Synthesis and magnetic properties of Zr doped ZnO Nanoparticles
© Zhang et al; licensee Springer. 2011
Received: 1 June 2011
Accepted: 10 November 2011
Published: 10 November 2011
Zr doped ZnO nanoparticles are prepared by the sol-gel method with post-annealing. X-ray diffraction results show that all samples are the typical hexagonal wurtzite structure without any other new phase, as well as the Zr atoms have successfully entered into the ZnO lattices instead of forming other lattices. Magnetic measurements indicate that all the doping samples show room temperature ferromagnetism and the pure ZnO is paramagneism. The results of Raman and X-ray photoelectron spectroscopy indicate that there are a lot of oxygen vacancies in the samples by doping element of Zr. It is considered that the observed ferromagnetism is related to the doping induced oxygen vacancies.
KeywordsZn1-xZrxO nanoparticles Room temperature ferromagnetism Oxygen vacancies
Diluted magnetic semiconductors (DMSs) have attracted intense interest due to their potential applications in spintronic devices [1–3]. DMSs are usually produced by doping semiconductors with transition metals (TMs). Through theoretically predicting, GaN and ZnO as typical n-type semiconductors would be ideal candidates for room-temperature (RT) DMSs . The room temperature ferromagnetism (RTFM) in TM-doped GaN has been reported in experiment and theroy, such as, Mn [5, 6], Gd , and Cr [8, 9]. Compared with GaN, ZnO has a lot of outstanding superiorities, as is known to all, which has a wide band-gap (3.37 eV at RT) and a high excitation binding energy (60 meV at RT), so ZnO has been got more and more attention. Otherwise, since Dietl et al. predicted that Mn-doped ZnO can show the clear RTFM and also has a higher Curie temperature (T C ) than RT , which triggered worldwide interest in research of the doping ZnO materials. At first, RTFM has been demonstrated for various kinds of TM-doped ZnO, for example, Mn , Co , Ni , and Fe . However, the origin of their magnetism remains controversy, because it is not yet clear whether the observed RTFM is truly intrinsic or related to secondary phases such as clusters . To avoid the impact from ferromagnetic (FM) elements, in recent years, RTFM in ZnO doping with other non-ferromagnetic elements has been discovered in experiment and theory, for instance, Cu [15, 16], V , Cr [18, 19], Li [20, 21], C , Er -doped ZnO. However, until now there is no consensus on the origin of FM in doping ZnO, so we researched the origin of RTFM in the doping ZnO materials, it was hoped that we could get a better explanation about this intractable issue.
Paul et al. prepared the Zr doped ZnO films using a sol-gel technique with post-annealing successfully and found the films of extremely great properties, such as in the structural, optical, and electrical aspects, otherwise, at higher Zr concentrations, increasing dopant atom forms some kinds of defects . Defects may cause FM to appear reported before [15, 23], so in this paper, we prepared Zr doped ZnO nanoparticles (NPs) by the same method and studied the structure and their magnetic property with the different Zr doping contents.
Zn1-xZrxO NPs were prepared by the sol-gel method with post-annealing. All the chemical reagents used as starting materials are analytic grade reagents and purchased without any further treatment. Firstly, 0.1 M Zn(NO3)2·6H2O and y M (y = 0.0005, 0.001, 0.0015, and 0.002) Zr(NO3)4·5H2O were dissolved into the ethylene glycol monomethylether (C3H8O2). Then, the dissolved solution was stirred for 4 h at 80°C and dried at 80°C in the oven to form the precursor. Finally, the precursor was annealed at 500°C for 1.5 h in the air and the series of Zn1-xZrxO NPs were obtained. At the same time, Zr contents of Zn1-xZrxO samples are consistent with the mole percentage (x = 0.005, 0.01, 0.015, and 0.02).
The morphologies of samples were characterized by scanning electron microscope (SEM, Hitachi S-4800, Hitachi High Technologies America, Inc., Schaumburg, IL, USA) and transmission electron microscope (TEM, JEM-2010, JEOL Ltd., Tokyo, Japan). Selected area electron diffraction (SAED) and x-ray diffraction (XRD, X' Pert PRO PHILIPS with Cu Kα radiation, PANalytical, Shanghai, People's Republic of China) were employed to study the structure of the samples. The vibration properties were characterized by the Raman scattering spectra measurement, which was performed on a Jobin-Yvon LabRam HR80 spectrometer (Horiba Jobin Yvon Inc., Edison, NJ, USA) with a 325 nm line of Torus 50 mW diode-pumped solid-state laser under backscattering geometry. X-ray photoelectron spectroscopy (XPS, VG ESCALAB 210, VG Scientific Ltd., East Grinstead, UK) was utilized to determine the bonding characteristics and the composition of the particles. The measurements of magnetic properties were made using vibrating sample magnetometer (VSM, Lakeshore 7304, Lakeshore Cryotronics, Inc., Westerville, OH, USA) and Quantum Design MPMS magnetometer based on superconducting quantum interference device (SQUID).
Results and discussion
In other element-doping systems, different mechanisms of FM have been reported. Hou et al. reported that the carrier-induced FM (RKKY or double exchange mechanism) might be applied to explain the FM in Cu-doped ZnO films, in which the free carrier concentration is vital to determine whether the material is PM or FM . Meanwhile, Hu et al. found that Cr ion substitution is necessary for establishing FM in Cr-doped ZnO films containing VZn. However, Ran et al. suggested that defects of Cu-doped ZnO films, such as oxygen vacancies and/or zinc interstitials, might contribute to the RTFM, thus, the observed RTFM was explained in terms of defect-related models . Otherwise, Qi et al. concluded that an exchange mechanism associated with oxygen vacancies was responsible for the FM in the Zn1-xErxO thin films . At the same time, the RTFM was clearly observed in In-doped ZnO nanowires, which may be associated with oxygen vacancies induced by In doping . In our system, the pure ZnO NPs show the PM behavior, but all of the other doping samples exhibit the clear RTFM, so it's sure that the RTFM is induced by doping of Zr. In the XRD patterns, all the intense peaks from Zn1-xZrxO (x = 0.005, 0.01, 0.015, 0.02) could be indexed the same hexagonal wurtzite structure as pure ZnO NPs, the increase in a and c parameter as a function of Zr concentration is consistent with the substitution of Zn2+ ions (0.74 Å) by Zr4+ ions (0.84 Å) [25, 26]. The more Zn2+ were substituted by Zr4+, the greater lattice distortion of ZnO would be generated, the more vacancies and/or interstitials should be got. After measured the Raman and XPS, our supposition has been affirmed that there are lots of oxygen vacancies in our samples. As a result, oxygen vacancies should be considered as the origin of FM in our samples, which seems to be similar to the series of Er , In -doped ZnO, where the oxygen vacancies also play a crucial role in the RTFM.
We successfully prepared Zn1-xZrxO NPs with the typical pure ZnO hexagonal wurtzite structure by the sol-gel method with post-annealing. All the samples have the clear RTFM, and M s per Zr atom of samples is sensitive to the content of Zr, and decreases continuously as the increase of the doping Zr content through the magnetic measurement at RT. Combining with the results of Raman and XPS, we suppose that the FM of the Zn1-xZrxO NPs is owing to the oxygen vacancies inducing by doping of the nonmagnetic element of Zr.
This work is supported by National Science Fund for Distinguished Young Scholars (Grant No. 50925103 and 11034004), the Keygrant Project of Chinese Minisity of Education (Grant No. 309027), and NSFC (Grant No.50902065).
- Dietl T, Ohno H: Ferromagnetic III-V and II-VI Semiconductors. Mrs Bull 2003, 28: 714. 10.1557/mrs2003.211View ArticleGoogle Scholar
- Hong NH, Sakai J, Huong NT, Poirot N, Ruyter A: Role of defects in tuning ferromagnetism in diluted magnetic oxide thin films. Phys Rev B 2005, 72: 045336.View ArticleGoogle Scholar
- Liu H, Zhang X, Li LY, Wang YX, Gao KH, Li ZQ, Zheng RK, Ringer SP, Zhang B, Zhang XX: Role of point defects in room-temperature ferromagnetism of Cr-doped ZnO. Appl Phys Lett 2007, 91: 072511. 10.1063/1.2772176View ArticleGoogle Scholar
- Dietl T: Ferromagnetic semiconductors. Semicond Sci Technol 2002, 17: 377. 10.1088/0268-1242/17/4/310View ArticleGoogle Scholar
- Chambers SA: Ferromagnetism in doped thin-film oxide and nitride semiconductors and dielectrics. Surf Sci Rep 2006, 61: 345. 10.1016/j.surfrep.2006.05.001View ArticleGoogle Scholar
- Aoki M, Yamane H, Shimada M, Kajiwara T: Single crystal growth of manganese gallium nitride using Mn-Ga-Na melt. J Alloy Compd 2004, 364: 280. 10.1016/S0925-8388(03)00506-1View ArticleGoogle Scholar
- Litvinov VI, Dugaev VK: Room-temperature ferromagnetism in dielectric GaN(Gd). Appl Phys Lett 2009, 94: 212506. 10.1063/1.3143670View ArticleGoogle Scholar
- Cui XY, Medvedeva JE, Delley B, Freeman AJ, Newman N, Stampfl C: Role of Embedded Clustering in Dilute Magnetic Semiconductors: Cr Doped GaN. Phys Rev Lett 2005, 95: 256404.View ArticleGoogle Scholar
- Wang Q, Sun Q, Jena P, Kawazoe Y: Ferromagnetic to ferrimagnetic crossover in Cr-doped GaN nanohole arrays. Phys Rev B 2007, 75: 075312.View ArticleGoogle Scholar
- Dietl T, Ohno H, Matsukura F, Cibert J, Ferrand D: Zener Model Description of Ferromagnetism in Zinc-Blende Magnetic Semiconductors. Science 2000, 287: 1019. 10.1126/science.287.5455.1019View ArticleGoogle Scholar
- Yang T, Li Y, Zhu MY, Li YB, Huang J, Jin HM, Hu YM: Room-temperature ferromagnetic Mn-doped ZnO nanocrystal synthesized by hydrothermal method under high magnetic field. Mater Sci Eng B 2010, 170: 129. 10.1016/j.mseb.2010.03.037View ArticleGoogle Scholar
- Chaudhary S, Bhatti KP, Pandya DK, Kashyap SC, Nigam AK: Effect of indium incorporation in Zn 1-x Co x O thin films. J Magn Magn Mater 2009, 321: 966. 10.1016/j.jmmm.2008.03.009View ArticleGoogle Scholar
- Tong LN, He XM, Han HB, Hu JL, Xia AL, Tong Y: Effects of H 2 annealing on ferromagnetism of Ni-doped ZnO powders. Solid State Commun 2010, 150: 1112. 10.1016/j.ssc.2010.03.029View ArticleGoogle Scholar
- Hong NH, Sakai J, Brize V: Observation of ferromagnetism at room temperature in ZnO thin films. J Phys: Condens Matter 2007, 19: 036219. 10.1088/0953-8984/19/3/036219Google Scholar
- Gao DQ, Xue DS, Xu Y, Yan ZJ, Zhang ZH: Synthesis and magnetic properties of Cu-doped ZnO nanowire arrays. Electrochim Acta 2009, 54: 2392. 10.1016/j.electacta.2008.10.051View ArticleGoogle Scholar
- Kim CO, Kim S, Oh HT, Choi SH, Shon Y, Lee S, Hwang HN, Hwang CC: Effect of electrical conduction properties on magnetic behaviors of Cu-doped ZnO thin films. Physica B 2010, 405: 4678. 10.1016/j.physb.2010.08.061View ArticleGoogle Scholar
- Wang Q, Sun Q, Jena P, Hu Z, Note R, Kawazoe Y: First-principles study of magnetic properties in V-doped ZnO. Appl Phys Lett 2007, 91: 063116. 10.1063/1.2768628View ArticleGoogle Scholar
- Shi HL, Duan YF: First-Principles Study of Magnetic Properties of 3 d Transition Metals Doped in ZnO Nanowires. Nanoscale Res Lett 2009, 4: 480. 10.1007/s11671-009-9260-7View ArticleGoogle Scholar
- Zhuge LJ, Wu XM, Wu ZF, Chen XM, Meng YD: Effect of defects on room-temperature ferromagnetism of Cr-doped ZnO films. Scrirta Mater 2009, 60: 214. 10.1016/j.scriptamat.2008.10.002View ArticleGoogle Scholar
- Chawla S, Jayanthi K, Kotnala RK: Room-temperature ferromagnetism in Li-doped p -type luminescent ZnO nanorods. Phys Rev B 2009, 79: 125204.View ArticleGoogle Scholar
- Meyer BK, Hofstaetter A, Laguta VV: Tunneling phenomena of trapped holes in ZnO: Li. Physica B 2006, 376: 682.View ArticleGoogle Scholar
- Pan H, Yi JB, Shen L, Wu RQ, Yang JH, Lin JY, Feng YP, Ding J, Van LH, Yin JH: Room-Temperature Ferromagnetism in Carbon-Doped ZnO. Phys Rev Lett 2007, 99: 127201.View ArticleGoogle Scholar
- Qi J, Yang YH, Zhang L, Chi JH, Gao DQ, Xue DS: Room-temperature ferromagnetism in Er-doped ZnO thin films. Scrirta Mater 2009, 60: 289. 10.1016/j.scriptamat.2008.10.015View ArticleGoogle Scholar
- Paul GK, Bandyopadhyay S, Sen SK, Sen S: Structural, optical and electrical studies on sol-gel deposited Zr doped ZnO films. Mater Chem Phys 2003., 79(71):
- Mezdrogina MM, Danilevskii EY, Kuz'min RV, Poletaev NK, Trapeznikova IN, Chukichev MV, Bordovskii GA, Marchenko AV, Eremenko MV: The effect of Fe, Cu, and Si impurities on the formation of emission spectra in bulk ZnO crystals. Semiconductors 2010, 44: 426. 10.1134/S1063782610040032View ArticleGoogle Scholar
- Fornasiero P, Monte RD, Rao GR, Kaspar J, Meriani S, Trovaralli A, Graziani M: Rh-Loaded CeO 2 -ZrO 2 Solid Solutions as Highly Efficient Oxygen Exchangers: Dependence of the Reduction Behavior and the Oxygen Storage Capacity on the Structural Properties. Journal of Catalysis 1995, 151: 168. 10.1006/jcat.1995.1019View ArticleGoogle Scholar
- Reddy BM, Chowdhury B, Reddy EP, Fernandez A: Characterization of MoO 3 /TiO 2 -ZrO 2 catalysts by XPS and other techniques. J Mol Catal A 2000, 162: 431. 10.1016/S1381-1169(00)00336-8View ArticleGoogle Scholar
- Wei XQ, Man BY, Liu M, Xue CS, Zhuang HZ, Yang C: Blue luminescent centers and microstructural evaluation by XPS and Raman in ZnO thin films annealed in vacuum, N 2 and O 2 . Physica B 2007, 388: 145. 10.1016/j.physb.2006.05.346View ArticleGoogle Scholar
- Chen M, Wang X, Yu YH, Pei ZL, Bai XD, Sun C, Huang RF, Wen LS: X-ray photoelectron spectroscopy and auger electron spectroscopy studies of Al-doped ZnO films. Appl Surf Sci 2000, 158: 134. 10.1016/S0169-4332(99)00601-7View ArticleGoogle Scholar
- Pradhan AK, Zhang K, Loutts GB, Roy UN, Cui Y, Burger A: Structural and spectroscopic characteristics of ZnO and ZnO:Er 3+ nanostructures. J Phys: Condens Matter 2004, 16: 7123. 10.1088/0953-8984/16/39/043Google Scholar
- Coey JMD, Venkatesan M, Fitzgerald CB: Donor impurity band exchange in dilute ferromagnetic oxides. Nat Mater 2005, 4: 173. 10.1038/nmat1310View ArticleGoogle Scholar
- Herng TS, Qi DC, Berlijn T, Yi JB, Yang KS, Dai Y, Feng YP, Santoso I, Sanchez-Hanke C, Gao XY, Wee ATS, Ku W, Ding J, Rusydi A: Room-Temperature Ferromagnetism of Cu-Doped ZnO Films Probed by Soft X-Ray Magnetic Circular Dichroism. Phys Rev Lett 2010, 105: 207201.View ArticleGoogle Scholar
- Hou DL, Ye XJ, Zhao XY, Meng HJ, Zhou HJ, Li XL, Zhen CM: Room-temperature ferromagnetism in n-type Cu-doped ZnO thin films. J Appl Phys 2007, 102: 033905. 10.1063/1.2764203View ArticleGoogle Scholar
- Hu YM, Hsu CW, Wang CY, Lee SS, Wang SJ, Han TC, Chou WY: Room-temperature ferromagnetism in co-sputtered Zn 1-x Cr x O films with low Cr content. Scrirta Mater 2009, 61: 1028. 10.1016/j.scriptamat.2009.08.018View ArticleGoogle Scholar
- Ran FY, Tanemura M, Hayashi Y, Hihara T: Effect of substrate temperature on the room-temperature ferromagnetism of Cu-doped ZnO films. J Cryst Growth 2009, 311: 4270. 10.1016/j.jcrysgro.2009.07.008View ArticleGoogle Scholar
- Liu KW, Sakurai M, Aono M: Indium-doped ZnO nanowires: Optical properties and room-temperature ferromagnetism. J Appl Phys 2010, 108: 043516. 10.1063/1.3464229View ArticleGoogle Scholar
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