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APPLIED PHYSICS LETTERS 97, 172503 2010

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. Saitovitch

2

1 Department of Physics, University of Rajasthan, Jaipur 302055, India

2 CBPF, Rua Dr. Xavier Sigaud 150, Urca, Rio de Janeiro 22290–180, 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 CeO 2 . The magnetization measurements establish that paramagnetic CeO 2 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 V O 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 CeO 2 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

cancies form donor impurity band that assist in establishing exchange coupling in ZnO, TiO 2 , SnO 2 , etc. 4,5 Besides these

semiconductors, some dielectrics/insulators like CeO 2 are also found to show the room temperature ferromagnetism RTFM , 6,7 however, the exchange mechanism in them is ex- pected to be different than that in the magnetic semiconduc- tors. Systematic studies are therefore needed to explore the mechanism causing the ferromagnetic interactions in these magnetic dielectrics.

CeO 2 can be a potential candidate as a magnetic insula- tor due to its interesting properties like, high dielectric con- stant; a stable structure that can exist with large off- stoichiometric oxygen, and the redox properties. 2 Within the fluorite phase, it exhibits several defects, e.g., the O vacan- cies and polarons electrons localized on Ce cations depend-

ing on the partial pressure of oxygen. Tiwari et al. 8

showed

that the Co-doped CeO 2 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 3 d transition metals TMs

doped CeO 2 Refs. 813 systems, however, no clear mecha- nism of ferromagnetism could be established. Some re- searchers have claimed ferromagnetism in thin films, nan-

opowders, and nanocubes forms of nondoped CeO 2

by

irradiation and other manipulations. 9,14 On the contrary, there are hardly any such reports on nondoped bulk CeO 2 , how- ever, 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 clus- ter formation, the nondoped systems are free from such fears. Hence, we have pursued study of the bulk CeO 2 to focus on potential role of V O in the RTFM mechanism. High purity 99.99% ceria powder from Koch light, En- gland was heated at 500 °C to get rid off the impurities like

semiconductors. 14 It is proposed that oxygen va-

a Electronic mail: singhal46@yahoo.co.in. Tel.: 91 141 2545931.

water molecules and CO 2 , 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 profile refinements were performed using the FULLPROF program. 15 The magnetization measurements were carried out using superconducting quantum interference de- vice 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 CeO 2 was annealed for 10 h in vacuum 10 7 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 confirmed that vacuum annealing neither altered the structure nor generated any impurity phase. Figure 1 displays the refined XRD patterns of the pure and the vacuum-annealed CeO 2 . The Rietveld analysis con- firmed a single phase fluorite face centered cubic structure space group Fm 3 m , no. 225 without any impurity phase.

group Fm 3 m , no. 225 without any impurity phase. FIG. 1. Color online The

FIG. 1. Color online The refined XRD patterns of pure CeO 2 and the vacuum-annealed CeO 2 :Vac at 300 K. The observed calculated profiles are shown by open circle solid line curves. The short vertical marks rep- resent the Bragg reflections. The lower curve is the difference plot.

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

97 , 172503-1

Author complimentary copy. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp

© 2010 American Institute of Physics

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Singhal et al.

172503-2 Singhal et al. FIG. 2. Color online The Ce 3 d XPS spectra for pure

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

The lattice parameter a=5.4107 3 Å for CeO 2 is in good agreement with the standard value. The evacuation leads to a small expansion in the cell volume V=158.40 Å 3 for CeO 2 and V=159.64 Å 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 1 s peak at 284.6 eV was used to calibrate the spectra. The Ce 3 d core-level spectra for the pure CeO 2 , the evacuated sample CeO 2 :Vac, and the heated sample CeO 2 :Htd are dis- played in Fig. 2. The Ce 3 d spectrum can be described by

five spin-orbit doublets 3 d 5 / 2 and 3 d 3 / 2 . 16 The peaks U, U 2 , and U 3 referring to 3 d 3 / 2 levels and the peaks V, V 2 , and V 3 referring to 3 d 5 / 2 levels, are characteristic of Ce 4+ 3 d states. The peaks U 0 , U 1 referring to 3 d 3 / 2 level, and the peaks V 0 , V 1 to 3 d 5 / 2 levels are indicative of Ce 3+ 3 d final states. The peaks V and V 2 are due to mixture of Ce 3 d 9 4 f 2 O 2 p 4 and Ce 3 d 9 4 f 1 O 2 p 5 of Ce 4+ states, and the peak V 3 corre- sponds to Ce 3 d 9 4 f 0 O 2 p 6 of Ce 4+ state. The peaks V 0 and V 1 are assigned to Ce 3 d 9 4 f 2 O 2 p 5 and Ce 3 d 9 4 f 1 O 2 p 6 of Ce 3+ final state. The same assignment can be made to U structures of Ce 3 d 3 / 2 levels. No extra peaks corresponding to clusters are noticed. The spectra show notable differences between the pure CeO 2 and the CeO 2 :Vac. The features V 0 , V 1 , and U 1 cor- responding to Ce 3+ state, not visible in the spectrum of pure CeO 2 , appear dominantly in the CeO 2 :Vac. Also the peak U 3 , corresponding to Ce 4+ , gets suppressed in the CeO 2 :Vac see the difference spectrum CeO 2 :Vac minus CeO 2 . These observations demonstrate that the Ce ions transform from 4 + to 3+ state upon evacuation. This is consistent with Ri- etveld analysis which revealed that unit cell expands upon evacuation, owing to bigger ionic size of Ce 3+ 1.034 Å than that of Ce 4+ 0.92 Å . A similar transformation of Ce va- lence, followed by magnetization, was reported in ion irradi-

ated CeO 2 films

and Co-doped CeO 2 bulk samples. 2 Nota-

bly, the Ce 3+ features smear out when the CeO 2 :Vac is reannealed in air. The asymmetric O 1 s spectra were fitted with three Gaussians inset, Fig. 3 to separate out the bulk O 2 content present in the samples. The main peak at 531.5 eV be- longs to the bulk O 2 while the small structures on the higher

17

Appl. Phys. Lett. 97 , 172503 2010

on the higher 17 Appl. Phys. Lett. 97 , 172503 2010 FIG. 3. Color online The

FIG. 3. Color online The O 1 s Gaussian bulk oxygen peaks for pure CeO 2 , the vacuum-annealed CeO 2 :Vac, and the air-heated CeO 2 :Htd. Inset shows the O 1 s XPS spectra, along with Gaussian fits for CeO 2 .

energy side arise due to surface contaminations. 3 The bulk oxygen peaks are shown separately in Fig. 3. There is a notable deficiency in the bulk O 2 in CeO 2 :Vac than that in the pure CeO 2 by 12% which is a clear indication of

creation of significant density of V O upon evacuation. Inter- estingly, upon air heating the CeO 2 :Vac, the bulk O 2 content is almost recovered. The irradiation of CeO 2 is also reported to cause a similar decrease in coordination number of O at- oms around the Ce, followed by a reduction in Ce valence from +4 to +3. 18 The formation of V O , in order to maintain

the charge neutrality,

explained by following: 19

when the Ce 4+ ions reduce to Ce 3+ , is

2Ce 4+ Lattice + 4O 2 Lattice V O + O

+ 2Ce 3+ Lattice + 3O 2 Lattice.

The pure CeO 2 is paramagnetic Fig. 4 , interestingly, the vacuum-annealed CeO 2 :Vac shows the ferromagnetic or- dering at 300 K, as revealed by hysteresis loop with a satu- ration 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

CeO 2 . The measured resistance for CeO 2 is 40 G which reduces to 3 G for CeO 2 :Vac measured on rectangular bricks, 4.0 2.0 0.5 mm 3 each . Of course, it is still very

high, in the gigaohm range, indicating a low concentration of

in the gigaohm range, indicating a low concentration of FIG. 4. Color online The M -

FIG. 4. Color online The M - H curves for pure CeO 2 , the vacuum-annealed CeO 2 :Vac, and the air-heated CeO 2 :Htd.

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Singhal et al.

carriers, despite the evacuation. The resistance for the heated CeO 2 :Htd again increases to 35 G . The creation of V O is equivalent to creating conduction electrons consistent with

depression in the resistance revealing that the carrier concen- tration in CeO 2 is affected by the O vacancies. Finally, it was important to confirm that the O deficiency is not confined 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 measure- ments which show the consistent results. Our results present a quantitative relationship between

, similar to the reports on

the induced RTFM and the V

ZnO, TiO 2 , and In 2 O 3 systems. 2022 Also in recent studies the

Ti ions in TiO 2 transforming from 4+ to 3+ state, accompa-

Our

nied by creation of V

results agree with those of Shah et al. 2 who have shown that the Co-doped bulk CeO 2 samples exhibit ferromagnetic or-

dering which is intimately linked with the V O . However, our findings show a contradiction with their prediction regarding

the nondoped CeO 2 . 2 Their first principle calculations

that the V O can pull the d and f orbits of Ce closer to the E F to cause an exchange splitting in nondoped CeO 2 , however, due to very small density of states the V O ’s are not sufficient to induce an RTFM in it. Our findings also contradict with Liu et al. 13 who showed M S to be independent of V O in CeO 2 nanopowders. Since the defect induced ferromagnetism de-

23 we feel

that the probing technique used in Ref. 13 lacks sensitivity to

claim

detect small changes in the stoichiometry. Li et al.

that the RTFM does not relate to the V O but to the mixed valent Ce 3+ / Ce 4+ pairs at the surface layers. But despite their refusal, the role of V O cannot be ruled out because our find-

ings confirm that occurrence of Ce mixed valence in CeO 2 :Vac is accompanied by creation of V O as a subsequent electronic phenomenon. To account for the connection of V O to the observed RTFM in CeO 2 :Vac, we consider a subcategory of the bound magnetic polaron BMP model, known as the F-center exchange 2,4 mechanism which has been used to ex- plain ferromagnetism in insulators, e.g., TiO 2 and SnO 2 . In this framework, three possible states of the V O ’s can be i the F 2+ center with no trapped electrons; ii the F + center with one trapped electron; and iii the F 0 center with two trapped electrons. The F 0 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. How- ever, in pure CeO 2 , these F+ centers are strongly localized and the F-electron orbital is too large 46 Å Refs. 2 and 4 which weigh against a long range ferromagnetic coupling in it. Obviously, the pure CeO 2 is likely to retain a paramag- netic state that is in agreement with our findings. On the other hand, a sufficient density of the V O ’s is created in evacuated CeO 2 :Vac, as determined by our x-ray photoemis- sion spectroscopic results. These vacancies form significant density of F + center, which reduce the F-electron orbital size

pends on locations of V O in the fluorite structure,

show

O

O

, were related to the giant RTFM.

3

2

24

Appl. Phys. Lett. 97 , 172503 2010

considerably, that eases the observed mediation of the ferro- magnetic coupling in the CeO 2 :Vac. Further theoretical work to estimate the F-electron orbital size as a function of density of V O would be very helpful in this context. We demonstrate that starting from the pristine paramag- netic CeO 2 , without oxygen deficiency, it is possible to ob- tain 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 im- mense inspiration who sadly passed away during this work.

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