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Journal of Magnetism and Magnetic Materials 272276 (2004) e1245e1246

Magnetic study on Co3O4 nanoparticles


Y. Ichiyanagi*, Y. Kimishima, S. Yamada
Department of Physics, Yokohama National University, 79-5 Tokiwadai, Hodogaya, Yokohama 240-8501, Japan

Abstract Magnetization measurements for the Co3O4 nanoparticles were performed. From the X-ray diffraction patterns Co3O4 nanoparticles surrounded by amorphous SiO2 were expected for the samples annealed between 623 and 873 K. Their diameters were estimated to be 2 or 3 nm. DC magnetization curves of zero-eld cooled and eld-cooled bifurcated around Tt 10 K, while the bulk Co3O4 crystal exhibits antiferromagnetic transition temperature at TN 33 K. Characteristic properties of extremely small Co3O4 nanoparticles were conrmed. r 2003 Elsevier B.V. All rights reserved.
PACS: 75.60.Ej; 75.50.Ee Keywords: Nanoscopic systems; Magnetization; Co-oxide

1. Introduction Because of their unique magnetic properties as well as their technological applications, magnetism of nanoscopic systems attracts much attention. As for antiferromagnetic systems, N! el has originally e suggested their superparamagnetic relaxation of their spin lattices yielded by uncompensated surface spins. The authors have reported magnetic properties of Ni(OH)2 nanoclusters [1], FeO nanoparticle systems [2] and NiO nanoparticles [3]. Ni(OH)2 nanoclusters showed ferromagnetic transition at near ! 10 K, while bulk crystal of Ni(OH)2 has Neel temperature at 25.75 K. Fe2O3 (g-phase) exhibited blocking temperature between 30 and 120 K though bulk crystal orders ferrimagnetically below Tc 1020 K. Ferromagnetic behavior due to the uncompensated surface spins under 5 K was observed in NiO nanoparticles. In this study, Co3O4 nanoparticles with 2 or 3 nm sizes were produced by wet method and magnetic properties were observed.

2. Experiment The Co3O4 surrounded by amorphous SiO2 network precursor was chemically precipitated by mixing a cobalt chloride CoCl2 6H2O aqueous solution and a sodium metasilicate nonahydrate Na2SiO3 9H2O solution. The resulting pink colored precipitates were washed several times with distilled water and dried at about 350 K. The obtained glassy solids were made into powder by crashing and calcined between 623 and 923 K in the air. X-ray powder diffraction patterns were obtained at room temperature CuKa radiation. X-ray absorption ne structure (XAFS) experiments were performed for the conrmation of the microscopic structure. Magnetization was measured by VSM and SQUID magnetometer under the magnetic eld between 750 kOe in the temperature region from 2 to 300 K.

3. Results and discussion X-ray diffraction (XRD) patterns indicate amorphous SiO2 and the formation of the Co3O4 spinel phase from the samples calcined between 623 and 923 K. From the half-width of XRD peaks, particle sizes were estimated

*Corresponding author. Tel./fax: +81-45-339-4185. E-mail address: yuko@ynu.ac.jp (Y. Ichiyanagi).

0304-8853/$ - see front matter r 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.jmmm.2003.12.377

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e1246 Y. Ichiyanagi et al. / Journal of Magnetism and Magnetic Materials 272276 (2004) e1245e1246 Table 1 Particle sizes of nanoparticles depending on various annealing temperatures estimated from XRD and average blocking temperatures Tt Sample No. 1 2 3 4 Annealing temp. (K) 623 723 773 873 d (nm) 2.0 2.2 2.4 3.1 Tt (K) 7.5 9.0 10.0 12.0

as between 2.0 and 3.1 nm. Various annealing temperatures and obtained average diameters of nanoparticles are summarized in Table 1. Average blocking temperatures Tt determined by magnetization curves are also indicated. Observed Tt of each sample was revealed from 7.5 to 12.0 K, while the N! el temperature of Co3O4 e bulk crystal was known as TN 30 K. This decrease of transition temperature maybe ascribed to smaller particle size indicating a nite size effect of phase transition of present system. Simply applying the relation between anisotropy energy and thermal uctuation Kv kB T to this case, particle size near Tt B10 K could be estimated as about 30 nm, assuming KB105 J/m3 though exact anisotropy constant is unknown. It is known that Co3O4 has normal spinel structure with antiferromagnetic exchange between ions occupying tetrahedral A sites and octahedral B sites. The Co3+ ions have no moment on B sites and Co2+ ions on A sites have permanent moment of 3.25 mB from the neutron diffraction experiments [4]. Temperature dependences of the magnetization of samples in zero-eld-cooled (ZFC) and eld-cooled (FC) cases are shown in Fig. 1. In each ZFC curve, very narrow cusp at 7.5, 9.0, 10.0 and 12.0 K was observed, respectively, and strongly bifurcated at lower temperature. For higher temperature, the plot of w1 vs. T was linear indicating that the magnetization obeyed the CurieWeiss law with negative y value about 40 K. From magnetization curves were measured at temperatures between 2 and 300 K in external elds within 750 kOe. From the MH curve paramagnetic behavior above 50 K, superparamagnetic behavior near Tt and ferromagnetic behavior with slight hysteresis below Tt were observed. Thus behaviors should be due to the uncompensated surface spins on the extremely small particle systems. From the inverse susceptibility, extremely larger effective magnetic moment per ion of 8.12 mB than expected as 4.14 mB was estimated. This result could be due to the exchange mechanism of Co3+ ion in complex octahedral symmetry of Co3O4 nanoparticles. Magnetic isotherms are summarized in Fig. 2. Magnetizations above Tt were linear with H=T y

Fig. 1. Magnetization for FC and ZFC of Co3O4 nanoparticles annealed at various temperatures.

Fig. 2. Magnetization vs. H=T y at the indicated temperatures.

and tended to describe curves in lower temperature than Tt : These are characteristic behaviors of the extremely small Co3O4 nanoparticles.

Acknowledgements This study was partially supported by the Japan Society for the Promotion of Science Grant-in-Aid Scientic Research (C)(2) 12650008.

References
[1] Y. Ichiyanagi, Y. Kimishima, Jpn. J. Appl. Phys. 35 (1986) 2140. [2] Y. Ichiyanagi, T. Uozumi, Y. Kimishima, Trans. Mater. Res. Soc. Japan 26 (2001) 1097. [3] Y. Ichiyanagi, et al., Physica B 329333 (2003) 862. [4] W.L. Roth, J. Phys. Chem. Solids 25 (1964) 1.