J Mater Sci: Mater Electron (2012) 23:20982103 DOI 10.

1007/s10854-012-0706-9

Magnetoelectric effect of the multilayered CoFe2O4/BaTiO3 composites fabricated by tape casting

Dongxiang Zhou Liangbin Hao Shuping Gong Qiuyun Fu Fei Xue Gang Jian

Received: 13 January 2012 / Accepted: 24 March 2012 / Published online: 21 July 2012 Springer Science+Business Media, LLC 2012

Abstract This paper presents the structural, ferroelectric, ferromagnetic, resonance and magnetoelectric (ME) properties of multilayered ME composites fabricated using tape casting method. The compositions corresponding to CoFe2O4 (CFO) with particle size of *150 nm and BaTiO3 (BTO) with particle size of *100 nm were chosen as ferromagnetic and ferroelectric phases, respectively. Delamination was found at the interface between CFO and BTO layers, which was related to the residual stress due to the difference in thermal expansion coefcient between the two layers. The largest direct magnetoelectric and converse magnetoelectric coefcients of the multilayered ME composite were, respectively, 36 lV/cm Oe at a bias magnetic eld of 2,800 Oe and 1.16 9 10-3 G/V at a frequency of 30 kHz. In addition, the corresponding interfacial coupling coefcient was calculated to be 3.2 9 10-5. For the multilayered ME composite, a resonance frequency of 4.96 MHz and a bandwidth of 40 kHz were obtained using capacitance-frequency spectrum method.

1 Introduction Magnetoelectric (ME) materials, due to their extrinsic ME effect, have been focused increasingly for their potential applications in inductors, sensors and lters [13]. The ME effect is dened as an electric polarization response to an

D. Zhou L. Hao S. Gong Q. Fu (&) F. Xue G. Jian Department of Electronic Science and Technology, Huazhong University of Science and Technology, 1037 Luoyu Road, Hongshan District 430074, Wuhan, Hubei, Peoples Republic of China e-mail: fuqy@mail.hust.edu.cn

applied external magnetic eld, also called direct magnetoelectric (DME) effect, or an induced magnetization response to an applied external electric eld, also called converse magnetoelectric (CME) effect [4, 5]. In general, the effect is quantitatively characterized by ME coefcient [5]. The DME coefcient aE and CME coefcient aB could be described by the following expressions [5, 6]: aE = dE/ (dHac) and aB = dB/(dV), where dE is the electric eld, dHac is the amplitude of ac magnetic eld, dV is the applied voltage, and dB is the magnetic induction. Up to date, the coefcients for various ME materials have been reported [7]. Among the ME materials, layered composites have become a central issue, since they possess stronger ME properties in comparison with the single-phase materials or particulate composites [8, 9]. Most recently, the layered ME composites are mainly fabricated by epoxy-bonding method [8, 9] and deposition method [1012]. Nevertheless, these two methods have following drawbacks: (1) the epoxy layer lessens the ME effect and results in aging [9, 13]; (2) the substrate clamping effect makes ME effect weak [1416]. Alternatively, tape casting technique has been used to obtain multilayered ME composites such as 0.2Pb(Zn1/3Nb2/3)-0.8Pb(Zr0.5Ti0.5)O3 (PZNT)/(Ni0.6Cu0.2 Zn0.2) Fe2O3 (NCZF) and CoFe2O4 (CFO)/Pb(Zr0.52 Ti0.48O3) (PZT) [6, 9]. Of the multilayers, however, little literature has been published about the resonance frequency and CME property of the multilayered ME composite. Furthermore, the ME effect of the multilayered CFO/BaTiO3 (BTO) composite is seldom investigated. In this paper, we chose CFO and BTO as ferromagnetic and piezoelectric phases, respectively. Multilayered CFO/BTO composite was fabricated using tape casting method. The structural, ferroelectric, ferromagnetic, resonance, DME and CME properties of the composite were investigated in detail.

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2 Experimental CFO powder was prepared through solid state reaction method: raw materials of Co2O3 (AR, Aladdin Chemistry Co., Ltd, Shanghai, China) and Fe2O3 (AR, Tianjin Dengfeng Chemical Reagent Factory, Tianjin, China) were mixed in molar ratios for 12 h, dried, sieved, and presintered at 900 C for 2 h; then the synthesized particles were ball milled for 2 h, dried, and sieved to get a ne powder with particle size of *150 nm. BTO powder with average particle size of *100 nm was commercially supplied (Hebei Kingway Chemical Industry Co., Ltd, Baoding, China). The CFO and BTO powders were mixed with the organic additives to prepare the slurries for tape casting. In order to get the slurries, secondary ball milling and double solvent additions methods were used. That is, the CFO and BTO powders were mixed with solvents (ethyl alcohol and trichloroethylene) and a dispersant (tributyl phosphate) in ball mills for 3 h, then a plasticizer (dibutyl phthalate), the foregoing solvents and a binder (polyvinyl butyral) were added into the ball mills and milled for 3 h. After preparing the CFO and BTO slurries, they were tape casted with 0.5 mm height of doctor blade. The tapes were dried at temperature of 70 C for 10 min and alternately laminated under high pressure (56 Mpa) and temperature (50 C). The laminated green bodies were cut and heated at 280 C for burnout of organic components. Afterwards, the sintering process was conducted at 1,250 C for 2 h with a heating rate of 1.7 C/min under a pressure of 3.5 kPa. Finally, electrical contacts were made with silver paste at 550 C for 15 min with a heating rate of 5 C/min, and the composites were polarized in silicon oil. To polarize the composites, they were heated up to 140 C and cooled down to room temperature under an electric eld of 1.3 kV/mm and kept for 15 min at room temperature. The microstructure and composition of the composite were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The polarization hysteresis loop was characterized by a ferroelectric test system (Multiferroic, Radiant Technologies, Inc.). The piezoelectric coefcient (d33, p) of the composite was measured by a quasi-state d33 meter (ZJ-3A, Shanghai institute of acoustics). The magnetization of the composite was measured using a vibrating sample magnetometer (VSM, Lakeshore 7400). The capacitance of the multilayered composite was determined using an impedance analyzer (4294A, Agilent). The DME effect of the multilayered composite was investigated in transverse mode. A small ac magnetic led dHac with an amplitude of 12 Oe at a low frequency of 1 kHz was generated by the Helmholtz coils driven by a power amplier (BP4610, NF, Yokohama, Japan). The dHac superimposed onto a bias magnetic led Hdc was applied parallel to the plane of the composite. The induced

voltage from the composite was measured with a digital lock-in amplier (SRS Inc., SR850, Sunnyvale, CA, USA) under various bias magnetic eld Hdc. For CME effect measurement, the composite was placed in a bias magnetic eld Hdc = 1,000 Oe produced by an electromagnet. A sine electric eld with an amplitude of 3 V from a signal generator was applied to the sample. Both directions of the magnetic and electric elds were perpendicular to the surface of the sample. A search coil around the sample was connected to an oscilloscope for measuring the induced voltage due to the change of magnetic ux dB in the multilayered composite.

3 Results and discussion Figure 1 shows the XRD pattern of the composite after grinding into a powder form. The XRD pattern reveals spinel structure CFO and perovskite structure BTO phases without any impurity. After further analysis of the XRD pattern, the tetragonal BTO (space group: P4 mm) and cubic CFO (space group: Fd3 m) are found. Also the lattice , for BTO are parameter for CFO is a = 8.3981 A a = 4.0039 A and c = 4.0318 A. The micro-morphology of the CFO/BTO composite is shown in Fig. 2. Figure 2a displays the cross-sectional image of the composite, from which it can be found that CFO and BTO layers are alternately arranged. The thicknesses of CFO and BTO layers are *50 and 65 lm except the middle layer, respectively. The microstructure of the interface between CFO and BTO layers is shown in Fig. 2b. It is found that a transition layer which is composed of interfacial delamination exists at the interface. Figure 2c and d illustrate that

Fig. 1 XRD pattern of the multilayered CFO/BTO composite after grinding into a powder form

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2100 Fig. 2 a The cross-sectional SEM image of the multilayered CFO/BTO composite, b SEM image of the interface between CFO and BTO layers, c SEM image of BTO layer, d SEM image of CFO layer

J Mater Sci: Mater Electron (2012) 23:20982103

sintered BTO is much denser than CFO. And the particle sizes of BTO and CFO phases are found to be, respectively, *200 nm and 500 nm. The polarizationelectric eld (PE) hysteresis loop of the composite measured at room temperature is shown in Fig. 3. The loop demonstrates typical ferroelectric characteristic for the ME composite, in which a coercive eld (Ec) of 16 kV/cm is obtained. The remnant polarization (Pr) of the loop is *0.4 lC/cm2, which is smaller than those of both bulk BTO and CFO/BTO core-shell composite [17]. In addition, the present CFO/BTO composite exhibits a lower d33,p value of 16 pC/N. Magnetization property of the ME composite measured at room temperature with the applied magnetic eld parallel to the plane of the composite (in-plane) is presented in Fig. 4. Evident ferromagnetic property is observed. The saturation magnetization (Ms), remnant magnetization (Mr) and coercive eld (Hc) are 91 emu/cm3, 43 emu/cm3 and 677 Oe, respectively. ME effect will be enhanced signicantly at resonance frequency by contrast with the effect at nonresonance

Fig. 3 PE hysteresis loop of the multilayered CFO/BTO composite

frequencies [18], so the experiments of the ME effect are often conducted near the resonance frequency [7, 18]. To determine the resonance frequency of the layered ME

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Fig. 4 Magnetic hysteresis loop of the multilayered CFO/BTO composite

Fig. 6 DME coefcient aE as a function of bias magnetic eld Hdc for the multilayered CFO/BTO composite

Fig. 5 Capacitance as a function of frequency for the multilayered CFO/BTO composite

composite, the capacitance-frequency spectrum method has been used [7]. For the multilayered CFO/BTO composite, the capacitance as a function of frequency is shown in Fig. 5. It shows that the electromechanical resonance frequency is measured to be 4.96 MHz, which is twenty times larger than that in PZT/CFO/PZT composite prepared by using conventional ceramic processing [19]. To the best of our knowledge, seldom report has been made on such high resonance frequency in the range of electromechanical resonance frequency. Also the antiresonance frequency is measured to be 5 MHz. Therefore, the bandwidth of the CFO/BTO composite is found to be 40 kHz, which is larger than that of the trilayered ME composite fabricated using pressure assisted sintering [20]. In the process of measuring DME effect, an ac magnetic led produced by a Helmholtz coil is needed [7].

Because of the impedance of the coil, the ME effect is often investigated at low frequency [7]. Thus the frequency of the ac magnetic led is xed at 1 kHz in this study. Figure 6 shows the DME coefcient aE for the CFO/BTO composite. It is noteworthy that aE shows a strong dependence on bias magnetic eld Hdc varying from 27 to 7,200 Oe. In the range of 27400 Oe, aE decreases with the increasing bias magnetic eld. For Hdc [ 400 Oe, aE rst increases to a peak value under a bias eld of 2,800 Oe, then decreases with the increasing bias magnetic eld. Evidently the shape of aE curve is similar to that of piezomagnetic coefcient of the BTO lms/CFO substrates as reported previously, since the Hdc dependence of ME coefcient aE tracks the Hdc dependence of the piezomagnetic coefcient [21]. Furthermore, the maximal aE (Fig. 6) is 36 lV/cm Oe, and its corresponding induced voltage is 30 lV. Although the two values are comparable to those reported by Hrib et al. [22] and Yang et al. [23], the maximal aE is two to three orders of magnitude less than the value previously reported in literature on the PZT/(Ni1xZnx)Fe2O4 thicklm composite [24]. Besides, the maximal aE for the CFO/BTO composite is an order of magnitude smaller than that for the NFO/BTO composite synthesized using tape casting method [25]. This NFO/BTO composite consists of 15 layers of BTO and 16 layers of CFO, and its corresponding aE is estimated to be 0.8 mV/cm Oe in transverse mode [25]. Since the interfacial coupling coefcient k is directly related to ME coefcient [9], and the piezomagnetic coupling of CFO is larger than that of NFO [6], it could be deduced that k of the CFO/BTO composite should be much smaller than that of the NFO/BTO composite. To conrm this, aE is given by [6, 25, 26]

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aE

kf 1 f p d31 m q11 m q21

2 p p p T p m s11 m s21 p eT 33 kf s11 s21 e33 1 f 2 d31 k1 f

where f is the volume fraction of the piezoelectric phase, pm sij are compliance coefcients for piezoelectric (magnetostrictive) phases, p d31 is the transverse piezoelectric coefcient for piezoelectric phase, m qij is the piezomagnetic coefcients, and p eT 33 is the effective permittivity. The material parameters for BTO, CFO and NFO are listed elsewhere [6, 26], and f for CFO/BTO and NFO/BTO composites are 0.66 and 0.48, respectively. Substituting these corresponding parameters into Eq. (1), the interfacial coupling coefcients k of the CFO/BTO and NFO/BTO composites are calculated to be *3.2 9 10-5 and 2.3 9 10-3, respectively, demonstrating that the result is consistent with our deduction. As mentioned above, the DME coefcient aE and interfacial coupling coefcient k of the multilayered CFO/BTO composite are smaller than those of the NFO/BTO composite. This could be attributed to two reasons. One is that chemical reaction and interdiffusion at the interface may degrade the ME properties [8]. Another is concerned with residual stress generated at the interface of the multilayered composite due to the difference in thermal expansion coefcient (TEC) between the BTO and CFO phases. BTO has the TECs of a1 = a2 = 15.7 9 10-6 K-1, and a3 = 6.4 9 10-6 K-1; and the TECs for CFO are a1 = a2 = a3 = 10 9 10-6 K-1 [27]. Moreover, He [28] has reported that the TEC of BTO is greater than 10 9 10-6 K-1 at a temperature above 120 C (the Curie temperature of BTO). Therefore, when the multilayered composite is cooled down after being sintered, residual stress will be produced at the interface. According to [29], compressive residual stress will be generated in CFO layers, while tensile residual stress will appear in BTO layers. Although the compressive residual stress in CFO layers is advantageous to piezomagnetic coefcient and ME coupling effect [30], the residual stress leads to cracking and delamination at the interface [29]. Thus these defects could decrease the interfacial coupling between BTO and CFO layers, thereby lowering the DME effect. To clarify the existence of delamination, the SEM image of the interface between BTO and CFO layers was captured as shown in Fig. 2b. It shows that the delamination does exist at the interface. Therefore, it could be inferred that the interfacial delamination should be responsible for the DME coefcient and interfacial coupling coefcient of the CFO/BTO composite. The frequency dependence of CME coefcient aB was measured as shown in Fig. 7. The frequency is in the range

Fig. 7 CME coefcient aB together with phasic difference as functions of frequency for the multilayered CFO/BTO composite

of 30200 kHz because of the limitation of the instruments. The gure shows that, in general, aB decreases with increasing frequency, thus it is expected that aB will be enhanced if the frequency is less than 30 kHz. The maximal value of aB here, 1.16 9 10-3 G/V at 30 kHz, is about two orders of magnitude bigger than that of the CFO/BTO coreshell composite [17]. This could be attributed to the percolation and imperfect polarization in the coreshell structure [17]. Furthermore, the largest aB for the multilayered CFO/BTO composite is comparable to that for the three-phase composite prepared by bonding piezoceramic, metal cap and magnet [31]. Additionally, the phasic difference of the multilayered composite is larger than that of PZT/Terfenol-D composite [7, 18]. Although the DME and CME effects exhibit reverse characteristics [4, 5], both of the effects are achieved via interfacial coupling in ME composites [9]. Consequently, a low (high) interfacial coupling coefcient may result in weak (strong) CME effect. As explained above, interfacial coupling coefcient could be reduced owing to the interfacial interdiffusion and delamination. Therefore, the CME coefcient could be further improved when the interfacial coupling coefcient increases.

4 Conclusions We have successfully fabricated multilayered CFO/BTO composites by using tape casting method. XRD pattern shows that no impurity other than CFO and BTO phases

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exists. The SEM images illustrate that the CFO and BTO layers are alternately arranged but with delamination at the interface. The coexistence of ferroelectric and ferromagnetic properties indicates that the multilayered composite is magnetoelectric. The DME, CME and interfacial coupling coefcients are found to be 36 lV/cm Oe under the bias magnetic eld of 2,800 Oe, 1.16 9 10-3 G/V at a frequency of 30 kHz and 3.2 9 10-5, respectively. The interfacial coupling coefcient is inuenced by, in addition to the interfacial interdiffusion of the CFO/BTO composite, the interfacial delamination caused by residual stress due to the difference in TEC between BTO and CFO layers. Consequently, it is concluded that the ME effect will be enhanced if the interfacial property is optimized. Besides, the electromechanical resonance frequency of the multilayered composite is measured to be 4.96 MHz, which may provide the possibility of designing high frequency ME devices.
Acknowledgments The authors would like to thank National Natural Science Foundation of China (Grant No. 60871017/f010612) and Provincial Nature Science Foundation of Hubei in China. The authors also acknowledge the support of Shaanxi Normal University and Tsinghua University for the CME and DME coefcients measurement, respectively.

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