department of Physics and AstronomySeoul National UniversitySeoulSouth Korea

Personalised recommendations