APPLIED PHYSICS LETTERS 97, 172503 2010

Role of electronic structure and oxygen defects in driving ferromagnetism in nondoped bulk CeO2
R. K. Singhal,1,2,a P. Kumari,1 A. Samariya,1 Sudhish Kumar,3 S. C. Sharma,1 Y. T. Xing,2 and Elisa B. Saitovitch2
1 2

Department of Physics, University of Rajasthan, Jaipur 302055, India CBPF, Rua Dr. Xavier Sigaud 150, Urca, Rio de Janeiro 22290180, Brazil 3 Department of Physics, M.L. Sukhadia University, Udaipur 313002, India

Received 2 September 2010; accepted 8 October 2010; published online 28 October 2010 This article reports on reversible manipulation of room temperature ferromagnetism RTFM in nondoped bulk CeO2. The magnetization measurements establish that paramagnetic CeO2 is driven to a ferromagnetic state, without change in structure, when vacuum annealed at 600 C. The Ce ions transform from 4+ to 3+ state, accompanied by evolution of oxygen vacancies VO during the RTFM transition, as determined by x-ray photoemission. The F+ centers the electrons in singly occupied oxygen vacancies play key role in the exchange mechanism. The transition shows complete reversibility where the RTFM is removed by removing the vacancies through re-heating the vacuum-annealed CeO2 in air. 2010 American Institute of Physics. doi:10.1063/1.3507290 Defects, especially, the oxygen vacancies, and their link to ferromagnetism, have been focus of recent research in magnetic semiconductors.14 It is proposed that oxygen vacancies form donor impurity band that assist in establishing exchange coupling in ZnO, TiO2, SnO2, etc.4,5 Besides these semiconductors, some dielectrics/insulators like CeO2 are also found to show the room temperature ferromagnetism RTFM ,6,7 however, the exchange mechanism in them is expected to be different than that in the magnetic semiconductors. Systematic studies are therefore needed to explore the mechanism causing the ferromagnetic interactions in these magnetic dielectrics. CeO2 can be a potential candidate as a magnetic insulator due to its interesting properties like, high dielectric constant; a stable structure that can exist with large offstoichiometric oxygen, and the redox properties.2 Within the uorite phase, it exhibits several defects, e.g., the O vacancies and polarons electrons localized on Ce cations depending on the partial pressure of oxygen. Tiwari et al.8 showed that the Co-doped CeO2 displays RTFM with high magnetic moment 8.2 B / Co and Curie temperature 725 K . The giant magnetization was attributed to unquenched orbital magnetic moments of the dopant Co. This was followed by number of reports in various 3d transition metals TMs doped CeO2 Refs. 813 systems, however, no clear mechanism of ferromagnetism could be established. Some researchers have claimed ferromagnetism in thin lms, nanopowders, and nanocubes forms of nondoped CeO2 by irradiation and other manipulations.9,14 On the contrary, there are hardly any such reports on nondoped bulk CeO2, however, the theoretical predictions deny the possibility of RTFM ordering in it.2 While the reports of ferromagnetism in the TM doped oxides are suspected in terms of metallic cluster formation, the nondoped systems are free from such fears. Hence, we have pursued study of the bulk CeO2 to focus on potential role of VO in the RTFM mechanism. High purity 99.99% ceria powder from Koch light, England was heated at 500 C to get rid off the impurities like
a

water molecules and CO2, owing to its hygroscopic nature, and then transformed in to pellets. The crystal structure was investigated by analyzing the x-ray diffractograms XRD recorded on PHILIPS diffractometer using Cu K radiation. The Rietveld prole renements were performed using the 15 FULLPROF program. The magnetization measurements were carried out using superconducting quantum interference device SQUID and the resistances were measured using a Keithley Electrometer. The x-ray photoemission spectra XPS were recorded using VG3000 spectrometer equipped with Mg source and a hemispherical analyzer with an overall resolution of 0.8 eV. The CeO2 was annealed for 10 h in vacuum 107 Torr at 600 C. The vacuum-annealed sample was re-heated in air for the same duration at 600 C. The structural and magnetic characterizations performed in identical conditions conrmed that vacuum annealing neither altered the structure nor generated any impurity phase. Figure 1 displays the rened XRD patterns of the pure and the vacuum-annealed CeO2. The Rietveld analysis conrmed a single phase uorite face centered cubic structure space group Fm3m, no. 225 without any impurity phase.

Electronic mail: singhal46@yahoo.co.in. Tel.:

91 141 2545931.

FIG. 1. Color online The rened XRD patterns of pure CeO2 and the vacuum-annealed CeO2 : Vac at 300 K. The observed calculated proles are shown by open circle solid line curves. The short vertical marks represent the Bragg reections. The lower curve is the difference plot. 2010 American Institute of Physics

0003-6951/2010/97 17 /172503/3/$30.00

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FIG. 2. Color online The Ce 3d XPS spectra for pure CeO2, the vacuumannealed CeO2 : Vac, the air-heated CeO2 : Htd, and the difference spectrum CeO2 : H - CeO2 .

FIG. 3. Color online The O 1s Gaussian bulk oxygen peaks for pure CeO2, the vacuum-annealed CeO2 : Vac, and the air-heated CeO2 : Htd. Inset shows the O 1s XPS spectra, along with Gaussian ts for CeO2.

The lattice parameter a = 5.4107 3 for CeO2 is in good agreement with the standard value. The evacuation leads to a small expansion in the cell volume V = 158.40 3 for CeO2 and V = 159.64 3 for evacuated sample . The XPS were recorded immediately after turning the x-ray source on to avoid any induced artifacts by possible reduction in ceria by heating from the beam. The samples were loaded together for recording the spectra. The C 1s peak at 284.6 eV was used to calibrate the spectra. The Ce 3d core-level spectra for the pure CeO2, the evacuated sample CeO2 : Vac, and the heated sample CeO2 : Htd are displayed in Fig. 2. The Ce 3d spectrum can be described by ve spin-orbit doublets 3d5/2 and 3d3/2 .16 The peaks U, U2, and U3 referring to 3d3/2 levels and the peaks V, V2, and V3 referring to 3d5/2 levels, are characteristic of Ce4+ 3d states. The peaks U0, U1 referring to 3d3/2 level, and the peaks V0, V1 to 3d5/2 levels are indicative of Ce3+ 3d nal states. The peaks V and V2 are due to mixture of Ce 3d94f 2O 2p4 and Ce 3d94f 1O 2p5 of Ce4+ states, and the peak V3 corresponds to Ce 3d94f 0O 2p6 of Ce4+ state. The peaks V0 and V1 are assigned to Ce 3d94f 2O 2p5 and Ce 3d94f 1O 2p6 of Ce3+ nal state. The same assignment can be made to U structures of Ce 3d3/2 levels. No extra peaks corresponding to clusters are noticed. The spectra show notable differences between the pure CeO2 and the CeO2 : Vac. The features V0, V1, and U1 corresponding to Ce3+ state, not visible in the spectrum of pure CeO2, appear dominantly in the CeO2 : Vac. Also the peak U3, corresponding to Ce4+, gets suppressed in the CeO2 : Vac see the difference spectrum CeO2 : Vac minus CeO2 . These observations demonstrate that the Ce ions transform from 4 + to 3+ state upon evacuation. This is consistent with Rietveld analysis which revealed that unit cell expands upon evacuation, owing to bigger ionic size of Ce3+ 1.034 than that of Ce4+ 0.92 . A similar transformation of Ce valence, followed by magnetization, was reported in ion irradiated CeO2 lms17 and Co-doped CeO2 bulk samples.2 Notably, the Ce3+ features smear out when the CeO2:Vac is reannealed in air. The asymmetric O 1s spectra were tted with three Gaussians inset, Fig. 3 to separate out the bulk O2 content present in the samples. The main peak at 531.5 eV belongs to the bulk O2 while the small structures on the higher

energy side arise due to surface contaminations.3 The bulk oxygen peaks are shown separately in Fig. 3. There is a notable deciency in the bulk O2 in CeO2 : Vac than that in the pure CeO2 by 12% which is a clear indication of creation of signicant density of VO upon evacuation. Interestingly, upon air heating the CeO2 : Vac, the bulk O2 content is almost recovered. The irradiation of CeO2 is also reported to cause a similar decrease in coordination number of O atoms around the Ce, followed by a reduction in Ce valence from +4 to +3.18 The formation of VO, in order to maintain the charge neutrality, when the Ce4+ ions reduce to Ce3+, is explained by following:19 2Ce4+ Lattice + 4O2 Lattice VO + O + 2Ce3+ Lattice + 3O2 Lattice. The pure CeO2 is paramagnetic Fig. 4 , interestingly, the vacuum-annealed CeO2 : Vac shows the ferromagnetic ordering at 300 K, as revealed by hysteresis loop with a saturation magnetization M S 0.040 emu/ g . The induced RTFM disappears upon annealing the sample in air for 10 h , as evidenced by the linear M-H curve, similar to the pure CeO2. The measured resistance for CeO2 is 40 G which reduces to 3 G for CeO2 : Vac measured on rectangular bricks, 4.0 2.0 0.5 mm3 each . Of course, it is still very high, in the gigaohm range, indicating a low concentration of

FIG. 4. Color online The M-H curves for pure CeO2, the vacuum-annealed CeO2 : Vac, and the air-heated CeO2 : Htd.

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carriers, despite the evacuation. The resistance for the heated CeO2 : Htd again increases to 35 G . The creation of VO is equivalent to creating conduction electrons consistent with depression in the resistance revealing that the carrier concentration in CeO2 is affected by the O vacancies. Finally, it was important to conrm that the O deciency is not conned to the surface layers and rather uniformly created in, and also removed out, from the bulk, after annealing the samples in vacuum and air, respectively. For this purpose, we etched as well as broke the pellets and performed the SQUID measurements which show the consistent results. Our results present a quantitative relationship between the induced RTFM and the VO, similar to the reports on ZnO, TiO2, and In2O3 systems.2022 Also in recent studies the Ti ions in TiO2 transforming from 4+ to 3+ state, accompanied by creation of VO, were related to the giant RTFM.3 Our results agree with those of Shah et al.2 who have shown that the Co-doped bulk CeO2 samples exhibit ferromagnetic ordering which is intimately linked with the VO. However, our ndings show a contradiction with their prediction regarding the nondoped CeO2.2 Their rst principle calculations2 show that the VO can pull the d and f orbits of Ce closer to the EF to cause an exchange splitting in nondoped CeO2, however, due to very small density of states the VOs are not sufcient to induce an RTFM in it. Our ndings also contradict with Liu et al.13 who showed M S to be independent of VO in CeO2 nanopowders. Since the defect induced ferromagnetism depends on locations of VO in the uorite structure,23 we feel that the probing technique used in Ref. 13 lacks sensitivity to detect small changes in the stoichiometry. Li et al.24 claim that the RTFM does not relate to the VO but to the mixed valent Ce3+ / Ce4+ pairs at the surface layers. But despite their refusal, the role of VO cannot be ruled out because our ndings conrm that occurrence of Ce mixed valence in CeO2 : Vac is accompanied by creation of VO as a subsequent electronic phenomenon. To account for the connection of VO to the observed RTFM in CeO2 : Vac, we consider a subcategory of the bound magnetic polaron BMP model, known as the F-center exchange2,4 mechanism which has been used to explain ferromagnetism in insulators, e.g., TiO2 and SnO2. In this framework, three possible states of the VOs can be i the F2+ center with no trapped electrons; ii the F+ center with one trapped electron; and iii the F0 center with two trapped electrons. The F0 centers in the singlet state S = 0 form the shallow donor levels above the conduction band. These can, however, mediate only weak antiferromagnetic exchanges. Contrary to this, the F+ centers, basically the electrons in the singly occupied oxygen vacancies lying deep in the gap, could be able to favor a ferromagnetic state. However, in pure CeO2, these F+ centers are strongly localized and the F-electron orbital is too large 46 Refs. 2 and 4 which weigh against a long range ferromagnetic coupling in it. Obviously, the pure CeO2 is likely to retain a paramagnetic state that is in agreement with our ndings. On the other hand, a sufcient density of the VOs is created in evacuated CeO2 : Vac, as determined by our x-ray photoemission spectroscopic results. These vacancies form signicant density of F+ center, which reduce the F-electron orbital size

considerably, that eases the observed mediation of the ferromagnetic coupling in the CeO2 : Vac. Further theoretical work to estimate the F-electron orbital size as a function of density of VO would be very helpful in this context. We demonstrate that starting from the pristine paramagnetic CeO2, without oxygen deciency, it is possible to obtain the ferromagnetism by reducing Ce ions from 4+ to 3+ state and inducing the oxygen vacancies through vacuum annealing. The induced ferromagnetism bounces back upon re-annealing the sample in air. The observed induction and disappearance of ferromagnetism shows close relationship with oxygen vacancies and the F+ centers. This work is dedicated to Mr. G. K. Singhal for an immense inspiration who sadly passed away during this work.
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