The search for ferromagnetism above room temperature in dilute magnetic semiconductors has been intense in recent years. We report the first observations of ferromagnetism above room temperature for dilute (<4 at.%) Mn-doped ZnO. The Mn is found to carry an average magnetic moment of 0.16 μB per ion. Our ab initio calculations find a valance state of Mn2+ and that the magnetic moments are ordered ferromagnetically, consistent with the experimental findings. We have obtained room-temperature ferromagnetic ordering in bulk pellets, in transparent films 2–3 μm thick, and in the powder form of the same material. The unique feature of our sample preparation was the low-temperature processing. When standard high-temperature (T > 700 °C) methods were used, samples were found to exhibit clustering and were not ferromagnetic at room temperature. This capability to fabricate ferromagnetic Mn-doped ZnO semiconductors promises new spintronic devices as well as magneto-optic components.
Subscribe to Journal
Get full journal access for 1 year
only $8.25 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Ohno, H. Making nonmagnetic semiconductors ferromagnetic. Science 281, 951–956 (1998).
Dietl, T., Ohno, H., Matsukura, F., Cibert, J. & Ferrand, D. Zener model description of ferromagnetism in zinc-blende magnetic semiconductors. Science 287, 1019–1022 (2000).
Matsumoto, Y. et al. Room-temperature ferromagnetism in transparent transition metal-doped titanium dioxide. Science 291, 854–856 (2001).
Ando, K. et al. Magneto-optical properties of ZnO-based dilute magnetic semiconductors. J. Appl. Phys. 89, 7284–7286 (2001).
Takamura, K., Matsukura, F., Chiba, D. & Hono, H. Magnetic properties of (Al,Ga,Mn)As. Appl. Phys. Lett. 81, 2590–2592 (2002).
Chambers, S.A. A potential role in spintronics. Mater. Today 34–39 (April 2002).
Ohno, H., Matsukura, F. & Ohno, Y. Semiconductor spin electronics. JSAP Int. 5, 4–13 (2002).
Nazmul, M., Ahsan, S. & Tanaka, M. High ferromagnetic transition temperature (∼172K) in Mn δ-doped GaAs with p-type selective doping. Cond-mat/0208299 (2003).
Ueda, K., Tabata, H. & Kawai, T. Magnetic and electric properties of transition-metal-doped ZnO films. Appl. Phys. Lett. 79, 988–990 (2001).
Thaler, G.T. et al. Magnetic properties of n-GaMnN thin films. Appl. Phys. Lett. 80, 3964–3966 (2002).
Stampe, P.A., Kennedy, R.J., Yan, X. & Parker, J.S. Investigation of the cobalt distribution in TiO2:Co thin films. J. Appl. Phys. 92, 7114–7121 (2002).
Chambers, S.A. et al. Clusters and magnetism in epitaxial Co-doped TiO2 anatase. Appl. Phys. Lett. 82, 1257–1259 (2003).
Kim, J.H., Kim, H., Ihm, Y.E. & Choo, W.K. Magnetic properties of epitaxially grown semiconducting Zn1-xCoxO thin film by pulsed laser deposition. J. Appl. Phys. 92, 6066–6071 (2002).
Fukumura, T., Jin, Z., Ohtomo, A., Koinuma, H. & Kawasaki, M. An oxide-diluted magnetic semiconductor: Mn-doped ZnO. Appl. Phys. Lett. 75, 3366–3368 (1999).
Fukumura, T. et al. Magnetic properties of Mn-doped ZnO. Appl. Phys. Lett. 78, 958–960 (2001).
Jung, S.W. et al. Ferromagnetic properties of Zn1-xMnxO epitaxial thin films. Appl. Phys. Lett. 80, 4561–4563(2002).
Tiwari, A. et al. Structural, optical and magnetic properties of diluted magnetic semiconducting Zn1-xMnxO films. Solid State Commun. 121, 371–374 (2002).
Egerton, R.F. Electron Energy-Loss Spectroscopy in the Electron Microscope 370 (Plenum, New York and London, 1996).
Kurata, H. & Colliex, C. Electron energy-loss core-edge structure in manganese oxides. Phys. Rev. B 48, 2102–2108 (1993).
Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).
Kresse, G. & Hafner, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Blöchel, P.E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Perdew, J.P. & Wang, Y. Accurate and simple analytic representation of the electron- gas correlation energy. Phys. Rev. B 45, 13244–13249 (1992).
Sato, K. & Katayama-Yoshida, H. First principles materials design for semiconductors spintronics. Semicond. Sci. Technol. 17, 367–376 (2002).
Korzhavy, P.A. et al. Defect-induced magnetic structure in (Ga1-xMnx)As. Phys. Rev. Lett. 88, 187202 (2002).
R.A., J.G. and B.J. acknowledge the support from the ATOMICS and EXCITING programmes by the Swedish Strategic Foundation and the EU network. Some of the theoretical calculations were carried out at the National Supercomputer Centre at Linköping, Sweden. P.S., A.G. and K.V.R. acknowledge partial support for this research from the Swedish Agency VINNOVA. G.G. would like to acknowledge a visiting fellowship from the Swedish foundation STINT, and the hospitality during her stay at the Department of Materials Science of the Royal Institute of Technology. The use of the Center for High Resolution Electron Microscopy (CHREM) is gratefully acknowledged. Finally, we wish to thank very much the excellent and fruitful exchanges we have had with the reviewers of this manuscript. It has been the most enjoyable part of the scientific work.
The authors declare no competing financial interests.
About this article
Cite this article
Sharma, P., Gupta, A., Rao, K. et al. Ferromagnetism above room temperature in bulk and transparent thin films of Mn-doped ZnO. Nature Mater 2, 673–677 (2003). https://doi.org/10.1038/nmat984
Structural and magnetic properties of polycrystalline Zn1−xMnxO films synthesized on glass and p-type Si substrates using Sol–Gel technique
Applied Physics A (2021)
Optical, photoluminescence and ferromagnetic properties of Ni-doped ZnO for optoelectronic applications
Journal of Materials Science: Materials in Electronics (2021)
Observation of Ferromagnetism in Heavy Ion Bi-doped Nanocrystalline Zinc Oxide Prepared by Co-precipitation
Journal of Superconductivity and Novel Magnetism (2020)
New investigation of nanosized co-doped Gd-Sm anatase TiO2 structural, magnetic, optical, and first-principles study
Applied Physics A (2020)
Fabrication of Al-doped ZnO nanoparticles and their application as a semiconductor-based gas sensor for the detection of ammonia
Journal of Materials Science: Materials in Electronics (2020)