J Mater Sci: Mater Electron DOI 10.

1007/s10854-012-0745-2

Influence of annealing temperature on structural, optical and magnetic properties of Zn0.97Cu0.01V0.02O nanoparticles
Huilian Liu • Xin Cheng • Hongbo Liu • Jinghai Yang Jian Cao • Yang Liu • Xiaoyan Liu • Ming Gao • Maobin Wei • Lianhua Fei • Xu Zhang

Received: 18 February 2012 / Accepted: 28 April 2012 Ó Springer Science+Business Media, LLC 2012

Abstract Zn0.97Cu0.01V0.02O nanoparticles have been successfully prepared by the sol–gel method and sintered in air at the different temperature. The effects of the annealing temperature on the structural, optical and magnetic properties of the obtained samples were studied. The X-ray diffraction (XRD) results showed that the Zn0.97Cu0.01V0.02O nanoparticles was single phase with the ZnO-like wurtzite structure when the annealing temperature was00 °C. The photoluminescence (PL) spectra revealed that as the annealing temperature increased, the intensity of the UV emission increased and the green emission enhanced significantly. Magnetic measurements indicated that the samples exhibited ferromagnetism at the room temperature. The results of XRD, transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) revealed that there was no ferromagnetic-related secondary phase in Zn0.97Cu0.01V0.02O nanoparticles, the ferromagnetism of the Zn0.97Cu0.01V0.02O samples was originated from the fact that the Cu and V ions doped into the ZnO lattice. In addition, the saturation magnetization (Ms) increased with the enhancement of the annealing temperature.

1 Introduction Zinc oxide (ZnO) has been attracted considerable attention for its potential applications in ultraviolet light emitters, nonlinear optical devices, gas sensors, spin functional devices, piezoelectric transducers and surface acoustic wave devices [1–5] due to the excellent chemical and thermal stability, and specific electrical properties. Recently, ZnO-based diluted magnetic semiconductors (DMS) have been recognized as the ideal candidate materials for spintronics, by virtue of the fact that ZnO doped with the transition metal (TM) elements showed room temperature ferromagnetism (RTFM) [6–13]. However, there is still no definite conclusion on the nature of the RTFM for the DMS, some reports claim that the magnetic signature arises from clustering or impurities while others claim that the magnetic property is intrinsic. In order to avoid the controversies, non-magnetic elements doped ZnO have been studied [14–17]. Since that Cu is a kind of non-magnetic element and CuO (Cu2O or clustering) is non-ferromagnetic, which is easy to avoid the controversies regarding the origin of the ferromagnetism, making the interpretation of the ferromagnetism more easily [18–20]. Theoretical studies had predicted that doping the V element in the semiconductor oxide may lead to the RTFM [21]. Although many researchers had studied the effects of the structure on the optical and magnetic properties in the ZnVO nanomaterials, the origin of the ferromagnetism for the ZnO based DMS is still in dispute [22–24]. From the point view of the mean field theory, the carrier concentration in the TM doped ZnO-based DMS can influence the ferromagnetic property [25, 26]. Recently, several researchers [27–30] proposed that doping another ion into the TM doped ZnO-based DMS may be an effective way to change the magnetic property of the original sample by introducing the additional

H. Liu Á X. Cheng Á H. Liu Á J. Yang (&) Á J. Cao Á Y. Liu Á X. Liu Á M. Gao Á M. Wei Á L. Fei Á X. Zhang Institute of Condensed State Physics, Jilin Normal University, Siping 136000, People’s Republic of China e-mail: jhyang1@jlnu.edu.cn H. Liu Á X. Cheng Á H. Liu Á J. Yang Á J. Cao Á Y. Liu Á X. Liu Á M. Gao Á M. Wei Á L. Fei Á X. Zhang Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, Jilin Normal University, Siping 136000, Jilin, China

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97Cu0. which was excited by a continuous He– Cd laser at a wavelength of 325 nm and a power of 10mW.02O particles annealed at 500 and 600 °C. We focused on the structural and physical properties caused by the different annealing temperatures.which indicates that sintering temperature should be below 700 °C so as to obtain the single-phase Zn0. the powders were dissolved in water to get a homogeneous solution.02O powders have been prepared by the sol–gel method to investigate the influence of the annealing temperature on their structural. The PL measurements of the samples were performed on an HR800 Labram Infinity Spectrophotometer. 9.01V0.02O samples annealed at different temperatures.J Mater Sci: Mater Electron carriers. vanadium metal and any other impurity phases are detected when the samples are sintered at 400.9 %) highpurity powders were thoroughly mixed according to the desired stoichiometry.02O sample was performed by XRD on D/max-2500 copper rotating-anode X-ray diffractometer with Cu Ka radiation (40 kV. When the temperature was 00 °C.5 %) while stirring for 2 h.97Cu0. 600 and 700 °C). After the swelled xerogel was completed at 130 °C. Moreover. which indicates that the wurtzite structure is not changed by doping. The solution was dried at 80 °C to obtain xerogel. No trace of the copper metal.9 %). 1 XRD patterns of Zn0.01V0. The chemical composition of the Zn0. However.02O powders annealed at the different temperatures are shown in Fig.02O powders was enlarged without altering the crystal structure when increasing the annealing temperature.97Cu0. the deliberate co-doping with acceptor is essential for the enhancement of the solubility of the acceptors with the stabilization of the ionic charge distributions and the reduction of acceptor binding energy [27. 500 and 600 °C. 200 mA).1 Structural characteristics Typical XRD patterns of the Zn0. In air atmosphere. The size distribution and interplanar distance were investigated by the TEM (200 keV. when the annealing temperature is 700 °C.0.97Cu0.01V0. which is in accordance with the results of the XRD.01V0. the Zn0. The morphologies of all the samples are found to be nearly spherical in nature with the diameters ranging from 10 to 30 nm.97Cu0.01V0. it can be observed that the intensity and the full width at half maximum (FWHM) of the diffraction peak increases when the annealing temperature increase from 400 to 600 °C. Since that annealing treatment have a great effect on the properties of the TM-ZnO DMS.5 and 30. Figure 2a and b show the representative TEM images of the Zn0. From Fig. 1. a reticular substance was obtained. However. there is little detail report on the effects of the annealing temperature on the properties of the Cu and V co-doped ZnO powders. the crystallinity of the sample is not very good.97Cu0. the average particle size was calculated to be 6. respectively.02O powders annealed at 500 and 600 °C were determined by XPS (VG ESCALAB Mark II). In our work.01V0. But when the sample annealed at 400 °C. Filled diamond indicates the peaks of the impurity phase of CuO 2 Experimental details Appropriate proportions of Zn(NO3)2Á6H2O (99. Consequently. a second phase (CuO as deduced from the X-ray diffraction) is showed. NH4VO3(99. the precursors were sintered for 10 h at the different annealing temperature (400. 1. The mixture was mixed into C6H8O7ÁH2O (99. 3 Results and discussion 3. Fig. 31].01V0. Japan). optical and magnetic properties. It can be 123 . which indicate that the crystalline quality of the samples improves with the annealing temperature increased. 500 and 600 °C.97Cu0. then transferred it to an agate mortar and grind to a fine powder. Hence the Cu doped ZnVO DMS is worth to be studied. And the origin of the ferromagnetism was also discussed.02O. such as crystal quality. electric and magnetic property. The structural characterization of the Zn0.9 %) and Cu(NO3)2Á3H2O (99. JEM-2100HR. The magnetic hysteresis loops of samples were measured by a Lake Shore 7407 vibrating sample magnetometer (VSM). optical.3 nm approximately by the Debye–Scherer formula when the annealing temperature was 400. respectively. 500.97Cu0. the samples have the hexagonal wurtzite structure of ZnO (space group P63mc) according to the standard JCPDS card within the sensitivity limitation of XRD.01V0. the grain size of the Zn0. Figure 2c shows the microstructure of the samples annealed at 500 °C examined by the high resolution transmission electron microscopy (HRTEM).

3 eV. which illustrates that the Cu and V atoms have substituted into the ZnO lattice sites.02O nanoparticles as shown in Fig.8 and 524.97Cu0.J Mater Sci: Mater Electron Fig. 3. As we know.29 nm.01V0.02O particles annealed at 500 °C (a).02O particles annealed at 500 °C (c) clearly observed that the measured interplanar distance of the fringes is 0. 2 TEM images of Zn0. Therefore.02O nanoparticles annealed at 600 °C.4 eV can be ascribed to the Cu 2p3/2 and Cu 2p1/2 peak respectively. The survey scans show no magnetic impurity within the detection limit. the radius of Cu? and Cu2? are close to the Zn2? ions. a very slight deviation (0. the V 2p3/2 and V 2p1/2 peaks are located at 516.02O nanoparticles annealed at 500 °C.97Cu0. so doping the Cu? or Cu2? ions should not cause much change of the lattice spacing. V. But the radius of V3?.01V0.6 eV.01V0.01V0. the substitution of the V ions for the Zn ions whould increase the lattice spacing of ZnO.97Cu0.6 and 952. respectively.5 and 952.97Cu0. Cu.97Cu0. It is expected that the Cu? 2p3/2 and Cu? 2p1/2 peaks would locate at 932.97Cu0.7 and 953.0 eV corresponding to the V5? ions [32]. All the indexed peaks can be identified to the C. 600 °C (b). the carbon arises during the process of sintering since that the citrate was not completely decomposed.02O nanoparticles annealed at 500 °C [26. The insets of Fig.2 Chemistry state The high resolution XPS spectra have been performed to study the chemical binding states of the Cu and V ions for the Zn0. while Cu2? 2p3/2 and Cu2? 2p1/2 peaks would locate at 933. we can conclude that the Cu ions present ?1 valence state in the Zn0.03 nm) in the lattice spacing can be observed compared the Cu and V dope ZnO to the pure ZnO (0. The peaks located at 932. Among them. In addition.01V0. O and Zn. Figure 3b shows the XPS spectra collected from the Zn0. 33]. which is corresponding to the (0 0 2) planes of the wurtzite ZnO. The V 2p3/2 and V 2p1/2 core levels are 123 . Based on the Gauss fitting.26 nm). This discloses that the Cu and V doping have affected slightly on the size and morphology of ZnO. 3a show the valence bonds of the V and Cu in the Zn0.01V0. 3a (500 °C) and b (600 °C). V4? and V5? ions are smaller than the Zn2? ions. HRTEM image of Zn0.

As for the ultraviolet emission centered at about 380 nm. 3.8 and 952.97Cu0. From Fig.4 and 524. The XPS results further explain the deviation of the lattice spacing for the two samples.02O nanoparticles is plotted in Fig. As for the samples annealed at 400 °C. one strong and broad green emission band. we deduce that the Cu and V ions are incorporated into the crystal lattice of the ZnO when the annealing temperature is 00 °C according to the results of the XRD. the relatively weak ultraviolet emission may result from the relatively poor crystalline quality due to the low annealing temperature. O-interstitial (Oi) and Zn-interstitial (Zni) [36].02O powders sintered at different temperature all show two distinct peaks: one weak and narrow ultraviolet peak. so the Cu ions also present ?1 valence state in the Zn0. the intensity of the ultraviolet emission is strongly dependent on the density of the free excitons. the PL spectra of the Zn0. Recently.01V0. 600 °C (b). this deep level emission band had been identified and at Fig. As shown in Fig.01V0. 4 PL spectra of Zn0.01V0.97Cu0.97Cu0. it is widely accepted that this emission results from the recombination of free excitons [34. Since that the zero-valence states of the metal clusters or particles are not traced in above two samples. And the peaks of Cu 2p3/2 and Cu 2p1/2 are detected at 932.97Cu0. So we can deduce that the V ions incorporate into the ZnO lattice as the V5? ions and the Cu ions incorporate into the ZnO lattice as the Cu? ions on the basis of the XPS results in these samples sintered at 500 and 600 °C. 4. 500 and 600 °C interplanar distance is increased.7 eV. 3 XPS spectrum of the Zn0. The chemistry states of the element do not change with the increasing of the annealing temperature.J Mater Sci: Mater Electron Fig.02O nanoparticles annealed at 400. respectively. HRTEM and XPS. The ionic radius of V5? is smaller than the Zn2? ions and thus the 123 . 4. Therefore. which suggests that the V dopant is incorporated into the ZnO lattice as V5? ions [31].3 Optical properties To investigate the effects of the annealing temperature on the optical properties of the samples. In addition. Inset shows local enlargement part of the spectra located at 517. Hence. 33]. respectively. the intensity of the visible emission is also increasing with the annealing temperature. the room temperature PL spectra of the Zn0. 35]. Zn-vacancy (VZn). The deep level emission band has previously been attributed to several defects in the crystal structure such as O-vacancy (VO).01V0.02O nanoparticles annealed at 500 °C (a).01 V0.97Cu0. 4. it can be seen that the samples annealed at 600 °C have the strongest ultraviolet emission. which means the samples have the best crystalline quality just consistent with the XRD results. It is well known that the density of free exciton is closely connected with the crystalline quality.7 eV.02O nanoparticles annealed at 600 °C [32.

When the sintering temperature increases from 400 to 600 °C. With the temperature increased. it is more likely that the type and concentration of the defects in ZnO nanostructures have a significant influence on the visible emission peak. Cu co-doping ZnO samples is very sensitive to the annealing temperature.4 Magnetic properties The magnetic measurements on the Zn0. Because the additional oxygen can fill into the O vacancy place during the annealing process. Cu is non-magnetic element. and Vo levels.01V0. other phases of vanadium and copper oxide. 40. VZn. 5.J Mater Sci: Mater Electron least two different defect origins (VO and VZn) with different optical characteristics [37].02O nanoparticles in our study is an intrinsic property of the sample. it can be concluded that VZn is probably involved in the green light emission.02O nanoparticles sintered at 400. the Ms of the samples increase from 0. In our work. In addition. so that the PL intensity of green light emission will be much higher. which would compensate the electrons arising from Zn2? interstitial in the ZnO sample [26]. the magnetization can be achieved with a reasonable amount of the acceptor concentration. In addition. the concentration of the defects (VZn) increased. the magnetic moment increases steadily with the increase of the annealing temperature.01V0. CuO and Cu2O or clustering are antiferromagnetic [19. which results in the green emission blue-shift. which reveal that they have a good Fig. In our sample.01V0. Therefore.02O is not come from clustering or impurities but expected to be intrinsic. the local density of states (DOS) at the Fermi level and the exchange interaction are large [33]. By acceptor doping. So we conclude that the ferromagnetism of the Zn0. So they should not be the sources of the ferromagnetism in our samples. which will strongly decrease the concentration of VO. Since that VO2 is non-magnetic. The Cu? acting as an acceptor plays the critical role in establishing the ferromagnetic order. Besides. Theoretical studies suggest that the defects can bring 123 . 500 and 600 °C were performed at room temperature using VSM. 500 and 600 °C ferromagnetism property at room temperature. the changed type and quantity of the defects will leads to the blue-shift and the increase of the green emission. A number of studies indicate that the FM in the TM-doped ZnO may come from the precipitation of magnetic clusters or the secondary magnetic phases. it has been proposed that defects (VZn and VO) may play an important role in the magnetic origin for DMS. which lead to the observed ferromagnetism at room temperature. In our experiment. Thus.97Cu0. 20]. when the concentration of the defects exceeds the percolation threshold. So the ferromagnetism in Zn0. That is to say.00926 emu/g. Recently.97Cu0.01V0. inducing a ferromagnetic coupling between the dopant spins. and the VO will decrease. From Fig. 5. when the sample was annealed in air.00683 to 0. 43]. the blue-shift of the green emission is possible attributed to the two temperature related transitions between the conduction band. 39]. 3. no V-related impurity phase was detected according to the XRD results. From the results of many researchers [36–38]. Thus. many researchers reported the V doped DMS materials have RTFM [22. we can observe that all the samples show the clear magnetic hysteresis loop. the magnetic coupling between the V ions is ferromagnetic mediated by the defects at the interfaces of the nanoparticles. the interfacial defects can overlap many dopant ions as well as the adjacent defects.02O annealed at 400. the magnetic ordering in V. V6O13 and ZnV2O4 are antiferromagnetic [22. V2O3. 5 Magnetic hysteresis (M–H) loops of Zn0.97Cu0. The addition of the acceptors to the system will therefore increase the magnetization as observed. Within the framework of the BMP theory [42. During the thermal treatment process at the high annealing temperature. the possible origin of the magnetism is micro V and Cu clusters. which consistent with the increasing trend of the visible emission. it is unlikely to form the V clusters because that our samples were calcined in air.97Cu0. 41]. And different defect emissions also exhibit different temperature dependences. Consequently. The substitution of the Cu and V ions for the Zn sites inconsistently leads to the ferromagnetism in ZnO. we can increase the local hole concentration at the anion site. In Fig. it can be observed that all the green emission positions show small blue-shift with the increasing temperature. Therefore. Since that there are many uncompensated or localized acceptors in our co-doped powders. the concentration of the VZn increase. only V metal clusters are ferromagnetic at room temperature among V metal and oxides. therefore. it is expected that the rich O environment can make VO concentration decrease.

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