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Journal of Magnetism and Magnetic Materials 272276 (2004) e1563e1564

First-principles calculations on magnetism of transition metal doped zinc oxide

Sun Young Yun, Gi-Beom Cha, Youngsoo Kwon, Sunglae Cho, Soon C. Hong*
Department of Physics, University of Ulsan, Mugeo-Dong, Nam-Gu, Ulsan 690-749, South Korea

Abstract We calculated the electronic structure and magnetism of 3d or 4d transition metal-doped ZnO (TM0.25Zn0.75O: TM=Ti, Cr, Mn, Fe, Co, Ni, Ru, Pd, and Ag), using the full potential linearized augmented plane method based on general gradient approximation for exchangecorrelation potential. The magnetic moments of Ti, Cr, Mn, Fe, Co, Ni, Ru, Pd, and Ag in the systems were calculated to be 1.24, 3.78, 4.93, 4.24, 3.00, 2.00, 0.74, 1.00, and 0.00 mB, respectively. The calculated magnetic moment of Ti is not negligible in marked contrast to the previously calculated zero magnetic moment with KorringaKohnRostoker. The magnetic moment of a type of oxygen is sizable (up to 0.18 mB). r 2003 Elsevier B.V. All rights reserved.
PACS: 75.50.Pp; 71.15.Mb; 71.20.b Keywords: Diluted magnetic semiconductor; ZnO; First principles calculation; Magnetic moment

Recently, diluted magnetic semiconductor (DMS) is a very interesting subject due to its promising application to spintronics. There has been much interest in magnetic semiconductors, which exploit both the spin and the charge of the carriers, because the combination of the two degrees of freedom promises new functionality of memories, detectors, and light-emitting sources. A traditional method in the integration of DMS is to dope magnetic elements such as Mn, Cr, Co, and Fe into conventional IIVI or IIIV semiconductors. Recently, Dietl et al. [1] predicted that Mn-doped ZnO would show ferromagnetic (FM) behavior with a TC above room temperature. Several 3d transition metal (TM)doped ZnO lms have been prepared since the thermal equilibrium solubility of transition metals in the host materials is higher than 10 mol%. In order to investigate the magnetism of TM-doped ZnO, we calculated the electronic structure and magnetism of 3d or 4d TM-doped ZnO (TM0.25Zn0.75O: TM=Ti, Cr, Mn, Fe, Co, Ni, Ru, Pd, and Ag), using
*Corresponding author. Tel.: +82-52-259-2331; fax: +8252-259-1693. E-mail address: schong@mail.ulsan.ac.kr (S.C. Hong).

the highly precise full-potential linearized augmented plane wave (FLAPW) method [2] within general gradient approximation (GGA) for exchangecorrelation potential. The lattice is considered as an experimental wurtzite crystal structure of ZnO with ( c 5:2069 A, ( and u 0:345 [3]. One a 3:2495 A, hundred and eight special k-points within the irreducible Brillouin zone were used for the integration and about 700 basis functions were used for each k-point. Table 1 shows the calculated magnetic moments per TM atom (within mufn-tin sphere) of Ti, Cr, Mn, Fe, Co, Ni, Ru, Pd, and Ag in the systems. The magnetic moments are 1.24(0.83), 3.78(3.03), 4.93(4.03), 4.24(3.48), 3.00(2.46), 2.00(1.56), 0.74(0.42), 1.00(0.56), and 0.00(0.00) mB, respectively. The overall trend except Ti is quite similar to the previous calculational results on 3d TM-doped ZnO with KorringaKohnRostoker (KKR) method [4]. However, for Ti0.25Zn0.75O our highly precise calculation resulted in a quite large magnetic moment (1.24 mB per Ti and 0.86 mB within the MT sphere) in contrast to the previously calculated zero magnetic moment with KKR. As expected, the 3d TMs have larger magnetic moments compared to those of the 4d TMs. The Mn atom has the largest magnetic

0304-8853/$ - see front matter r 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.jmmm.2003.12.566

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e1564 S.Y. Yun et al. / Journal of Magnetism and Magnetic Materials 272276 (2004) e1563e1564 Table 1 Total energy difference (meV) between paramagnetic and ferromagnetic states and magnetic moment (mB) in total, within the TM MT spheres, and in interstitial regions DTE Ti Cr Mn Fe Co Ni Ru Pd Ag 161 1469 2405 1432 1262 768 36 52 0 MM 0.83 3.03 4.03 3.48 2.46 1.56 0.42 0.56 0.01 Total MM 1.24 3.78 4.93 4.24 3.00 2.00 0.74 1.00 0.02 Interstitial MM 0.36 0.60 0.56 0.32 0.19 0.07 0.18 0.09 0.00 Fig. 1. Atom projected density of state of (a) Pd0.25Zn00.75O and (b) Mn0.25Zn00.75O. Solid (dotted) lines represent majority (minority) spin states.

moment of almost 5 mB corresponding to the full polarization of the half-lled d bands. It is noticeable that one of the oxygen atoms, bridging the TM atoms, has sizable magnetic moment with ferromagnetic coupling to the TM atom. For example the oxygen atom in Fe0.25Zn0.75O has magnetic moment of 0.18 mB that is contributed mainly from p electrons. The strong directional hybridization between O-p and TM-d bands to retain the tetrahedral bonding leads to a polarization of p electrons. As a result, Fe0.25Zn0.75O has a larger magnetic moment (4.24 mB) than the maximum magnetic moment that an isolated Fe atom with d6 electron conguration can have according to Hunds rule. Fig. 1 shows the density of states (DOS) of (a) Pd0.25Zn0.75O and (b) Mn0.25Zn0.75O as representative examples of 3d and 4d doped ZnO. The solid (dotted) lines represent the majority (minority) spin states. As shown in Fig. 1(b), minority spin states are almost unoccupied due to large exchange splitting. The 3d TMdoped ZnOs (except Co-doped) show half-metallic behavior whereas 4d TM-doped ZnOs show normal metallic behavior. Co0.25Zn0.75O has a band gap at Fermi level due to crystal eld splitting of eg and t2g bands [5]. Hence, we expect that the magnetism might be quite different depending on the TM elements. The different magnetism will be discussed elsewhere [5]. In summary, we calculated the electronic structure and magnetism of 3d or 4d transition metal-doped ZnO

(TM0.25Zn0.75O: TM=Ti, Cr, Mn, Fe, Co, Ni, Ru, Pd, and Ag), using the highly precise FLAPW method. The calculated magnetic moments are quite large (1.24 4.93 mB) and 3d TM-doped ZnOs show half-metallic behavior except the Co-doped that has a calculated band gap of about 0.5 eV due to crystal eld splitting of eg and t2g bands. The 4d TM-doped ZnOs have nite DOS at Fermi level for both the minority and majority spin states. This work was supported by KOSEF through ASSRC at Yonsei University and the Brain Korea 21 Project in 2003.

References
[1] T. Dietl, H. Ohno, F. Matsukura, J. Cibert, D. Ferrand, Science 287 (2000) 1019. [2] E. Wimmer, H. Krakauer, M. Weinert, A.J. Freeman, Phys. Rev. B 24 (1981) 864 and references therein. [3] R.W.G. Wyckoff, Crystal Structures, Vol. 1, 2nd Edition, Wiley, New York, 1986, p. 112. [4] K. Sato, H. Katayama-Yoshida, Physica E 10 (2001) 251. [5] S.Y. Yun, et al., unpublished.