Journal of Alloys and Compounds 465 (2008) 227231

Review

Structural, magnetic and electrical properties of cobalt ferrites prepared by the solgel route
I.H. Gul, A. Maqsood
Thermal Physics Laboratory, Department of Physics, Quaid-i-Azam University, Islamabad 45320, Pakistan Received 18 August 2007; received in revised form 28 October 2007; accepted 1 November 2007 Available online 19 December 2007

Abstract Nanosized cobalt ferrites having the general formula CoFe2x Alx O4 (for x = 0.00, 0.25, 0.50) have been synthesized by the solgel route. The effect of Al3+ ions on structural, Curie temperature, DC electrical resistivity and dielecltric properties are presented in this paper. From the analysis of powder X-ray diffraction patterns, the nanocrystallite size was calculated by the most intense peak (3 1 1) using Scherrer formula. The crystallite size decreases with increase in aluminium concentartion. The lattice parameter a also decreased with increase in aluminum concentration. The magnetic and electrical properties have been studied as a function of temperature. The Curie temperature was determined from AC magnetic susceptibility measurement. It is observed that Curie temperature decreases and DC electrical resistivity increases with increasing concentration of Al3+ ions. The observed variations in DC electrical resistivity have been explained by Verweys hopping mechanism. The activation energy was found to increase with increasing Al3+ ions. The variations of dielectric constant for all the samples have been studied as a function of frequency in the range 500 Hz to 1 MHz at room temperature. The room temperature dielectric constant decreases with increase of trivalent Al3+ ions. The observed variation in dielectric constant has been explained on the basis of space charge polarization. 2007 Elsevier B.V. All rights reserved.
PACS: 75.30.Cr; 82.80.Jp; 84.37.+q; 78.20.Ci; 75.50.Gg; 61.46.Df; 61.10.Nz Keywords: AC magnetic susceptibility; Electrical resistivity; Dielectric constant; Ferrite; Nanoparticles; X-ray diffraction

Contents
1. 2. 3. 4. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227 228 228 231 231 231

1. Introduction Cobalt ferrite, a ferrimagnetic ceramic, emerged as one of the important material due to high electrical resistance with low eddy current losses. There is an increasing interest in magnetic

Corresponding author. Tel.: +92 51 2601014; fax: +92 51 90642240. E-mail addresses: iftikhar qau@yahoo.com (I.H. Gul), tpl.qau@usa.net (A. Maqsood). 0925-8388/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2007.11.006

ferrite nanoparticles because of their broad applications in permanent magnets, drug delivery, microwave devices and highdensity information storage [14]. The interesting and useful magnetic and electrical properties of the spinel ferrites are governed by the choice of the cations along with Fe2+ , Fe3+ ions and their distribution between tetrahedral (A) and octahedral (B) sites of the spinel lattice as well as preparation conditions, chemical composition, sintering temperature, sintering time, doping additives and the method of preparation [58]. It is very important in many applications to control the electrical resistivity of

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I.H. Gul, A. Maqsood / Journal of Alloys and Compounds 465 (2008) 227231 The tangent of dielectric loss angle can be calculated using the relation tan = 1 , 2fRs Cs (3)

the spinel ferrite. For this purpose two major possibilities are available, controlling the sintering temperature and substitutions. Ferrites are also very good dielectric materials and have many applications in technology ranging from microwave to radio frequency. They are also used as microwave absorbers. Some ferrites absorb microwave by losing interaction of the electric and magnetic eld vector of incident wave and in the process transfer microwave energy into thermal energy. Radar absorbing paint made from ferrite can be used to coat military aircraft for stealth operation. The order of magnitude of the electrical conductivity greatly inuences the dielectric and magnetic behaviour of ferrites. Cobalt ferrite possesses an inverse spinel structure and the degree of inversion depends upon heat treatment [911]. In this paper an attempt is made to present the behaviour of structural, magnetic and electrical properties such as dielectric constant ( ), tangent of dielectric loss angle (tan) and dielectric loss factor ( ) of the system CoFe2x Alx O4 (for x = 0.00, 0.25, 0.50) as a function of frequency.
2. Experimental
The starting materials were iron nitrate, aluminum nitrate, cobalt nitrate, citric acid and ammonia, all of analytical grade. The solutions of CoCl2 6H2 O, Fe(NO3 )3 9H2 O and Al(NO3 )3 9H2 O in their stoichiometry (200 ml of 0.1 M Co(NO3 )2 6H2 O, 200 ml of 0.15 M Fe(NO3 )3 9H2 O, 200 ml of 0.05 M Al(NO3 )2 9H2 O in the case of CoFe1.5 Al0.5 O4 and similarly for the other values of x) were dissolved in a deionized water. Citric acid was then added to the prepared aqueous solution to chelate Co2+ , Fe3+ and Al3+ , in the solution. The molar ratio of citric acid to total moles of nitrate ions was adjusted at 1:1. The mixed solution was neutralized to pH 7 by adding 2 M solution of ammonia. The neutralized solution was evaporated to dryness by heating at 100 C on a hot plate with continuous stirring, until it becomes viscous and nally formed a very viscous gel. Increasing the temperature up to 200 C led to the ignition of the gel. The dried gel burnt completely in a self-propagating combustion manner to form a loose powder. Finally, the as-burnt powders were calcined in air at temperatures of 800 C for 6 h with a heating rate of 5 C/min to obtain the spinel phase. The structural characterization of all the samples was carried out by the X-ray diffraction (XRD) and conrmed the formation of well-dened singlephase spinel structures. XRD data were taken at room temperature using Cu radiation. The crystallite size, t311, was calculated using the K ( = 1.5406 A) Scherrer formula [12]. DC electrical resistivity for all these samples was measured by two-probe method. A low value of constant voltage was applied across the sample and the current through the sample was measured as a function of temperature. The sample was heated with microfurnace tted to the sample holder assembly. Temperature of the pellets was measured with ChromelAlumel thermocouple. The DC electrical resistivity of all the samples decreases with increasing temperature according to Arrhenius equation [13] = 0 exp E kB T , (1)

where is the loss angle, f is the frequency, Rs is the equivalent series resistance and Cs is the equivalent series capacitance. The dielectric loss factor ( ) is also measured in terms of tangent loss factor (tan) dened by the relation [14] = tan , (4)

3. Results and discussion The X-ray patterns of the synthesized samples CoFe2x Alx O4 (for x = 0.00, 0.25, 0.50) are shown in Fig. 1. All the samples can be indexed as the single-phase cubic spinel structure. No additional phase was detected. The borad peaks signies lower crystallite size of the synthesized samples. The average crystallite size for each composition was calculated using the Scherrer formula [12] from the line broadining of the XRD peak corresponding to the (3 1 1) plane of the spinel structure. The crystallite size remains with in the range 1823 nm. The lattice

where kB is Boltzmann constant, T is temperature and E is the activation energy. The dielectric constant ( ) measurements were carried out in the frequency range from 500 Hz to 1 MHz at room temperature using LCR meter bridge (WK LCR 4275). The dielectric constant was determined from the formula = Cd , o A (2)

where C is the capacitance of the pellet in farad, d the thickness of the pellet in meter, A the cross-sectional area of the at surface of the pellet and o the constant of permittivity of free space.

Fig. 1. Indexed X-ray pattern of CoFe2x Alx O4 ferrite nanoparticles.

I.H. Gul, A. Maqsood / Journal of Alloys and Compounds 465 (2008) 227231 Table 1 Crystallite size (t), lattice parameter (a), lattice volume (V), X-ray density (x ), measured density (m ), Curie temperature (Tc ), activation energy ( E), correlation coefcient (R), DC electrical resistivity (), dielectric constant ( ), tangent of dielectric loss angle (tan) and the dielectric loss factor ( of CoFe2x Alx O4 ferrite nanoparticles Parameter t(3 1 1) (nm) a (A) 3) V (A x (g cm3 ) m (g cm3 ) Tc (5K) E 0.001 R ( cm) at 373 0.01 K at 1 MHz tan at 1 MHz at 1 MHz x = 0.00 23 8.474(5) 609 5.129 3.138 667 0.557 0.999 2.59 106 13 0.41 5.26 x = 0.25 20 8.455(6) 604 5.010 2.995 594 0.590 0.999 4.49 108 11 0.36 4.03 x = 0.50 18 8.414(3) 596 4.957 2.402 528 0.660 0.999 1.06 109 5 0.24 1.21

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constant a, was calculated using the relation a = dh k l h2 + k 2 + l 2 , (5)

Fig. 2. Inverse AC magnetic susceptibility vs. temperature of CoFe2x Alx O4 ferrite nanoparticles.

where the values of lattice constant a, for each composition are calculated and tabulated in Table 1. The lattice parameter with Al3+ concentration (x). The decreases from 8.4748.414 A decrease in lattice parameter may be due to the substitution of for large Fe3+ ions (0.64 A) in the smaller Al3+ ions (0.51 A) system CoFe2x Alx O4 . Since smaller ions are replacing larger ones, a decrease in the lattice parameter is expected. Hence the observed behaviour of the lattice parameter can be understood. Measured density was calculated from the weight and dimensions of the sintered samples according to the following relation: (m = m/V) [12], where m is the mass of the sample and V its volume and the values are tabulated in Table 1. From the table, it is seen that the measured density decreases from 3.138 to 2.402 g cm3 with Al3+ concentration. This may be due to the fact that Al has smaller atomic weight (26.98 amu) than the Fe (55.85 amu) atoms. The X-ray density was calculated using the relation: (x = 8M/Na3 ) [12], where N is the Avogadros number, a is the lattice parameter and M is the atomic weight. The X-ray density decreases from 5.129 to 4.957 g cm3 with Al3+ concentration for all the compositions, because the decrease in mass over takes the decrease in volume of the unit cell. The AC magnetic susceptibility () measurements for all the samples were carried out in the temperature range from 300 to 800 K. Fig. 2 shows the AC magnetic susceptibility spectra for CoFe2x Alx O4 ferrites. The inverse susceptibility rise sharply when the magnetic state of the ferrite nanoparticles changes from ferromagnetic to paramagnetic states. It is observed from the gure that the Curie temperature is lower when Al3+ concentration is high. This is expected because of the insulation of non-magnetic Al3+ ions preferentially occupy the B sites [15] of the spinel lattice. According to Neel model, the AB interaction is most dominant in ferrites, therefore, Curie temperature of ferrites are determined from the overall strength of AB interaction [16]. The value of Curie temperature with Al3+ concentration is also tabulated in Table 1 The decrease of Curie temperature

with an increasing Al3+ concentration has been explained by a modication of the AB interaction strength due to the change of Fe3+ concentration between A and B sites, reducing thereby the AB exchange interaction. This could be attributed to the decrease in distance between the moment of A and B sites, which is conrmed by the decrease in lattice parameter with Al3+ concentration. Temperature variation of DC electrical resistivity has been measured by two-probe method as a function of temperature in Fig. 3. It is evident from the gure that as the concentration of Al3+ increases, the DC electrical resistivity increases. It is well known that Al3+ occupy octahedral site B, while Co2+ and Fe3+ ions occupy A and B sites [15,2]. The observed variation in DC electrical resistivity may be explained by Verveys hopping mechanism [17]. According to Vervey, the conduction mechanism in ferrite occurs mainly through the hopping between Fe2+ and Fe3+ in the B sites. The hopping probability depends upon the separation between the ions involved and activation

Fig. 3. Variation of DC electrical resistivity (ln) with inverse temperature (1/kB T) for CoFe2x Alx O4 ferrite nanoparticles.

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energy. The distance between the two metal ions at B sites are smaller than the distance between two metal ions one at B site and another A site. The electron hopping between B and A sites under normal conditions therefore has a very small probability compared with that for BB hopping. Hopping between A and B sites does not exit for the simple reason that there are only Fe3+ ions at A site and only Fe2+ ions formed during processing preferentially occupy B sites only. Thus, the decient of Fe2+ ions with increasing Al3+ concentration gives further reason for the increase of the DC electrical resistivity. The measured values of DC electrical resistivity at 373 K were found to vary from 2.59 106 to 1.06 109 cm as the concentration of Al3+ increases from x = 0.00 to 0.50. High DC electrical resistivity and relatively easy preparation make CoFe2x Alx O4 ferrite nanoparticles widely useable for the cores of intermediate and high frequency electromagnetic absorbers. The activation energy of each sample in the measured temperature range can be determined from the slope of the linear plots (Fig. 3) of DC electrical resistivity. The value of activation energy ranges from 0.557 to 0.660 eV. In ferrite samples, the activation energy is often associated with the variation of mobility of the charge carriers rather than with their concentration. The charge carriers are considered as localized at the ions or vacant sites and conduction occurs via a hoping process. The hopping depends upon the activation energy, which is associated with the electrical energy barrier experienced by the electrons during hopping. The dielectric properties of ferrite nanoparticles are inuenced mainly by the method of preparation, cations distribution, grain size, sintering temperature, oxygen parameter, the ratio of Fe2+ /Fe3+ ions and oxygen anion vacancies in lattices. Fig. 4 shows the variation of dielectric constant ( ) as a function of frequency at room temperature from 500 Hz to 1 MHz. A sample with high DC electrical resistivity acquires low values of dielectric constant and vice versa [18,19]. The dielectric behaviour can be explained qualitively by the supposition that the mechanism of the polarization process in ferrites is similar to that in the conduction process. The value of the dielectric constant is very high

at lower frequencies and decreases with the increase of frquency. At lower frequencies the grain boundaries are more effective than grains in electrical conduction. This is in agreement with ealier observations of other workers on ferrites [20,21]. By the electronic exchange Fe2+ Fe3+ + e1 , one obtains local displacements of electrons in the direction of the applied electric eld. These displacements determine the polarization in the ferrites. It is well known that the effect of polarization is to reduce the eld inside the media. The decrease of polarization of the dielectric constant with increasing frequency is due to the fact that beyound certain frequency of the electric eld, the electronic exchange between Fe2+ and Fe3+ ion cannot follow the alternating eld. Since an assembly of space charge carriers in a dielectric requires nite time to line up their axes parallel to an alternating electric eld, if the frequency of the eld reversal increases, a point will reached when the space charge carriers cannot keep up with the eld and the alternation of their direction lags behind the eld. As the frequency of the eld continues to increase, at some stage the space charge carriers will barely have started to move before the eld reverses and make virtually no contribution to the polarization of the dielectric. Therefore, dielectric constant of a material may decrease substantially as the frequency is increased. The tangent of dielectric loss angle (tan) was determined using Eq. (3). Fig. 5 shows the variation of tan at room temperature as a function of applied eld frequency in the range 500 Hz to 1 MHz for all the samples. It can be seen that a small abnormal behaviour was observed for all the samples at different frequencies. According to Rezlescu model the relaxation peak may be due to the collective contribution of both p and n type of charge carriers [22]. The electronic exchange between Fe2+ Fe3+ and hole transfer between Co2+ Co3+ in octahedral sites are responsible for such behaviour. Furthermore, the jumping frequencies of localized charge carriers are almost equal to that of the applied AC electric eld. The dielectric loss factor ( ) was determined using Eq. (4). Dielectric loss is an important part of the total core loss in fer-

Fig. 4. Variation of dielectric constant with lnf (Hz) of CoFe2x Alx O4 ferrite nanoparticles at room temperature.

Fig. 5. Variation of tangent of dielectric loss angle with lnf (Hz) of CoFe2x Alx O4 ferrite nanoparticles.

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samples increases with the increase of Al3+ concentration. The dielectric constant decreases with increasing frequency for these all cobalt ferrite nanoparticle compositions. The values of , tan and decreases from 11 to 5, 0.41 to 0.24 and 5.27 to 1.21, respectively, at 1 MHz. Low dielectric constants increase the penetration depth of the electromagnetic waves by decreasing the skin effect. Hence, the much lower dielectric constants obtained for the ferrites warrant their application at high frequencies as microwave absorbers. Acknowledgements The authors would like to acknowledge Higher Education Commission (HEC) Islamabad, Pakistan and Quaid-i-Azam University Research fund (URF) for providing nancial support for this work. The authors are grateful to Mr. Naeem Ashiq, Department of Chemistry of this university for his kind help in preparation of ferrite nanoparticles. References
[1] A.T. Ngo, M.P. Pileni, J. Phys. Chem. B 105 (2001) 53. [2] S. Singhal, J. Singh, S.K. Barthwal, K. Chandra, J. Solid State Chem. 178 (2005) 3183. [3] M.H. Sousa, F.A. Tourinbo, J. Phys. Chem. B 105 (2000) 168. [4] K. Raj, R. Moskowitz, R. Casciari, J. Magn. Magn. Mater. 149 (1995) 174. [5] J. Smit, H.P.J. Wijn, Ferrites, Wiley, London, 1959, p. 140. [6] C.B. Kolekar, P.N. Vasambekar, S.G. Kulkarni, A.S. Vaingankar, J. Mater. Sci. 30 (1995) 5784. [7] B.P. Ladgoankar, C.B. Kolekar, P.N. Vasambekar, A.S. Vaingankar, Ind. J. Eng. Mater. Sci. 7 (2000) 419. [8] B. Vishwanathan, V.R.K. Murthy, Chemistry of Ferrites, Norosa Publication House, New Delhi, 1990, p. 58. [9] D.R. Mane, U.N. Devatwal, K.M. Jadhav, Mater. Lett. 44 (2000) 91. [10] G.A. Sawataky, F. Van der Wouds, A.H. Morrish, J. Appl. Phys. 39 (1968) 1204. [11] X.M. Liu, S.Y. Fu, H.M. Xiao, C.J. Huang, Physica B 370 (2005) 14. [12] I.H. Gul, F. Amin, A.Z. Abbasi, M. Anis-ur-Rehman, A. Maqsood, Scripta Mater. 56 (2007) 497. [13] I.H. Gul, A.Z. Abbasi, F. Amin, M. Anis-ur-Rehman, A. Maqsood, J. Magn. Magn. Mater. 311 (2007) 494. [14] D. Ravinder, K.V. Kumar, Bull. Mater. Sci. 24 (2001) 505. [15] A.A. Sattar, J. Mater. Sci. 39 (2004) 451. [16] L. Neel, C. R. Acad. Sci., Paris 230 (1950) 275. [17] E.J.W. Vervey, J.H. De Boer, Rec. Trans. Chim, des Pays-Bas 55 (1936) 531. [18] F.G. Brockman, P.H. Dowling, W.G. Steneck, Phys. Rev. 75 (1949) 1440. [19] D. Ravinder, B.R.P. Vijaya, Mater. Lett. 57 (2003) 4344. [20] D. Kothari, S. Phanjoubam, J.S. Baijal, J. Mater. Sci. 25 (1990) 5142. [21] R. Manjula, V.R.K. Murthy, J. Sobhanadri, J. Appl. Phys. 59 (1986) 2929. [22] N. Rezlesecu, E. Rezlescu, Phys. Stat. Sol (a) 23 (1974) 575. [23] J. Zhu, K.J. Tseng, C.F. Foo, IEEE Trans. Magn. 36 (2000) 3408. [24] A.S. Hudson, Marconi Rev. 37 (1968) 43.

Fig. 6. Variation of dielectric loss factor with lnf (Hz) of CoFe2x Alx O4 ferrite nanoparticles.

rites [23]. The dielectric loss factor as a function of frequency for all the compositions is depicted in Fig. 6. The dielectric loss proles are similar to those of dielectric constant. The increase in hoping electrons result in a local displacement in the direction of the extent electric eld causing an increase in electric polarization enhances dielectric loss. Hudson [24] has shown that, the dielectric losses in ferrite is reected in the conductivity measurements where the materials of high conductivity exhibiting high losses and vice versa. Thus, the present ferrite nanoparticles with relatively lower losses could be useful at frequencies higher than those of the individual ferrites. 4. Conclusions Single-phase well-crystallized ferrite nanoparticles CoFe2x Alx O4 (for x = 0.00, 0.25, 0.50) were successfully synthesised using the solgel route. The particle size was calculated from the most intense peak (3 1 1) using the Scherrer formula. The crystallite size of all the samples decreases the substitution of Al3+ in the lattice. The lattice parameter a decreases with increase of Al3+ concentration due to smaller ionic radius of Al3+ compared to Fe3+ . The Curie temperature decreases from 667 to 528 K with increase of Al3+ concentration. The decrease of Curie temperature with non-magnetic Al3+ concentration has been explained by the AB exchange interaction strength due to the change of Fe3+ distribution between A and B sites. Temperature dependent DC electrical resistivity decreases with increase in temperature ensuring the semiconductor like behavior of the samples. Activation energy calculated from the DC electrical resistivity versus temperature for all the