Solid State Sciences 12 (2010) 839844

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Solid State Sciences

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Low temperature synthesis of zinc ferrite nanoparticles

A. Bardhan a, C.K. Ghosh a, b, M.K. Mitra a, G.C. Das a, S. Mukherjee a, K.K. Chattopadhyay a, b, *
a b

School of Materials Science and Nanotechnology, Jadavpur University, Kolkata 700032, India Thin Film and Nanoscience Laboratory, Department of Physics, Jadavpur University, Kolkata 700032, India

a r t i c l e i n f o
Article history: Received 11 November 2009 Received in revised form 28 January 2010 Accepted 2 February 2010 Available online 8 February 2010 Keywords: Zinc ferrites X-ray photoelectron spectroscopy Dielectric property a.c. conductivity

a b s t r a c t
Zinc ferrite (ZnFe2O4) nanocrystalline powder materials with various particle sizes were prepared by a unique solid-state combustion method. Phase purity of ZnFe2O4 was conrmed by X-ray diffraction studies. High resolution transmission electron microscopic analysis and selected area diffraction pattern also conrmed the correct crystalline phase formation. Particle size was determined from both the transmission electron microscopic images and also from the XRD peak broadening analysis. Oxidation states of different elements present in ZnFe2O4 were determined by X-ray photoelectron spectroscopy. Frequency dependent dielectric constant and a.c. conductivity were measured as a function of particle size and both of them were found to decrease with decreasing particle size. These studies indicated that good quality zinc ferrite nanocrystalline powdered materials can be synthesized at low temperature. 2010 Elsevier Masson SAS. All rights reserved.

1. Introduction The special attributes of nanomaterials arising due to their unique physical properties like electrical conductivity, optical band gap, refractive index, magnetic properties and superior mechanical properties such as hardness of nanomaterials are being revealed and understood gradually by the scientists. As the research community is gaining deeper understanding of these unique behaviors and applications of nanostructured materials, a new eld of study known as nanotechnology has emerged [1,2]. Among various nanomaterials, magnetic nanoparticles mainly spinel ferrite (MFe2O4, M Ni, Co, Mn, Zn etc.) nanoparticles, are of special interest for their attractive scientic and technological aspects in different elds such as magnetic recording and separation, catalyst, photocatalyst, drug delivery, pigments, ferrouids, magnetic resonance imaging (MRI), hot gas desulfurization etc. [311]. Apart from these applications spinel ferrites can also be used in many electronic devices due to their high permeability at high frequencies, high mechanical hardness, chemical stability and reasonably low cost. The spinel ferrites are highly suitable for computer memories, logical devices, transformer cores, recording heads etc. The size of the grain plays a crucial role in all these applications [12]. Another important

application of ferrites is as a highly insulating material. Its high resistivity prevents the induction of eddy currents in the presence of alternating magnetic eld and proves the necessity of these ferrite nanoparticles in the high frequency applications [13]. It has been observed by many researchers that the conductivity decreases with decrease in particle size [14]. So, ferrite nanoparticles can be of better use to prevent eddy current. Currently, the synthesis of spinel ferrites is being carried out by different techniques to achieve desired size and shape (in nano dimension) in order to improve their physical properties and widen the scope of their applications [15,16]. Different methods, such as ion implantation [17], co-precipitation [18], thermal decomposition of zinciron tartrate precursor [19], ball milling [20] etc. have been adopted by the scientists to prepare zinc ferrite (ZFO) nanoparticles. Here, we have rst successfully synthesized ZFO nanoparticles using combustion technique at very low temperature that has not been reported so far. The electrical properties of ZFO nanoparticles as a function of their sizes have also been measured and reported in this paper.

2. Experimental details 2.1. Sample preparation

* Corresponding author. Thin Film and Nanoscience Laboratory, Department of Physics, Jadavpur University, Kolkata 700032, India. Tel.: 91 33 2413 8917; fax: 91 33 2414 6007. E-mail address: kalyan_chattopadhyay@yahoo.com (K.K. Chattopadhyay). 1293-2558/$ see front matter 2010 Elsevier Masson SAS. All rights reserved. doi:10.1016/j.solidstatesciences.2010.02.007

The appropriate amounts of the nitrate salts of the Fe3 and Zn2 ions i.e. 8.1486 g of Fe(NO3)3,9H2O [Merck Co.]; 3 g of Zn(NO3)2,6H2O [Merck Co.] were taken (in 2:1 M ratio) in a beaker. Then hydrated citric acid (5.6476 g) of the combined equivalent

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Fig. 1. (a) a: Thermogravimetric analysis (TGA) curve of the gel precursor; b: Differential scanning calorimetry (DSC) plot of the gel precursor. (b) Derivative of the TGA plot.

weight of the salts was added in that beaker. In this mixture, 80 mL of double distilled water was added dropwise along with continuous stirring by a magnetic stirrer to prepare a saturated solution. The citrate ions present in the solution helped in the formation of the gel and also acted as a fuel. In the freshly prepared solution, ethylenediamine (EDA, Merck Co.) was added drop wise under continuous stirring. The addition

process was slowly carried out until the solution (pH 5) became a highly viscous gel-like mass. The gel was then dried by heating at 120  C for 4 h. The dry mass was then grounded into powders by a mortar and pestle. The powders were then heated at 150  C in a pot furnace for 40 min to complete the combustion process and a uffy blackish brown mass of ZFO was obtained. The synthesized ZFO was then annealed at various temperatures 150  C, 250  C and

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Table 2 Variation of particle size and strain for samples at annealed at different temperatures. ZFO-150  C-2 h ZFO-250  C-2 h 29 4.3 ZFO-900  C-2 h 60 1.0

(311)

(422) (511)

(440)

Intensity (a.u.)

(22 0 )

(111)

(222)

(400)

Particle size (nm) Strain (10-3)

25 10.6

c b a
10 20 30 40 50 2 (degree) 60 70

been annealed at higher temperatures to systematically vary the particle size. 3.2. Structural property studied by X-ray diffraction (XRD) Fig. 2 shows the X-ray diffraction patterns for the as-prepared and annealed (at 150  C, 250  C & 900  C) samples. All the appeared peaks can be assigned to the spinel ZFO as summarized in Table 1. Absence of any peak from ZnO, Fe2O3 or any other oxide phases conrmed the formation of phase pure ZFO. To investigate the variation of particle size as a function of annealing

Fig. 2. XRD patterns of samples prepared at (a) ZF-150  C-2 h, (b) ZF-250  C-2 h, and (c) ZF-900  C-2 h.

900  C for 2 h to study the size dependence of electrical properties of ZFO nanoparticles.

2.2. Characterization Thermal decompositions were studied by differential scanning calorimetric analysis (DSC) and thermogravimetry (TG) using a Pyris Diamond TG/DTA (Perkin Elmer) instrument. The phase purity of ZFO and particle sizes were examined by X-ray diffraction (Rigaku-Ultima-III, by CuKa radiation, l 1.5404 ). Field emission scanning electron microscopy (FESEM, Hitachi, S-4800) was used for the morphological studies of the synthesized ZFO powder. High resolution transmission electron microscope (HRTEM) images and selected area electron diffraction patterns (SAED) were obtained with a JEOL 200 kV HRTEM. Binding energies of electrons at different energy levels of the elements were determined by X-ray photoelectron spectroscopy (HSA-3500, SPECS). Frequency dependent dielectric constant and a.c. conductivity were measured by an LCR meter (HP 4284A, Hewlett Packard) in the frequency range of 40 kHz1 MHz at room temperature.

3. Results and discussion 3.1. Thermal analysis Thermal analysis (Fig. 1a) was performed to understand the combustion process used for the synthesis of the ZFO samples. From the TG plot (Fig. 1a) and its derivative (Fig. 1b) one can observe that the maximum weight loss of the gel precursor has occurred at about 182  C. At about the same temperature, we have also observed an exothermic peak in the DSC plot (Fig. 1a). This means the rate of combustion is the highest at this temperature. However we have chosen this minimum temperature for the combustion to get the smaller size of ZFO nanoparticles. Further, this material has

Table 1 Comparison of d-values obtained from XRD, TEM with JCPDS. Plane (111) (220) (311) (222) (400) (422) (511) (440) 2.97 2.93 2.96 2.53 2.49 2.52 2.43 2.44 2.10 2.10 1.72 1.72 1.62 1.61 1.49 1.48

4.84 dXRD () 4.79 dSAED () dJCPDS () (Card No.075104) 4.87

Fig. 3. (a) FESEM image of a ZFO sample annealed at 150  C for 2 h. (b) HRTEM image of a ZFO sample annealed at 250  C for 2 h.

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Zn 2p3/2

Fe 2p3/2

Fe 2p1/2

Intensity (a.u.)

Intensity (CPS)

704

706

Fe 2p3/2

708

710

712

714

716

Intensity (a.u.)

Binding energy (eV)

1010

1020

1030

1040

Zn 2p1/2
1050
Binding Energy (eV)
[Fe2/(Fe2 Fe3)] 0.13 0.11 0.05

690

700

710 720 730 Binding Energy (eV)

740

750

Fig. 6. X-ray photoelectron spectrum of Zn2p3/2 and Zn2p1/2 states.

Fig. 4. X-ray photoelectron spectrum of Fe2p3/2 and Fe2p1/2 states. Deconvoluted Fe 2p3/2 spectra of ZFO sample prepared at 150  C is represented in the inset.

temperatures, we have analyzed the XRD patterns by WilliamsonHall method using the well known relation [21],

SAED patterns. From Table 1, it is observed that the estimated d-values both from the XRD and the SAED pattern matches well with the standard d-values of ZFO. Again, d-values obtained from lattice image are very close to the d-values calculated from the XRD and SAED.

bcos q=l 1=L 3sin q=l

where, b and l are the FWHM of the peaks and the wavelength of incident X-ray respectively. L and e represent the particle size and strain of the synthesized particles. The average particle size of the ZFO nanoparticles was found to increase with increasing annealing temperature and the results have been summarized in Table 2. From the WilliamsonHall analysis, it is also found that the strain of the nanoparticles is increasing as we decrease the particle size. It arises due to substitution of Zn2 ions by the larger size Fe2 ions (discussed in the later section). Fig. 3a shows a FESEM image of the synthesized BFO sample. The image clearly shows the presence of grains and the average particle size is about w2025 nm. This value agrees well with that calculated from the XRD peak broadening. A typical lattice image, obtained from high resolution transmission electron microscope (HRTEM), of the prepared samples is represented in Fig. 3b and the corresponding selected area electron diffraction (SAED) is shown in the inset of Fig. 3b. Table 1 contains the d-values computed from the XRD and the

3.3. Chemical analysis by X-ray photoelectron spectroscopy (XPS) To investigate the valence states of the ions present in ZFO, the samples were analyzed by X-ray photoelectron spectroscopy. Figs. 46 show the XPS spectra of the Zn, Fe and O, in which the adventitious C 1s peak at 284.6 eV binding energy has been removed by Ar sputtering. Binding energies of the Fe 2p3/2 and Fe 2p1/2 were measured as 711.0 and 724.8 eV respectively. The binding energy of O 1s is found to be 529.8 eV and those of Zn 2p1/2 and Zn 2p3/2 states are observed at 1044.2 and 1021.1 eV respectively. The binding energies of Fe 2p3/2 are 709.6 [22] and 711.6 eV [23] when Fe ion is present as FeO and Fe2O3 respectively. Thus the binding energy of Fe 2p3/2 in ZFO lies in between the binding energies of those found in FeO and Fe2O3. So from the observed binding energies, it is conrmed that Fe ion is not present either as FeO or Fe2O3. Binding energies of Zn 2p1/2 and Zn 2p3/2 states are also found to be different from the binding energies of those states in ZnO, which were 1044.8 eV and 1022.0 eV respectively [24,25]. These clearly reect that Zn, Fe and O are not present in the form of zinc oxide, ferrous oxide or ferric oxide. Therefore, we can conclude that Zn, Fe and O are present as ZFO. This phase purity is also supported by XRD analysis. We have observed Fe to be present in both Fe2 and Fe3 states in our samples and also the ratio of Fe2/Fe3 increased with decreasing temperature as can be found from Table 3. This is due to the fact that at ordinary atmosphere, as temperature increases Fe3 states become more stable than Fe2 states. Generally, bulk ZFO exhibits spinel structure with Zn2 and Fe3 ions at tetrahedral and octahedral sites respectively. But mixed spinel structure is observed in the case of ZFO nanocrystals. Mixed spinel structure is observed

Intensity(cps)

O 1s

Table 3 Fe2/(Fe2 Fe3) ratios for the samples annealed at different temperatures.

520

525

530

535

540

Sample 150 C-2 h 250  C-2 h 900  C-2 h



Binding Energy (eV)

Fig. 5. X-ray photoelectron spectrum of O 1s state.

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843

35

140

Dielectric constant ( )

30

a.c. conductivity (Scm )

120
-1

100 80 60 40 20 0 0.0 0.2 0.4 0.6 0.8 Frequency (MHz) b a 1.0

b a
0 0.0 0.2 0.4 0.6 0.8 1.0

Frequency (MHz)
Fig. 7. Dielectric constant vs. frequency plots of the samples (a) ZF-150  C-2 h, (b) ZF250  C-2 h, and (c) ZF-900  C-2 h.

Fig. 8. Variation of a.c. conductivity with frequency of the samples (a) 150  C-2 h, (b) 250  C-2 h, and (c) 900  C-2 h.

in the case of nanocrystalline ZFO where few zinc ions takes octahedral sites, displacing few iron ions to tetrahedral sites. From XPS analysis (Table 3), we have observed that as the temperature increases Fe2 concentrations increases. Again from Table 2, it can be concluded that with the decrease in temperature (which led to decrease in particle size) strain increases. The ionic radius of Fe2 (0.77 ) is greater than that of Zn2 (0.74 ) [26]. Therefore, the substitution of Zn2 by Fe2 at the tetrahedral sites would lead to increase strain. Similar phenomena were observed by Ponpandian et al. [27] and Mansingh et al. [28]. 3.4. Dielectric constant (3) Fig. 7 shows the variation of dielectric constants with frequency for samples annealed at different temperatures. It was observed that the dielectric constant, measured in the frequency range between 40 kHz and 1 MHz, initially decreases with frequency then reaches a constant value at higher frequency range. In the frequency range that we have chosen here the dielectric constant is mainly dominated by the orientational polarization [29,30]. Presence of minor Fe2 as impurity induces dipole moment within ZFO and is the reason for the origin of orientational polarization [31] in these samples. Polarization decreases with increasing frequency, reaching a constant value at high frequency, beyond which the dipoles cant follow the rapid variation of the alternating electric elds [32]. It has also been observed that the dielectric constant of ZFO decreases with decreasing particle size. Nanocrystalline ZFO exhibits mixed spinel structure, where some of the zinc ions occupy the tetrahedral sites, displacing an equal number iron ions to the octahedral sites [33]. This occupancy of tetrahedral sites by zinc atom increases with decreasing the particle size. It is well known that the size of tetrahedral void is lower than the size of octahedral void, therefore if Fe2 is present in tetrahedral void then the distance between Fe2 ion and the positively charged oxygen vacancy site will be lower than if Fe2 is in octahedral void [30]. Therefore the dipole moment created by Fe2 in tetrahedral voids will be lower than when it is in octahedral voids. As the particle size decreases Fe2 goes to tetrahedral sites as discussed earlier with the consequent decrement in dipole moment and therefore dielectric constant decreases with reduction in particle size. 3.5. a.c. conductivity (sa.c.) a. c. conductivities (sa.c.) of the synthesized samples, in the frequency range between 40 kHz and 1 MHz were measured by an

LCR meter. It was observed that a.c. conductivity of ZFO decreases as we lower the particle size (Fig. 8). In ferrite materials, there is very little possibility of overlapping between the wavefunctions of the adjacent ionic sites due to the localized nature of Fe 3d orbitals. However, transfer of electrons occurs only when the ions come very close together due to lattice vibration. In ferrite materials, the degree of covalency of cations either at tetrahedral sites or at octahedral sites also determines the conductivity. It is well known that the conductivity of ferrite materials decreases with increasing the degree of covalence of octahedral sites, occupied by iron ion [30,33]. Since the electronegativity of Fe2 is less than the electronegativity of Fe3, covalence of octahedral iron sites increases with increasing the ratio of Fe2/Fe3. Thus the increasing ratio of Fe2/Fe3, obtained by lowering the synthesis temperature and conrmed by XPS analysis [34], decreases conductivity of ZFO nanoparticles. 4. Conclusion A unique soft chemical route has been developed to synthesize crystalline ZFO nanoparticles at signicantly lower temperature (150  C) than other published reports. As the heat treatment temperature of the calcined uppy mass increases the ratio of ferric to ferrous ions increases along with the increase of the particle size of ZFO. The XRD and HRTEM studies conrmed the correct phase formation. The dielectric constant and the a.c. conductivity of the prepared samples at all frequencies were found to decrease with the reduction of the size of ZFO nanoparticles. Therefore the decrement in a.c. conductivity as well as the dielectric constant of ZFO nanoparticles may nd some applications in the eld of insulating materials. Acknowledgment One of us (CKG) wishes to thank the Council for Scientic and Industrial Research (CSIR), the Government of India, for awarding him a Senior Research Fellowship (SRF) during the execution of the work. The authors wish to thank the University Grants Commission (UGC), the Government of India for nancial assistance under the University with potential for excellence programme. References
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