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Functional Materials Letters Vol. 4, No. 1 (2011) 1–4 © World Scientiﬁc Publishing Company DOI: 10.1142/S179360471100152X
ROOM TEMPERATURE FERROMAGNETISM IN PURE AND Cu DOPED ZnO NANORODS: ROLE OF COPPER OR DEFECTS
SHALENDRA KUMAR∗ , B. H. KOO and C. G. LEE† School of Nano & Advanced Materials Engineering Changwon National University, 9 Sarim Dong Changwon 641-773, Republic of Korea ∗firstname.lastname@example.org †email@example.com SANJEEV GAUTAM and K. H. CHAE Nano Analysis Center, Korea Institute of Science and Technology Seoul 136-791, Republic of Korea S. K. SHARMA and M. KNOBEL Instituto de Fisica Gleb Wataghin, Universidade Estadual de Campinas (UNICAMP) Campinas, 13.083-859, SP, Brazil
Received 7 October 2010; Revised 10 January 2011
We report structural, magnetic and electronic structure studies of pure and Cu doped ZnO nanorods with the aim to understand the origin of ferromagnetism. A structural study indicates that all the samples exhibit single phase nature and rules out the formation of secondary phase. NEXAFS measurements reveal that Cu atom exists in Cu2+ state. Magnetic hysteresis loop measurements reﬂect that the pure and Cu doped ZnO nanorods exhibit room temperature ferromagnetism. The increase in the intensity of green emission in photoluminescence study indicates that defects density increases with Cu doping. Keywords: DMS; ZnO; x-ray diffraction; photoluminescence; NEXAFS; DC magnetization.
In the recent years dilute magnetic semiconductors (DMS) has attracted the interest of researchers due to their potential application in spintronics devices.1–3 Initially, it was assumed that DMS and their properties can be tailored by partial replacement of cations in semiconducting host matrix via transition metal (TM) cations. But the discovery of the unexpected magnetism in HfO2 ,4 TiO2 ,5 ZnO6 etc. has triggered a debate on the origin of ferromagnetism in the DMS. Several experimental as well as theoretical groups have reported the origin of ferromagnetism in the nanoparticles or thin ﬁlms of diamagnetic oxides. Though, among the diamagnetic oxides showing the d 0 ferromagnetism, zinc oxide (ZnO) has been recognized as one of the most important materials for the application in the multifunctional devices because of its various properties. Even though ferromagnetism has been observed in a number of systems, experimental studies on TM doped ZnO have produced inconsistent results and the mechanism of
ferromagnetism (FM) in TM doped ZnO remains unclear. It is considered that the TM dopants in ZnO form clusters or secondary phase therefore having many controversies about whether the observed FM is an intrinsic or extrinsic property of the material. These facts motivated us to study the FM in Cu doped ZnO. As it is well known that Cu is a potential magnetic ion only in +2 state with +1/2 spin and neither metallic Cu nor its oxide (CuO and Cu2 O) is ferromagnetic. In these circumstances, Cu doped ZnO has potential of showing magnetic behavior at RT because FM observed in Cu based system will undoubtedly be the intrinsic property of the material. Despite the above fact, Cu doped ZnO system is not far away from controversies. There are many contradictory reports in which some authors conﬁrmed the presence of FM in this system whereas others ruled out same.7–10 These controversial results indicate that FM in DMSs is very sensitive to preparation method and conditions. In this letter, we have reported room temperature ferromagnetism in Cu doped ZnO synthesized by co-precipitation
However.11.14 elucidated FM in the light of bound magnetic polarons (BMP) model. From the XRD analysis.13 predicted that FM in Cu–ZnO originates from the hybridization of the Cu 3d and O 2 p bands.0 ≤ x ≤ 0.0 ≤ x ≤ 0. transmission electron microscopy (TEM). Appropriate proportion of analytical grade metal nitrate [Zn(NO3)2 ·6H2 O and Cu(NO3 )2 · 3H2 O] were thoroughly mixed according to desired stoichiometry and is reported elsewhere. The inter-planer distance (d = 2.11 XRD measurements were carried out at room temperature using a Phillips X’pert (MPD 3040) with a Cu K α source (λ = 1. Zn1−x Cux O (0. The normalized room temperature photoluminescence (PL) spectra for pure and Cu doped ZnO nanorods is shown in Fig. The NEXAFS measurements of these samples along with the reference compounds were performed at the soft x-ray beam line at 7B1 XAS and 10B XRS of KIST-PAL. Kumar et al. technique. The NEXAFS measurements performed at Cu K -edge clearly indicate that Cu has 3d9 electronic conﬁguration. Moreover. the saturation magnetization (M S ) values are smaller than those obtained for Cu–ZnO. the HRTEM and SAED pattern (due to the brevity of article. it is agreed unanimously that the . 2011 20:31 S1793-6047 00152 2 S. size crystallite of Cu2 O and CuO. 2 represents the magnetic hysteresis loop of pure and Cu doped ZnO measured at 300 K.March 22. while other peaks were detected in blue-green region. The data was normalized and processed using Athena 0.05). DC magnetization and near edge x-ray absorption ﬁne structure spectroscopy (NEXAFS) measurements. 1 and 5% Cu doped ZnO is 88.0 ≤ x ≤ 0. it is observed that the peaks position shifted towards lower 2θ values with Cu contents (see inset in Fig. 2. It is clear from the M–H curve that the magnetic moment of Cu doped ZnO is higher compared to pure ZnO.10 explained FM in Cu-ZnO on the basis of indirect exchange interactions using the carrier mediated model and Herng et al. Inset shows M-H curve of Zn1−x Cux O (0.2.05) nanorods were prepared by co-precipitation method.05).05) performed as a function of magnetic ﬁeld shows that pure and Cu doped ZnO samples display the ferromagnetic ordering at RT. Ye et al. Figure 1 shows XRD patterns for Cu doped ZnO nanorods.54 Å). Inset in Fig.05). 2. The origin of FM in Cu-ZnO is still not clear. Hou et al.0 ≤ x ≤ 0.056/IFEFFIT 1. The patterns were analyzed and indexed using Powder-X software which indicates that all samples exhibit single phase nature with wurtzite lattice and exclude the possibility of secondary phase formation within the limit of XRD. Magnetization measurements were performed at room temperature using a commercial Quantum Design Physical properties measurement system (PPMS). therefore. Till now. 1.0 ≤ x ≤ 0. not shown here) also indicate that there is no formation of nano Fig. Such a shift in XRD with Cu doping has been reported in literature by Tiwari et al. 1) which suggest that the lattice parameters increased with Cu doping.63 = (002) plane) calculated from the HR-TEM corresponds to the wurtzite phase of ZnO which suggests that Cu ions are occupying the Zn position in ZnO matrix. The coercive ﬁeld at 300 K for pure. Magnetization of Zn1−x Cux O (0. (Color online) XRD pattern of Zn1−x Cux O (0. the FM may results due to the Cu doping as well as defects. By comparing our results to the reported in the literature. TEM measurements were performed using HR-TEM (JEM 2100F). The effect of Cu doping has been studied using x-ray diffraction (XRD). For pure ZnO. (Color online) Photoluminescence spectra of Zn1−x Cux O (0. photoluminescence. this observed magnetic behavior may be explained in the light of BMP model.10–13 In the present case. Inset shows the extended view of (002) plane. 48 and 40 Oe respectively.12 for Cu doped ZnO thin ﬁlms and assumed to be an additional evidence for Cu occupying the Zn sites in ZnO matrix. Fig.8. a high intensity sharp peak at 385 nm in the UV-region is observed.
. however the pre-edge intensity is mostly inﬂuenced by the Cu coordination geometry.. TM doping. we have observed two peaks with high intensity in UV and green region as compared to pure ZnO. The spectral features between 540 and 550 eV is attributed to the hybridization of O 2 p and Zn/Cu 4 p orbitals. it is clear from our results that TM doping can also vary the DLE position and relative intensities (see Fig.19 reported that blue-green emission positions and intensities vary with the annealing temperature and time. Figure 3 shows the Cu K -edge NEXAFS spectra of Cu doped ZnO along with reference spectra of Cu metal. (color online) (a) Cu K -edge spectra of Zn1−x Cux O (0. Figure 4(a) displays O K -edge NEXAFS spectra for pure and Cu doped ZnO nanorods. The observed NEXAFS spectral features of Cu of doped ZnO are very similar to those of CuO which indicates that Cu ions are in +2 state. It can be noticed that the pre-edge spectral feature located ∼8985 eV exist for spectra except Cu2 O and Cu metal foil (see inset of Fig. whereas the high intensity refer to noncentrosymmetric geometries (e. However. Wang et al. the room temperature PL spectrum of Cu doped ZnO shows that green emission has a blueshift with relatively high intensity compare to pure ZnO which further support that Cu ions are substituted for tetrahedrally coordinated Zn2+ ions in ZnO matrix.18 suggested that the unstructured green emission in ZnO results from a triplet excited state of neutral oxygen vacancy. which form the bottom of the conduction band. 2011 20:31 S1793-6047 00152 Room Temperature Ferromagnetism in Pure and Cu Doped ZnO Nanorods: Role of Copper or Defects 3 UV emission originated from the near-band-edge emission (NBE) transition in band gap of ZnO called recombination of free excitons through an exciton-exciton collision process while the mechanism of the blue-green emission is related to oxygen vacancy or Zn interstitials.g. this transition is allowed only when the empty d state are available such as in the 3d 9 electronic state of the Cu2+ ion and the structural unit around the absorbing atoms lacks centro-symmetry. The low intensity of the Fig. Dingle et al. By comparing the NEXAFS spectra of pure and Cu doped ZnO. a sharp emission peak similar to Dingle is originated due to short lived transfer of an electron from neighboring oxygen to the Cu ions. The appearance of these new spectral features (at ∼529 and 532 eV) and increase in their intensity with . The high intensity of the green emission in Cu doped ZnO suggests that the copper impurity creates deep level defect state in the band gap of ZnO.20 extended this theory and proposed that Cu may exist in Cu1+ or Cu2+ state. However.March 22. Based on the existing literature and band structure calculations.0 ≤ x ≤ 0. CuO and Cu2 O. 3. 4(b)]. In general. and the oxygen vacancies are responsible for the green emission in ZnO.g. Moreover it is found that UV emission has blueshift for 1 and 5% Cu doping in comparison to the pure ZnO. The spectral feature above 550 eV can be assigned to the hybridization between O 2 p and Zn and Cu 4d states. It can be seen from the PL spectra that 1% Cu doped ZnO has the highest intensity of the green emission peaks which indicate that the density of the defects is higher in case of 1% Cu doped ZnO. It is evident from spectra that the intensity of the peak at ∼529 increases with Cu doping which indicates the strong hybridization of O 2 p orbital with Cu 3d orbitals [see Fig. Various groups have reported different theory of green emission in ZnO. it is observed that two extra spectral features evolve at ∼529 (marked by A1 ) and 532 eV (marked by B1 ).15. pre-edge centroid position depends strongly on the Cu oxidation state. Reynold et al. 2).17 proposed that the structured green emission in ZnO is due to a transition from two shallow donors to a deep acceptor while Leiter et al. 3).05). Previously. the spectral feature in the energy range of 530–539 eV can be attributed to the hybridization between O 2 p and Zn/Cu 3d/4s states. pre-edge peak refer to the geometries with center of symmetry (e.16 suggested that DLE in Cu doped ZnO is due to the charge transfer between Cu2+ ions and adjacent oxygen atoms (hole transfers from d shell to sp3 orbitals). octahedral). tetrahedral). The Cu1+ ion prohibit such a transition due to 3d 10 electronic conﬁguration. in the present case. In line with their ﬁndings. Graces et al. If Cu is in +1 state then it will give the structure less emission that is due to donor-acceptor pair recombination involving the copper acceptor and a shallow donor impurity whereas in presence of Cu2+ ions. This spectral feature arises due to the quadrupole 1s → 3d transition and has a significant intensity because of 3d−2 p orbital mixing. However.16 The origin of bluegreen emission in ZnO has remained controversial for the last decades and it has been assumed that defects.
X. 622 (2002). Phys. Yang et al. Acta Phys. Phys. D. Buchhold. C.. Garces. McGuinness. H.-D. reﬂecting that the doping of Cu and oxygen vacancy barely inﬂuences the electronic state of Zn and thereby ruling out the existence of Zn interstitials. 4. Dorneles et al. Appl. 033203 (2006). Rev. Phys. Phys. H. Y. Ye. Nanotechnology 19. 20. Appl. Lett. we further analyzed the O K -edge spectra. 6189 (2001). Magn.05). Phys.. L. Hofstaetter et al. T. Meng et al. F. Lett. S. H. 082504 (2005). B. Lett. 89. Koo et al. 139 (2001). Bai et al. Song et al. 91. 23.22 also studied the effect of defects and oxygen vacancies using Ar-ion implantation and Ar annealing on O K -edge spectra of ZnO. 110 (1999). References Fig. SKS and MK acknowledge the ﬁnancial support from FAPESP and CNPq. Appl.. Science 282. Dietl. 162503 (2007). B. Acknowledgment This work was supported by BK21 project corp. 012501 (2007). J. S.. Singh et al. NEXAFS and magnetization results show that RTFM results from the defects and Cu ions. 21. Ma et al. 17. D. J.0 ≤ x ≤ 0. H. Zheng. J. Narayan and J. L. P. It can be seen from the inset in the Fig. R. 10. In order to see the effect of Cu or defect. Vanheusden. 4. A. J. J. 12. Mater. Lett. 2. Chang. Thakur et al. Chae. . which is in good agreement with PL studies. 1660 (1998). L. Phys. M. Inset shows normalized O K -edge NEXAFS spectra of Cu doped ZnO (0. 185505 (2009). Phys. Phys. D. Appl. Lett. Wang. Phys. 200. Brazil. 21. They observed that the intensity of peak at ∼532 eV increases with increase in number of defects in ZnO. NEXAFS measurements show that Cu ions exist in +2 states. P.. 105. R.. we observed same features at 537 eV. In contrast. 5. Z. 217205 (2005). Hou. 062509 (2008). 403 (1996). Magn. 062504 (2007). L. 2011 20:31 S1793-6047 00152 4 S. P.. Lett. The intensity of O K NEXAFS spectra is proportional to the density of unoccupied state and the oxygen concentration. 11. Phys.. Ye. Therefore. Q. 15. From NEXAFS study. C. J. The increase in the intensity of the spectral features is a direct indication of increase in the number of O 2 p holes in Cu doped samples. Cu doping demonstrates that doping of Cu introduced unoccupied 3d states within the band gap of ZnO. Y. Appl. J. Rev. S. 81. R. Delley. J. D. 951 (1998). Lau. H.21 reported similar results in case of Mn doped ZnO.. 142502 (2007). F. A. 94. Phys. Phys. S. PL study indicates that Cu doping enhanced the defects G. Sanvito. 19. A. R4 (2001). 9. 90. PL. J. Warren et al. Phys. Kumar et al. Y. T. Chakraborti. Phys. Pol. 13.23 reported that spectral features at 537 eV appears due to the presence of the O vacancy. 16.05). App. Krishnamurthy. H. Phys. In summary. Yoon. Jogai. C. Kim et al. Lett. X. 73. X. in ZnO. Thakur et al. Lett. H. H. Alves. S. S. 22.05). Kumar et al.. Ohno. Ohno. J. Kim. Appl. Keavney. T. 92. 4(b) shows the normalized O K -edge NEXAFS spectra. Prater. K. Look and B. 99. C. Kumar.B.March 22. (b) Difference spectra of Zn1−x Cux O (0. it is clear that Cu doping enhances the defects in the Cu doped ZnO. D.: Condens. J. C.. 87. R. 08M111 (2006). App. Appl. Krishnamurthy et al. Lett. Status Solidi B 226. J. 7. A 100. Seager. L. J. H. 3. Inset in Fig. Rev. Phys. 07C520 (2009). the Zn K -edge (due to the brevity of the article not shown in the manuscript) of all the samples closely resembles each other. R. Reynolds. 6. P.0 ≤ x ≤ 0. Yu et al. Tiwari. A. P. Zuo. 579 (1969). Dingle. 91. P. 90. Magnetization studies reﬂect that pure and Cu doped samples show RTFM and magnetization increases with Cu doping. Leiter. Singh.0 ≤ x ≤ 0. App. A. 103. Wang. we have successfully synthesized single phase Cu doped ZnO nanorods using co-precipitation method. Liu et al. H. D. Matter. In the present work... 07B911 (2008). Kumar. Herng. S. Phys. 086101 (2006).. Phys. W. 8. N. 18. Prinz. Appl. (Color online) (a) O K -edge spectra of Zn1−x Cux O (0. Das Pemmaraju and S. 68. Science 281. 455702 (2008). Snure. A. Freeman and B. 4(b) that the intensity of the spectral features increases with Cu doping and has maximum intensity for 1% Cu doped ZnO. which intensity increases with Cu doping and has a higher value for 1% doping. Lett. J. D. Appl. Appl. L. Thakur. D. J. 14. H. 23. 1. 99. Buchholz. K.
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