Solid State Communications 147 (2008) 479483

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Solid State Communications

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Structural investigations and magnetic properties of cobalt ferrite nanoparticles prepared by solgel auto combustion method
B.G. Toksha, Sagar E. Shirsath, S.M. Patange, K.M. Jadhav
Department of Physics, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad: 431 004 (MS), India

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a b s t r a c t
Morphological and magnetic characteristics of cobalt ferrite nanoparticles synthesized by solgel auto combustion method using nitrates of respective metal ions have been studied. X-ray diffraction pattern was indexed by a Rietveld program to calculate accurate unit cell dimension. A Transmission Electron Microscope (TEM) confirmed the formation of single phase cobalt ferrite nanoparticles in the range 1140 nm depending on the annealing temperature and time. The size of the particles increases with annealing temperature and time while the coercivity goes through a maximum, peaking at around 25 nm. A very large coercivity (10.2 kOe) is observed on cooling down to 77 K while typical blocking effects are observed below about 260 K. The high field moment is observed to be small for smaller particles and approaches the bulk value for large particles. Mossbauer spectra recorded at room temperature is a sextet indicating that there is a strong magnetic coupling and increase in sintering temperature from 570 C to 800 C do not affect Mossbauer parameters. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 27 May 2008 Received in revised form 26 June 2008 Accepted 27 June 2008 by E.V. Sampathkumaran Available online 8 July 2008 PACS: 75.50Gg 75.50Tt 75.70Rf 75.50.Vv 33.45._x Keywords: A. Magnetically ordered materials B. Chemical synthesis C. Scanning and transmission electron microscopy

1. Introduction Metal-oxide nanoparticles have been the subject of current interest because of their unusual optical, electronic and magnetic properties, which often differ from their bulk counter-part [1, 2]. Nanocrystalline magnetic particles are gaining attraction due to many important applications such as ferrofluids, magnetic drug delivery, hyperthermia for cancer treatment [35]. Among the magnetic particles, cobalt ferrite (CoFe2 O4 ) is a well-known hard magnetic material. The high coercivity [6] and moderate magnetization [7] makes CoFe2 O4 a good candidate for many applications. The remarkable properties such as high saturation magnetization, high coercivity, strong anisotropy along with good mechanical hardness and chemical stability are not observed in the bulk sample [8]. These properties, along with their great physical and chemical stability, make CoFe2 O4 nanoparticles suitable for magnetic recording applications such as audio and videotape and high-density digital recording disks etc. [9,10]. The magnetic character of the particles used for recording media depends

Corresponding author. E-mail address: drkmjadhav@yahoo.com (K.M. Jadhav).

crucially on the size, shape and purity of these nanoparticles. The particles should be single domain, of pure phase, should have high coercivity and medium magnetization for using them in recording media. Techniques to produce nanoparticles include wet chemical co-precipitation, hot spraying, evaporation condensation, matrix isolation, laser-induced vapor phase reactions and aerosols. Generally, in most types of nanoparticles prepared by these methods, control of size and size distribution is not possible [11]. In order to overcome these difficulties, nanometer size reactors for the formation of homogeneous nanoparticles of cobalt ferrite are used. To protect the oxidation of these nanoparticles from the atmospheric oxygen and also to stop their agglomeration, the particles are usually coated and dispersed in some medium like sodium dodecyl sulfate (NaDS) or oleic acid [12,13]. In general, the preparation methods for CoFe2 O4 nanoparticles have been quite complicated requiring special techniques to prevent agglomeration [14]. In this paper, we have presented the synthesis of cobalt ferrite (CoFe2 O4 ) nanoparticles by solgel method followed by heat treatment at 570 C. The size and size distribution of the particles prepared by this method was studied by XRD and TEM. The dependence of the particle size on the annealing temperature and annealing time was

0038-1098/$ see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.ssc.2008.06.040

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also studied. Finally, various magnetic properties of the particles have been studied as functions of field, temperature and size. 60 Co Mossbauer spectroscopy is a nuclear-probe technique that is very well suited for the investigation of the local symmetry, the magnetic state, and the charge states of iron ions in ironcontaining materials. The Mossbauer analysis of prepared samples is also presented in this paper. 2. Experimental procedure Nanocrystalline powder of CoFe2 O4 were prepared by solgel auto-ignition method. The A.R. Grade citric acid (C6 H8 O7 H2 O), Cobalt nitrate (Co(NO3 )2 6H2 O) (>99% sd-fine) were used as starting materials. Reaction procedure was carried out in air atmosphere without protection of inert gases. The molar ratio of metal nitrates to citric acid was taken as 1:3. The metal nitrates were dissolved together in a minimum amount of double distilled water to get a clear solution. An aqueous solution of citric acid was mixed with metal nitrates solution, then ammonia solution was slowly added to adjust the pH at 7. The mixed solution was kept on to a hot plate with continuous stirring at 90 C. During evaporation, the solution became viscous and finally formed a very viscous brown gel. When finally all water molecules were removed from the mixture, the viscous gel began frothing. After few minutes, the gel automatically ignited and burnt with glowing flints. The decomposition reaction would not stop before the whole citrate complex was consumed. The auto-ignition was completed within a minute, yielding the brown-colored ashes termed as a precursor. It is known that the pure CoFe2 O4 obtained by the solgel method can be formed at 570 C and thoroughly crystallized at temperatures above 570 C [15] The as-prepared powders of all the samples were heat treated separately at 570 C for 4 h to get the final product. The final product obtained was then confirmed by X-ray diffraction (XRD). The Rietvelds powder structure refinement analysis of XRD data is adopted to obtain the refined structural parameter and lattice parameter. Particle size and particle size distribution is done by transmission electron microscopy (TEM). Vibrating sample magnetometer (VSM) gave the values of saturation magnetization and coercivity. Mossbauer spectra of samples were used to identify magnetic phase of cobalt ferrite. Mossbauer spectra were recorded at room temperature using a constant acceleration drive and a personnel computer analyzer (PCA card with 1024 channel). The source was 60 Co in Rh matrix at room temperature with an initial activity of 25 mCi. The optimal weight of the absorber was approximately 10 mg/cm2 of natural iron. Metallic iron spectrum was used for the calibration of both observed velocities and hyperfine magnetic field. 3. Results and discussion The analysis of X-ray diffraction pattern of the calcined powder synthesized using this route shows that the final product is CoFe2 O4 with the expected inverse spinel structure. X-ray diffraction pattern was indexed by TREOR program to calculate accurate unit cell dimension. The data were processed to realize the conditions of the software program FullProof for the structure refinement. The XRD pattern is shown in Fig. 1. The value of lattice constant is found to be 8.3731 0.004 . The inversion parameter calculated from Rietveld refinement is 0.82 which is in good agreement for values reported in literature [16,17]. The value of discrepancy factor is 6.31 and expected value is 3.62 and the goodness of fit index was 1.74. The size of the particles was determined by Scherrer formula using most incense (311) peak. The average sizes of the particles calcined at 570 C were found to be 15 nm. By annealing 15 nm particles at 800 C and 900 C for 10 h, particle sizes of 24

Fig. 1. X-ray diffraction pattern (Cu K -radiation) of CoFe2 O4 nanoparticles prepared by solgel method, after calcinations at 570 C for 4 h.

Fig. 2. TEM micrograph of CoFe2 O4 nanoparticles prepared, after calcinations at 570 C for 4 h.

and 28 2 nm were obtained. Finally, on further annealing, at 1000 C for 8 and 12 h, respectively, 32 and 40 2 nm particles were obtained. Thus, the size variation has been achieved by the annealing conditions. The TEM images (Fig. 2) of CoFe2 O4 nanoparticles calcined at 570 C for 4 h (with average crystallite size of about 15 nm. The size distribution of these nanoparticles as observed in TEM images is shown in Fig. 3. The distribution seems to be symmetric (Gaussian) about 15 nm, with particles of sizes 1120 nm for this specimen. The maximum number lie between 1416 nm, peaking at 15 nm, in good agreement with XRD crystallite size. Most of the particles appear spherical in shape however some elongated particles are also present. Some moderately agglomerated particles as well as separated particles are present in the images. Agglomeration is understood to increase linearly with annealing temperature and therefore agglomeration at this temperature appears unavoidable. Fig. 4 shows the correlation between the particle size and annealing temperature. The size of the particles is observed to be increasing linearly with annealing temperature. It appears that that increase in size with temperature becomes rapid between 700900 C and appears to be slowing down above 900 C. While annealing generally decreases the lattice defects and strains, however it can also cause coalescence of crystallites that results in increasing the average size of the nanoparticles [18]. The Fig. 5 shows the dependence of particle size on annealing time at a fixed annealing temperature of 570 C. The particle size appears to increase almost linearly with annealing time, most likely due to the fact that longer annealing time enhances the coalescence process resulting in an increase in the particle size. Thus, it appears that particle size may be controlled by varying either of the two parameters i.e. annealing temperature and time.

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Fig. 3. Size distribution of CoFe2 O4 nanoparticles from TEM images (570 C calcinations for 4 h).

Fig. 6. Hysteresis loops for 15 nm CoFe2 O4 nanoparticles at room temperature (300 K) and 77 K at maximum applied field of 12 kOe.

Fig. 4. Particle size (nm) as a function of annealing temperature (570 C) for CoFe2 O4 nanoparticles.

found to be 67 emu/g and remanent magnetization (Mr) was 30.2 emu/g, while at 77 K the values for the same parameters were 43 emu/g and 35 emu/g, respectively. The very large coercivity and low saturation magnetization at 77 K are may be related with a pronounced growth of magnetic anisotropy inhibiting the alignment of the moment in an applied field. The remanance ratios at these temperatures indicate the same feature, rising from 0.45 to 0.81 at 77 K. The value of remanance ratio of 0.45 is close to that expected (0.5) for a system of noninteracting single domain particles with uniaxial anisotropy [19]. The existence of an effectively uniaxial anisotropy in magnetic nanoparticles has been attributed to surface effects [20,21] as evidenced by simulations of nanoparticles. Surface effects also tend to lead to large anisotropies. Some reports argued that due to the disorder near the surface, the typical two sublattice picture for antiferromagnetic or ferrimagnetic nanoparticles appears to break down and multiple sublattice picture appears to hold [22]. There appears to be a situation where several different spin configurations e.g. 2, 4, 6 sublattice models have very similar energies and hence multiple ground states are possible e.g. in a spinglass. The interaction between the core and surface spins leads to a variety of effects including large anisotropy and exchange bias effects. It is common to find higher effective anisotropy values in magnetic nanoparticles as compared to their bulk counterpart. In a fine particles system where the dominant mechanism is replaced by the rotation of magnetic moment, with the assumption that the particles are randomly oriented and the strain distribution is homogeneous in the samples, b is described as [23] b= 1
2 MS

8 105

2 K1 +

4 15

2 Ksh +

3 5

2 2 +

4 15

2 Ksf

Fig. 5. Correlation between particle size and annealing time in hrs (at 570 C).

where, K1 is the magneto-crystalline anisotropy constant, Ksh the shape anisotropy constant, Ksf the surface anisotropy, = |S | the magnetostriction constant and the internal strain. For simplicity and comparison with the bulk materials, here the effective magnetic anisotropy KE is defined as
2 2 KE = Ksh +

Magnetic characterization of the particles was done using vibrating sample magnetometer (VSM), at room temperature and at 77 K, with maximum applied field up to 12 kOe (Fig. 6). For the 15 nm size particles the coercivity at room temperature was 1215 Oe while at 77 K it had increased to 10.2 kOe. The saturation magnetization (MS ) obtained at room temperature was

9 4

2 2 2 + Ksf ,

so, b= 1
2 MS

8 105

2 K1 +

4 15

2 KE

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In the approaching saturation region, b can be determined from the approximation M = MS (1 b/H 2 ) and MS can be obtained by extrapolation of the line to the axis. From a fit of the magnetization data at high fields using the law of approach to saturation

2 M Keff . = H MS H 3

In the present study the value of the anisotropy constant is Keff = 3.7 107 ergs/cc, where = 0.524 for uniaxial anisotropy and the value of anisotropy constant for 800 C is Keff = 3.2 106 ergs/cc. For the samples sintered at 570 C the value of anisotropy constant is higher by one order of magnitude than the value for bulk cobalt ferrite [24]. The value for samples sintered at 800 C is very close to that of bulk samples. The coercivity of the nanoparticles was also studied as a function of particle size. Fig. 7. shows the coercivity as a function of particle size at room temperature (300 K). The Gaussian fit to the data shows the coercivity increases with size rapidly, attaining a maximum value of 1215 Oe at 25 nm and then decreases with size of the particles. This decrease at larger sizes could be attributed to either of two reasons. Firstly, it may be due to the expected crossover from single domain to multidomain behavior with increasing size. Secondly such an effect can arise from a combination of surface anisotropy and thermal energies. The former effect is expected in CoFe2 O4 particles for a size close to 40 nm [25] that is significantly higher than the critical size of 25 nm that we observed. The latter source of the effect is therefore considered as a more likely explanation for the peak. The initial increase of the coercivity with decreasing size can be understood due to the enhanced role of the surface and its strong anisotropy, as opposed to the weaker bulk anisotropy. This rise is followed by a decline at small enough sizes when the product of the anisotropy energy and volume becomes comparable to the thermal energy, leading to thermally assisted jumps over the anisotropy barriers. It is also likely that the two processes are operating simultaneously and the single domain effects may not be excluded, however the dominant role will be of the surface effects for smaller particles. The decrease of Hc at d 40 nm may very well have a contribution from the development of domain walls in the nanoparticles. Fig. 7 also shows the dependence of saturation magnetization on particle size. The MS values obtained for the samples are in the range 5076 emu/g. The maximum value of saturation magnetization is 76 emu/g for 40 nm particles which is close to the bulk value for CoFe2 O4 . The saturation magnetization increases consistently with particle size. For small particles the value of Ms is significantly lower than the bulk value of 80 emu/g while for the size of 40 nm the magnetization value approaches to the bulk value. A very sharp increase in the magnetization between the sizes of 1025 nm is observed while there is a slower increase thereafter, as in the case of coercivity and blocking temperature. The decrease in MS at small particle sizes is related with the effects of the relatively non-reactive surface layer that has low magnetization. This surface effect becomes less significant with increasing sizes and above 40 nm seems to be no longer relevant to the bulk magnetization. The magnetization of different size nanoparticles is shown as a function of temperature in Fig. 8. The samples were zero field cooled (ZFC) to 77 K. After cooling a field of 5kOe was applied and magnetization was recorded as function of temperature up to 300 K. A peak in the magnetization is evident in each case with the exact position of the peak depending on the size. It is understood that in the ZFC mode the magnetization of a collection of nanoparticles may go through a peak as the particles moments become blocked along the anisotropy axes. The blocking temperature (TB ) is defined as the temperature at which maximum magnetization is achieved. This temperature is a function of applied field and typical time scale of measurement. The Fig. 9

Fig. 7. The correlation between the coercivity (HC ) and mean particle diameter (nm), at room temperature and applied field of 15 kOe and saturation magnetization (MS ) as function of particle size (nm) at maximum applied field of 15 kOe.

Fig. 8. Temperature dependence of magnetic susceptibility for zero-field cooled (ZFC) CoFe2 O4 nanoparticles at applied field of 5 kOe.

shows the effect of size on the blocking temperature. There is a clear increase in the blocking temperature with size, it is also observed that this increase is very rapid in the beginning (at smaller sizes) and thereafter the increase becomes very slow appearing to reach a maximum at T 272 K. The larger particles seem to be blocked at high temperatures as compared to the smaller particles at the same field. For larger particles, the larger volume causes increased anisotropy energy which decreases the probability of a jump across the anisotropy barrier and hence the blocking is shifted to a higher temperature. From the data it appears that above about 25 nm the particle blocking becomes relatively insensitive to size. The analysis of the Mossbauer spectra provides very important information about the chemical, structural and magnetic properties of ferrite samples from hyperfine interaction, isomer shift and quadrupole splitting. Mossbauer absorption spectra measured at room temperature for cobalt ferrite powders annealed at 570 C and 800 C temperatures are shown in Fig. 10. The Mossbauer spectra of samples are fitted with two six-line sub-patterns that are assigned to A-ions in tetrahedral sites and B-ions in octahedral sites of a typical spinel crystal structure. The value of average line width (mm/s) for samples sintered at 570 C hereafter called as sample (a) and for samples sintered at 800 C hereafter called as sample (b) is found to be 0.539 0.003 and 0.548 0.003. It may be concluded from these values that increase in sintering temperature from 570 to 800 C do not much affect the site symmetry [26].

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Fig. 9. Dependence of blocking temperature (TB ) on particle size (nm).

was no agglomeration and that the size distribution of the prepared nanoparticles was small. The Rietveld-refined inversion parameter value shows the cobalt ferrite in the present study have partially inverted spinel structure. The size of the nanoparticles increase linearly with annealing temperature and time most probably due to coalescence that increases as annealing temperature increases. The very large coercivity and low saturation magnetization at 77 K in comparison with room temperature appear to be due to a pronounced growth of magnetic anisotropy at low temperatures. The observed magnetization remanance ratio of 0.45 at room temperature is close to the value of 0.5 typical of a system of non-interacting single domain particles suggests that CoFe2 O4 nanoparticles exhibit an effective uniaxial anisotropy. The effective uniaxial anisotropy in magnetic nanoparticles has been explained as arising from surface effects that also lead to large anisotropy energy in nanoparticles. The coercivity shows maxima with particle size at a value much smaller than the single domain range and is attributed to the thermal effects which are prominent at small particle sizes. For smaller particles the value of saturation magnetization was significantly lower than the bulk value while for the larger size particles the values were approaching to those of the bulk. The smaller value of MS in smaller particles is attributed to the greater fraction of surface spins in these particles that tend to be in a canted or spin glass like state with a smaller net moment. The coercivity of ferrite powder strongly depended on the annealing temperatures and can be directly related to the variation of cobalt ferrite particle sizes. The Mossbauer patterns of both the samples (a) and (b) are sextet indicating there is a magnetic coupling. Therefore, no doublet could be observed which is the significance of the superparamagnetic state. References
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Fig. 10. Mossbauer absorption spectra measured at room temperature for cobalt ferrite powders annealed at 570 C sample (a) and 800 C sample (b).

The values of average isomer shift for sample (a) and for sample (b) are 0.371 0.003 and 0.362 0.003, respectively. These values are in agreement with values reported in literature [27]. There is no significant change of isomer shift values by increase in sintering temperature. This means that the s electron charge distribution of Fe ions is negligibly influenced by temperature. The value of quadrupole splitting is 0.069 for sample (a) and 0.071 for sample (b), no much difference in quadrupole splitting values indicates that there is no electric field gradient generated with the change in sintering temperature. The hyperfine field values of tetrahedral site for sample (a) and sample (b) are 461 and 462 kOe, respectively, and that is of octahedral site for sample (a) and sample (b) are 430 and 432 kOe. These values are in good agreement with those reported in the literature [28]. In spinel lattice the values of hyperfine fields are attributed to Fe3+ and tetrahedral (A) site and octahedral [B] site. The hyperfine values for present study shows that the percentage of Fe3+ at A and B site do not change by change in temperature from 570 to 800 C. 4. Conclusion The synthesis of CoFe2 O4 nanoparticles in the range 1140 nm is done successfully by solgel auto combustion technique. The particle size measured by both XRD and TEM of the nanoparticles were in very good agreement with each other indicating that there