Applied Surface Science 254 (2008) 69726975

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Electronic structure studies of the spinel CoFe2O4 by X-ray photoelectron spectroscopy

Zhongpo Zhou a, Yue Zhang a, Ziyu Wang a, Wei Wei a, Wufeng Tang a, Jing Shi a,b, Rui Xiong a,c,*
a

Department of Physics and Key Laboratory of Acoustic and Photonic Materials and Devices of Ministry of Education, Wuhan University, Wuhan 430072, China International Center for Materials Physics, Shen Yang 110015, China c Hubei Key Laboratory on Organic and Polymeric Opto-electronic Materials, Wuhan 430072, China
b

A R T I C L E I N F O

A B S T R A C T

Article history: Received 20 December 2007 Received in revised form 6 April 2008 Accepted 1 May 2008 Available online 8 May 2008 Keywords: CoFe2O4 Electronic structure XPS Chemical state

The spinel CoFe2O4 has been synthesized by combustion reaction technique. X-ray photoelectron spectroscopy shows that samples are near-stoichiometric, and that the specimen surface both in the powder and bulk sample is most typically represented by the formula (Co0.4Fe0.6)[Co0.6Fe1.4]O4, where cations in parentheses occupy tetrahedral sites and those within square brackets in octahedral sites. The results demonstrate that most of the iron ions are trivalent, but some Fe2+ may be present in the powder sample. The Co 2p3/2 peak in powder sample composed three peaks with relative intensity of 45%, 40% and 15%, attributes to Co2+ in octahedral sites, tetrahedral sites and Co3+ in octahedral sites. The O 1s spectrum of the bulk sample is composed of two peaks: the main lattice peak at 529.90 eV, and a component at 531.53 eV, which is believed to be intrinsic to the sample surface. However, the vanishing of the O 1s shoulder peak of the powder specimen shows signicant signs of decomposition. 2008 Elsevier B.V. All rights reserved.

1. Introduction The cobalt ferrite CoFe2O4 is a very important magnetic materials, which has covered a wide range of applications including electronic devices, ferrouids, magnetic delivery microwave devices and high density information storage due to its wealth of magnetic and electronic properties, such as cubic magnetocrystalline anisotropy, high coercivity, moderate saturation magnetization, high Curie temperature TC, photomagnetism, magnetostriction, high chemical stability, wear resistance and electrical insulation, etc. [112]. In structure, the spinel cobalt ferrite CoFe2O4 crystallizes in a face-centered cubic structure with a large unit cell containing eight formula units. There are two kinds of lattices for cation occupancy, A and B sites have tetrahedral and octahedral coordination, respectively. In the normal spinel structure Co is a divalent atom, occupying tetrahedral A sites, while Fe is a trivalent atom, sitting on the octahedral B sites. When A sites being Fe3+ ions, while B sites equally populated by Co2+ and Fe3+ ions, the spinel structure is referred to as the inverse kind [13,14]. Commonly, the CoFe2O4 material is considered to be mostly an inverse spinel compound with most divalent Co ions occupying octahedral sites [7,15,16]. It

means that the Co and Fe cations distribute at both sites. Since the FeA3+FeB3+superexchange interaction is normally different from the CoA2+FeB3+ interaction, variation of the cation distribution over the A and B sites in the spinel leads to different magnetic properties of these oxides even though the chemical composition of the compound does not change [14]. The spinel cobalt ferrite CoFe2O4 materials have been synthesized by different methods [1719]. In most cases, variation of the magnetic properties was obtained due to the different distribution of the Co and Fe cations over the A and B sites. Thus, investigations on the distribution of the Co and Fe cations over the A and B sites in the spinel cobalt ferrite CoFe2O4 are important [4,7,13,14]. Quantitative X-ray photoelectron spectroscopy (XPS) gives not only the chemical composition, but also information on the chemical bonding and chemical state. This will help us to understand the distribution of the Co and Fe cations in the spinel cobalt ferrite CoFe2O4. Thus, in this paper, homogeneous CoFe2O4 powder and bulk were synthesized by combustion technique, and the XPS was taken to study on the valence of the elements and electronic conguration. 2. Experimental CoFe2O4 powder and bulk samples in our experiment were synthesized by combustion technique. In brief description, analytical reagent cobalt (II) nitrate hexahydrate, iron (III) nitrate

* Corresponding author. E-mail address: xiongrui@whu.edu.cn (R. Xiong). 0169-4332/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2008.05.067

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nonahydrate and urea were used. Stoichiometric amounts of the cobalt and iron nitrates were weighed out under dry conditions, intimately mixed in a widemouth vitreous silica basin and heated on a hot blanket inside a fume cupboard, under ventilation. With a rise in temperature, melting occurred and a dark liquid was produced. Soon after the thickened liquid began frothing, ignition took place, leading to rapid increase that propagated in swift ripples to walls of the basin. The reaction produced dry, very fragile foam, which transformed into powder [19]. The powders were ground in an agate mortar and pestle to a ne powder, and then, some powders were cold pressed into disks with diameter of 15 mm and thickness of about 1.4 mm at room temperature under a pressure of 12 MPa. In the nal, the compacted powders and the disks were directly put into silica boats separately, and sintered at 1200 8C for 4 h in argon atmosphere. X-ray diffraction (XRD) patterns were recorded on Bruker D8 ADVANCE powder diffractometer using Cu Ka radiation. The working voltage V, current I and time constant t were 40 kV, 40 mA and 0.2 s, respectively. X-ray Photoelectron Spectroscopy studies were performed using a KRATOS XSAM-800 ESCA/SIMS/ISS spectrometer with monochromatic Mg Ka (1253.6 eV) radiation, the binding energies of samples has been calibrated by taking the carbon 1s peak as reference (285.0 eV). 3. Results and discussion Fig. 1 is the X-ray powder diffraction patterns of the CoFe2O4 powder and bulk. It shows that the powder and bulk samples all have a single spinel phase and all peaks could be indexed according to the standard card of the spinel cobalt ferrite CoFe2O4 [JCPPS card No. 22-1086]. Fig. 2 gives the wide-scan XPS spectra of the CoFe2O4 bulk (curve 1) and powder (curve 2) samples in the binding energy of 0 1000 eV. As demonstrated in Fig. 2, the crystals contain Fe, Co, and O elements, and no other impurity element was detected in the spectrum up to 1000 eV except carbon. The carbon on the surfaces of the specimens is probably due to contamination caused by handling or pumping oil, since the samples have been undergone a 1200 8C high-temperature calcinations procedure. Stoichiometric information can be obtained from core photoemission intensity data. The element composition can be quantied by use of X-ray photoelectron intensity values (In) and appropriate sensitivity factors (Sn): rn = In/Sn. SFe, SCo and SO values of 3.8, 4.5 and 0.68 were found by procedures similar to that of Ref. [20]. Because the iron, cobalt and oxygen X-ray photoelectron peaks overlap signicantly, the spectrum must rst be

Fig. 2. Wide-Scan XPS spectra of the CoFe2O4, bulk (curve 1) and powder (curve 2).

integrated to obtain the N(E) vs. X-ray photoelectron spectrum and the individual components separated to obtain the integrated XPS intensity for each element independently [21]. Then, rCo:rFe:rO = 1:1.8:4.1 and 1:1.9:3.7 to bulk sample and powder sample were obtained separately. Regions in which detailed core spectra were collected including the 2p photoelectron regions of the metallic constituents of the oxides, as well as the oxygen 1s core photoelectron regions. The high-resolution narrow-scan XPS spectra of Fe 2p, Co 2p, and O 1s peaks of the CoFe2O4 specimen are shown in Figs. 35, respectively. Fig. 3 shows the Fe 2p core-electron spectrum of CoFe2O4 powder and bulk samples. The peak shape for the two samples is similar, and has an asymmetric shape. The spectrum apparently reveals the presence of two nonequivalent bonds of Fe ions in CoFe2O4 compounds, which is consistent with that there are two kinds of lattice sites for Fe ions occupancy in CoFe2O4 compounds. We attempt to resolve the data into two components to represent these two sites. For the CoFe2O4 powder, it yields Fe 2p3/2 binding energies of 710.65 and 713.26 eV, and Fe 2p1/2 binding energies of 724.23 and 725.36 eV. For the CoFe2O4 bulk, it yields Fe 2p3/2 binding energies of 710.48 and 713.00 eV, and Fe 2p1/2 binding energies of 723.60 and 725.70 eV. The doublets in powder and bulk samples can be ascribed to Fe3+ ions in octahedral sites and Fe3+

Fig. 1. XRD patterns of the CoFe2O4, (a) bulk and (b) powder.

Fig. 3. Fe 2p XPS for bulk (a) and powder (b) samples. (The arrow indicates the approximate position of the satellite characteristic of octahedral Fe2+.)

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Fig. 4. Co 2p3/2 XPS for bulk (a) and powder (b) specimens. (The arrow indicates the approximate position of the satellite characteristic of octahedral Co2+.)

ions in tetrahedral sites, respectively. In CoFe2O4 powder, the doublets of Fe 2p3/2 binding energies at 710.65 eV and Fe 2p1/2 binding energies at 724.23 eV are due to the contributions from Fe3+ ions in octahedral sites, while the doublets of Fe 2p3/2 binding energies at 713.26 eV and Fe 2p1/2 binding energies at 725.36 eV are due to the contributions from Fe3+ ions in tetrahedral sites. In CoFe2O4 bulk, the doublets of Fe 2p3/2 binding energies at 710.48 eV and Fe 2p1/2 binding energies at 723.60 eV are due to the contributions from Fe3+ ions in octahedral sites, while the doublets of Fe 2p3/2 binding energies at 713.00 eV and Fe 2p1/2 binding energies at 725.70 eV are due to the contributions from Fe3+ ions in tetrahedral sites. The relative contributions to the overall intensity of Fe3+ ions in octahedral sites and tetrahedral sites are 70% and 30% for both the powder and the bulk sample, which means that the Fe3+ ions occupy 60% tetrahedral sites and 70% octahedral sites in both the powder and the bulk sample. The result is consistent with that was reported by Nakagomi et al. [22], in which Co2+ was found to occupy both the tetrahedral and octahedral sites in spinel CoxFe3xO4 prepared by combustion reaction. The 2p3/2 to 2p1/2 separation and satellite structure are useful in characterizing the iron chemical environment. The iron 2p spectrum of the powder sample is different from that of the bulk samples, and shows developed satellite structure characteristic of

high spin octahedral cations, as that exhibited in the Fe2+ metal monoxides [23]. Thus, some Fe2+ may be present in the powder sample. This spectrum of the powder sample also broadens, although in this case the broadening of the iron is predominately to the higher binding energy side of the 2p transitions. The XPS spectrum of Co 2p3/2 in CoFe2O4 shown in Fig. 4 also exhibits asymmetric. The quantitative peak tting procedure for Co 2p3/2 is rather complicated owing to various physics effects including core and valence band interactions. Inspection of the measured Co 2p3/2 peak of the bulk sample (a) shows that it composes of two main doublets with peak position at 779.82 and 781.40 eV, and with relative contributions to the overall Co intensity of 60% and 40%, respectively. The two peaks with binding energy of 779.82 and 781.40 eV are ascribed to Co2+ ions in octahedral sites and Co2+ ions in tetrahedral sites, respectively. However, the Co 2p3/2 peak in powder sample (b) composes of three peaks positioned at 779.70, 781.00 and 782.80 eV, with relative contributions to the overall Co intensity of 45%, 40% and 15%, ascribes to Co2+ in octahedral sites, tetrahedral sites and Co3+ in octahedral sites. Compared with spectrum of the powder, the spectrum of the octahedral Co2+ cations in bulk sample has a very intense, characteristic satellite at 786 eV, which is some 46 eV higher in binding energy than the Co 2p3/2 signal. Therefore, majority high spin Co2+ cations occupy octahedral sites in the CoFe2O4 spinel lattice [21,15]. The intense satellite structure found at the high binding energy side of the Co 2p3/2 and Co 2p1/2 (not shown) transition is believed to be a direct consequence of the band structure associated with octahedral Co2+ in the oxide lattice, which allows for admixture of oxygen 2p character and leads two possible nal states in the photoemission process: 2p6 3d hn ! 2p5 3d e
7 7

or

2p5 3d V e ;

Fig. 5. The XPS spectrum of O 1s peak for the CoFe2O4 surface, bulk (a) and powder (b).

where V represents an electron vacancy in the 2p band of the neighboring O2 lattice anions. Because of the extreme sensitivity of the charge-transfer process to the overlap between adjacent Co2+ and O2 orbital, the satellite to main peak intensity is highly dependent upon the geometry and defect nature of the compound [21]. The possibilities of the oxidation of Co2+ to Co3+ is not entirely impossible if the oxidation of cobalt is compensated by a number of iron cations reduced from Fe3+ to Fe2+, or the migration of Co2+ to tetrahedral sites. The low spin Co3+ atom gives rise to much weaker satellite feature than do high spin Co2+, owing to the presence of unpaired valence electrons in the Co3+ orbital [15]. The exact form of this defect-cobalt structure cannot be unequivocally determined with XPS. However, the cobalt 2p spectrum corresponding to the powder sample has no signicant difference compared with the bulk specimen, although the spectral features broaden slightly, occurring at the higher binding energy side of the 2p peak in the intensity of the 781.00 eV peak. Fig. 5 shows the core-level spectrum of O 1s in CoFe2O4. The main peak of the bulk specimen (a) has a binding energy of 529.90 eV, which has been observed for lattice O2 at approximately this point in a number of rocksalt and spinel 3d metal oxides, including CoO, and Co3O4 [16]. A second higher-binding energy peak is found at 531.53 eV, and perhaps a third peak at 533.00 eV. The third peak is only present in about 7.7% of the total O 1s intensity and may simply be an artifact of tting asymmetric XPS peaks with symmetric Gaussian functions [21]. Establishing a unique assignment for the 531.53 eV O 1s peak is not straightforward. There are several possible defects and contaminants with a comparable XP binding energy and similar peaks in O 1s spectra taken on cobalt and iron containing oxides, those results may be from ambient adsorption, under-coordinated lattice oxygen,

Z. Zhou et al. / Applied Surface Science 254 (2008) 69726975 Table 1 The analysis results of Co 2p, Fe 2p and O 1s XPS spectra for the CoFe2O4 powder and bulk samples Sample Powder Spectrum Co 2p3/2 BE(eV) 779.70 781.00 782.80 710.65 713.26 530.17 532.29 779.82 780.40 710.48 713.00 529.90 531.53 533.00 Assignment Octahedral Co Tetrahedral Co2+ Octahedral Co3+ Octahedral Fe3+ Tetrahedral Fe3+ CoFe2O4 CoFe2O4 Octahedral Co2+ Tetrahedral Co2+ Octahedral Fe3+ Tetrahedral Fe3+ CoFe2O4 CoFe2O4 Artifact
2+

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Atomic percentage (%) 45 40 15 70 30 89 11 60 40 70 30 60 33 7

Fe 2p3/2 O 1s

Bulk

Co 2p3/2 Fe 2p3/2 O 1s

results show that the Fe3+ cations occupy 60% tetrahedral sites and 70% octahedral sites both in the bulk and powder specimens, but some Fe2+ may be present in the powder sample. The cobalt cations are predominantly present as Co2+ cations. For the bulk sample, 60% Co2+ cations located in octahedral sites, and 40% in tetrahedral sites. The Co 2p3/2 peak in powder sample consisted three peaks with relative contributions to the overall Co intensity of 45%, 40% and 15%, ascribes to Co2+ in octahedral sites, tetrahedral sites and Co3+ in octahedral sites. The O 1s spectrum of the bulk sample is composed of two peaks: one at 520.90 eV, similar to that was found for lattice O2 in the monoxides, and a second at 531.53 eV, which we believe to be characteristic of the surface spinel. Furthermore, the O 1s peak of the powder specimen show signicant signs of decomposition for depletion of oxygen. Acknowledgments This work was supported by the National Natural Science Foundation of China (Grant No. 10674105, No. 10474074 and No. 10534030) and 973 Program (2007CB607501). References
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Co2O3/Fe2O3 surface phases, or species intrinsic to the surface of the spinel. Thus, while it is not possible to rule out low levels of contaminants or defect species entirely, a fair percentage of oxygen intensity in the CoFe2O4 O 1s spectrum is believed to be representative of surface oxide intrinsic to the CoFe2O4 spinel lattice. In Fig. 5(b), the main peak is at 530.17 eV, and decreases slightly compared with that in Fig. 5(a), and the O 1s shoulder vanishes which shows signicant signs of oxygen depletion. The reduction of oxygen concentration may come from the oxidation of Co2+ to Co3+, or may be caused by calcination procedure for the loose compaction. Thermodynamic considerations have to be made in cases of high temperature and low oxygen partial pressure, as present in the surfaces when the spinel was formed. An attempt may be made to attribute this to the relative mobility of the ions concerned via tetrahedral and octahedral lattice sites, with the relative preferences for the two sites affecting rates of diffusion. The relative ion mobility may be deduced to be: Fe3+ > Fe2+ > Co2+. The mobility can be used to explain the enhanced surface concentration of cobalt and depletion of iron. The 532.29 eV peak is assigned an artifact also. Thus, the sample can be represented by (Co0.4Fe0.6)[Co0.6Fe1.4]O4 approximately, where cations in parentheses locate in tetrahedral sites and those within square brackets in octahedral sites. Table 1 summarizes the analysis results of the Co 2p, Fe 2p and O 1s XPS spectra for the CoFe2O4 powder and bulk samples. 4. Conclusion In conclusion, powder and bulk CoFe2O4 samples have been fabricated by combustion reaction and analyzed by XPS technique. The specimens are found to be near-stoichiometric, although subsequent calcinations tend to reduce oxygen concentration. The

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