Ferromagnetic enhancement and magnetic anisotropy in nonpolar-oriented (Mn, Na)-codoped ZnO thin films

B. Lu, L. Q. Zhang, Y. H. Lu, Z. Z. Ye, J. G. Lu et al. Citation: Appl. Phys. Lett. 101, 242401 (2012); doi: 10.1063/1.4770290 View online: http://dx.doi.org/10.1063/1.4770290 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v101/i24 Published by the AIP Publishing LLC.

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APPLIED PHYSICS LETTERS 101, 242401 (2012)

Ferromagnetic enhancement and magnetic anisotropy in nonpolar-oriented (Mn, Na)-codoped ZnO thin films
B. Lu,a) L. Q. Zhang, Y. H. Lu, Z. Z. Ye,b) J. G. Lu, X. H. Pan, and J. Y. Huang
State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, Peoples Republic of China

(Received 30 October 2012; accepted 21 November 2012; published online 10 December 2012) High-resistive Zn0.95Mn0.05O and weak p-type nonpolar-oriented Zn0.94Mn0.05Na0.01O thins lms were grown on quartz by pulsed laser deposition. Both samples exhibit room temperature ferromagnetism while with Mn-Na codoping, the saturation magnetic moment is greatly enhanced. It is revealed that the doped Mn impurities are substitutionally incorporated into the ZnO host. Magnetic anisotropy was also observed in the Zn0.94Mn0.05Na0.01O lm, which is the indication for intrinsic ferromagnetism. The rst-principles calculations reveal that codoping of Na in Zn0.94Mn0.05Na0.01O changes the antiferromagnetic interaction to ferromagnetic due to the hybridization between spin-split delocalized Mn 3d and shallow acceptor states of Na 2p, thereby enhancing the ferromagnetism. C 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4770290] V O2 (99.999% purity) atmosphere (PO2 45 Pa) with a deposition rate of $0.44 nm/s. Film composition was determined by inductively coupled-plasma (ICP) emission spectra with x being slightly greater than x0 (0.05) while y being slightly smaller than 0.01 after measuring the magnetic properties. The crystalline structures of the deposited lms were characterized by an x-ray diffractometer (XRD) (Bede D1) with Cu Ka radiation (k 0.15406 nm). The electrical properties were investigated using a four-point probe van der Pauw conguration (HL5500PC) at room temperature. To determine the valence state and local geometry of the Mn dopant in the ZnO lattice, Mn k-edge XANES was employed. Magnetization studies were carried out using a superconducting quantum interference device (SQUID) magnetometer using an in-plane geometry (magnetic eld parallel to the lm) on all samples, unless specied differently. In order to understand the experiment results, rst-principles calculations were utilized to investigate the electronic structures and magnetic interactions. Figure 1 shows the XRD spectra for Zn0.95Mn0.05O (designated as ZMO) and Zn0.94Mn0.05Na0.01O (designated as ZMNO) thin lms. Both samples are of the wurtzite structure of ZnO with no distinct evidence of secondary phases. In the

Diluted magnetic semiconductors (DMSs) have attracted immense interest for potential applications in spin electronics and magnetic devices.1,2 Among them, the most studied are ZnO-based DMSs due to the theoretical predictions of ferromagnetic above room temperature for these materials.3 Tremendous efforts have been devoted to the 3d transitionmetal (TM) doped ZnO and in particular, to the Mn-doped and Co-doped ZnO systems.410 Experimental studies on Mn-doped ZnO materials reached very conicting results concerning correlation between ferromagnetism (FM) and conduction polarity. FM above room temperature was reported for both n-type9,11 and p-type7,12 Mn-doped ZnO thin lms. Thus, the circumstance under which Mn-doped ZnO can be ferromagnetic is still debatable. Meanwhile, several theoretical approaches have concluded that doping with Mn atoms does not lead to a FM ground state in ZnO and suggesting the necessity of codoping, the presence of additional carriers plays an important role in stabilizing and/or enhancing the magnetic coupling by the codoping ions in Mn-doped ZnO,6,1316 which has been experimentally conrmed in recent works. In view of this, codoping appears to be a potential approach to obtain intrinsic and enhanced FM in Mn-doped ZnO. In this letter, we report on our experimental and calculated ndings of Mndoped and (Mn, Na)-codoped ZnO thin lms. The results show strong evidence for Na codopant effect in tuning the electrical activity and enhancing the effective magnetic moments per Mn ion and for the intrinsic nature of ferromagnetism in (Mn, Na)-codoped ZnO. Polycrystalline Zn1xyMnxNayO thin lms were grown on quartz substrates by pulsed laser deposition (PLD) using a KrF excimer laser (Compex102, 248 nm, 5 Hz) from corresponding ceramic oxide targets (nominal x0 0.05; y0 0, 0.01). The laser repetition rate is 5 Hz and the energy per pulse is 340 mJ. The base pressure of the deposition chamber is 1 104 Pa, and lms, $800 nm thick, were grown in an
a)

Author to whom correspondence should be addressed. Electronic mail: binlu@zju.edu.cn. b) Electronic mail: yezz@zju.edu.cn. 0003-6951/2012/101(24)/242401/4/$30.00

FIG. 1. XRD spectra of Zn0.95Mn0.05O and Zn0.94Mn0.05Na0.01O thin lms deposited on quartz substrates under identical growth conditions.
C 2012 American Institute of Physics V

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ZMO lm, the non-polar related phases are minority as compared to the polar one. While for the ZMNO lm, the c-axisrelated peak is completely suppressed and the preferential nonpolar 1010 plane predominant over other nonpolar planes such as 1120 and 2020 planes is seen. The results indicate that Mn-Na codoping facilitates the formation of nonpolar-oriented ZnO lm on quartz substrates. The Mn k-edge XANES spectrum of Zn0.94Mn0.05 Na0.01O is presented in Fig. 2 along with the reference materials of Mn metal, crystalline MnO, and MnO2. The existence of these reference materials can be easily excluded due to signicant difference in XANES spectral shapes and edge positions between that from them and from the ZMNO. Additionally, the pre-edge feature at h $ 6534 eV (marked A) allows a denitive assignment to be made, as was demonstrated for Mn-doped GaN.17 This small peak arises if Mn substitutes Zn in tetrahedral coordination and exhibits a 2 formal charge state. However, if the Mn is formally 3 , there will be a pre-edge doublet.18 Moreover, other accompanied near edge characteristics peaks of B (6547 eV), and C (6556 eV) observed in ZMNO can be reproduced by simulation19 and calculation20 when Mn dopants occupy Zn sites in ZnO, indicating that Mn is effectively substituted into the ZnO lattice and has been experimentally conrmed.21 Figure 3 shows the magnetization as a function of the applied eld at 300 K for the Zn0.95Mn0.05O and Zn0.94Mn0.05 Na0.01O thin lms. The diamagnetic contribution from the quartz substrate has been subtracted from the raw data. Both samples demonstrate ferromagnetic hysteresis. However, the saturation magnetic moment (Ms) of the ZMNO lm is 1.52 lB/Mn, greater than that ($0.15 lB/Mn) of ZMO lm. As we know, neither Mn metal nor any oxide of Mn is RT ferromagnetic, the possibility of ferromagnetism in our ZMO and ZMNO lms originating from the secondary phases such as Mn or Mn related oxides can be excluded, which is consistent with the above structural analyses. Figure 4 shows the out-of-plane (magnetic eld perpendicular to the lm) and in-plane (magnetic eld parallel to the lm) magnetic eld dependences for a ZMNO thin lm. The magnetic anisotropy is a further proof of the intrinsic nature of the ferromagnetism in ZnO DMS materials,5,22 since cluster-related ferromagnetism is generally isotropic. The

FIG. 3. Magnetization hysteresis loops of Zn0.95Mn0.05O and Zn0.94Mn0.05 Na0.01O thin lms at 300 K.

easy axis of the magnetization is perpendicular to the surface while the hard axis of magnetization is in the plane but with larger coercivity (see inset). Similar anisotropic results were also observed previously5,9 and the anisotropy is conjectured somehow arose from an orbital moment.5 Based on the above results, the RTFM observed should be intrinsic. In the ZMO sample, the Mn2 substitution of the Zn2 does not introduce any carriers. Indeed, the as-grown ZMO lms in the present study are found to be highly insulating with q > 105 X cm. However, the weak p-type ZMNO samples were reproducibly produced with hole concentration of 9.51 1015-1.86 1017 cm3, being electrically stable over several months. The realization of p-type conversion in Na-doped ZnO lms veries the suggestion that NaZn may be a shallow acceptor.23,24 Moreover, the p-type conduction in the Zn0.94Mn0.05Na0.01O with enhanced FM supports the prediction that the ferromagnetic Mn2:ZnO state should be more stable in p-type samples.3 In order to provide more insights into this issue, we employed rst-principles calculations on the electronic structures and magnetic interactions

FIG. 2. Experimental Mn k-edge XANES spectra of Zn0.94Mn0.05Na0.01O, Mn metal, MnO, and MnO2.

FIG. 4. Anisotropic magnetism for a (Mn, Na)-codoped ZnO thin lm (Zn0.94Mn0.05Na0.01O). The in-plane magnetization shows a smaller saturated moment than out-of-plane magnetization. The inset is a magnied plot near zero eld showing larger coercivity for in-plane magnetization.

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FIG. 5. Calculated spin DOSs in the close conguration for (a) Mn-doped and (b) (Mn, Na)-codoped ZnO.

between the Mn ions in the Mn doped and (Mn, Na)-codoped ZnO. Since it is previously suggested that in the Mn-doped ZnO, the Mn distribution is slightly weighted in favor of nearest-neighbor pairs as dimmers via an intervening O atom (rather than stochastic distributed),8,15,25 thus in the present calculations, the Mn-Mn positions were arranged in a close conguration, in which the Mn ions in the same unit cell were separated by a single O ion. Likewise, the Na codopant is unlikely to distribute stochastically in the lm due to the limited concentration. Our calculations show that it is energetically favored when Na is accommodated near the Mn-O-Mn dimmer. Thus, we consider the geometry in which the Na ion substituted the nearest neighboring Zn in the same chain of Mn dimer as MnOMnONabonds. The densities of states (DOSs) for the ZMO and the ZMNO are illustrated in Fig. 5. For the Mn-doped ZnO, it is noticing that, despite the hybridization between the Mn 3d and O 2p states (Fig. 5(a)), Mn 3d states are rarely introduced at the Fermi level and no free carriers to mediate the long range FM interaction. Therefore, the superexchange interaction between the neighboring Mn2 ions is antiferromagnetic (AFM) in character (AFM state is 0.05 eV lower in energy than FM state). The origin of the observed small moment (0.15 lB/Mn) in the insulated Zn0.95Mn0.05O lm should arise from other mechanism such as bound magnetic polaron, as suggested previously in a nonequilibrium process.25 Turning to the codoped sample, as Na atoms replace some of the Zn sites in the Mn-doped ZnO, FM ground state is about 0.3 eV lower in energy than AFM. The total energy calculations revealed that a Na dopant derived shallow acceptor-type impurity state (spin-split) in close proximity to

the valance band edge with binding energy around 320 meV appeared (see Fig. 5(b)), which accounts for the p-type conductivity in the lm. Meanwhile, the Mn 3d partial DOSs are strongly hybridized with the Na 2p gap state. This interaction (p-d hybridization) leads to a ferromagnetic coupling between the two Mn ions mediated by holes (introduced by Na codoping). That is, the codoping of Mn and Na in ZMNO changes the Mn-Mn antiferromagnetic interactions to ferromagnetic coupling and thereby enhances the magnetic moment in the Zn0.94Mn0.05Na0.01O. Our results are in agreement with previous theoretical works that ferromagnetism favors in p-type Mn2:ZnO3,8,26,27 and are an extension of the spin-split donor impurity band model (Ref. 5) considered exclusively ferromagnetism in n-type materials. In summary, Zn0.95Mn0.05O and Zn0.94Mn0.05Na0.01O thin lms with RTFM were grown on amorphous quartz substrate using PLD. The XRD and XANES analyses as well as electrical measurements show that Mn-Na codoping leads to p-type fully non-polar Zn(Mn, Na)O thin lm with Mn incorporated substitutionally into the ZnO lattice at Zn sites. Compared to the Mn monodoped ZnO, the saturation magnetic moment is greatly enhanced by almost a factor of ten for the Mn-Na codoped sample. The observation of magnetic anisotropy in p-type ZMNO lm indicates that the ferromagnetism is intrinsic. First-principles calculations reveal that intrinsic Mn-doped ZnO favors AFM ordering and codoping of Mn and Na in Zn0.94Mn0.05Na0.01O changes the antiferromagnetic interaction to ferromagnetic due to the hybridization between Mn 3d and Na 2p at band gap. The hole-mediated FM obtained in p-type Zn0.94Mn0.05Na0.01O is consistent with that there is requirement of a hole-rich environment for FM predicted by theory. This work was supported by the National Natural Science Foundation of China (Grant Nos. 51002134 and 11004171) and Qianjiang Talent Project of Zhejiang Province (Grant No. 2011R10044).
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