Materials Science and Engineering B 130 (2006) 94100

Effect of MnO addition on structure and electrical properties of (Na0.5Bi0.5)0.94Ba0.06TiO3 ceramics prepared by citrate method
Qing Xu a, , Xin-Liang Chen a , Wen Chen a , Min Chen a , Shu-Long Xu a , Bok-Hee Kim b , Joong-Hee Lee b
b a School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, PR China Faculty of Advanced Materials Engineering, Chonbuk National University, Chonju 561756, Republic of Korea

Received 15 October 2005; received in revised form 4 January 2006; accepted 19 February 2006

Abstract (Na0.5 Bi0.5 )0.94 Ba0.06 TiO3 ceramics added with 00.8 wt.% MnO were prepared by a citrate method, and the inuence of the MnO addition on the structure and electrical properties was investigated. The results indicate that the addition of small amounts of MnO did not cause a remarkable change in crystal structure, but resulted in an evident evolution in microstructure. The dielectric constant (r ) and piezoelectric constant (d33 ) signicantly decrease with increasing MnO content, while the electromechanical coupling factor (kp ) presents a slight variation in the range of 0.250.28. The dissipation factor (tan ) and mechanical quality factor (Qm ) attain a minimum value of 1.5% and a maximum value of 304 when adding 0.4 and 0.5 wt.% MnO, respectively. This research demonstrates that doping effect and microstructural evolution contribute cooperatively to the electrical properties of the ceramics. 2006 Elsevier B.V. All rights reserved.
Keywords: Doping effect; Ferroelectrics; Manganese; Microstructure; Perovskite; Piezoelectricity

1. Introduction In these years, there is a growing interest of investigating lead-free piezoelectric materials as a possible alternative to widely used lead zirconate titanate (PZT)-based ceramics. Sodium bismuth titanate (Na0.5 Bi0.5 )TiO3 (NBT), is a perovskite ferroelectric with a relatively large remanent polarization (Pr = 38 C/cm2 ) at room temperature and a relatively high Curie temperature (Tc = 320 C) [1]. Due to its strong ferroelectricity at room temperature, NBT has been considered to be a promising candidate material for lead-free piezoelectric ceramics. However, pure NBT suffers from a poling problem because of its high coercive eld (Ec = 73 kV/cm), making it difcult in obtaining the desired piezoelectric properties. To solve this poling problem, various NBT-based solid solutions have been developed [25]. Among these solid solutions (Na0.5 Bi0.5 )1x Bax TiO3 (NBT-BT) system has attracted a great deal of attention owing to the existence of a rhombohedraltetragonal morphotropic phase boundary (MPB) near x = 0.06.

Corresponding author. Tel.: +86 27 87863277; fax: +86 27 87864580. E-mail address: xuqing@mail.whut.edu.cn (Q. Xu).

Compared with pure NBT, the NBT-BT compositions near the MPB provide substantially improved poling and piezoelectric properties [2,6]. Recently, various oxides have been employed as additives for the NBT-BT compositions near the MPB, causing different effects on the electrical properties depending on the nature of the oxide additives [610]. Adding Mn is an often-adopted strategy to tailor the electrical properties of PZT-based piezoelectric ceramics [11]. MnO has been used as an additive for several NBT-based ceramics, including NBT [12], (Na0.5 Bi0.5 )0.87 (Sr0.5 Ca0.5 )0.13 TiO3 [3], (Na0.5 Bi0.5 )0.94 Ba0.06 TiO3 [9] and (Na0.5 Bi0.5 )0.92 Ba0.08 TiO3 [10]. The material constants of (Na0.5 Bi0.5 )0.94 Ba0.06 TiO3 ceramics added with various amounts of MnCO3 have been evaluated by Kaewkamnerd et al. with respect to the application of the material in Lamb wave devices [9]. It has been demonstrated that (Na0.5 Bi0.5 )0.94 Ba0.06 TiO3 added with 0.5 wt.% MnCO3 is characterized by improved dielectric property, high mechanical strength and satisfactory electromechanical coupling factor, and can be used as a new substrate material for Lamb wave devices. Despite of these investigations, the role of Mn on the structure and electrical properties of NBT-based ceramics remains somewhat ambiguous. Therefore, further investigation on this subject is necessary. On the other hand, NBT-based ceramics

0921-5107/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.mseb.2006.02.051

Q. Xu et al. / Materials Science and Engineering B 130 (2006) 94100

95

are usually produced by the conventional solid-state method. Recently, research efforts have been devoted to the preparation of the material by various wet chemical methods, such as citrate method [13], hydrothermal process [14] and stearic acid gel route [15]. In continuation of our earlier research on the electrical properties of NBT-BT ceramics prepared by a citrate method [16], (Na0.5 Bi0.5 )0.94 Ba0.06 TiO3 ceramics added with various amounts of MnO were prepared by the citrate method in this work, and the inuence of the MnO addition on the structure and electrical properties was examined. 2. Experimental The powders with the nominal composition of (Na0.5 Bi0.5 )0.94 Ba0.06 TiO3 + x wt.% MnO (x = 00.8) were synthesized by a citrate method. Reagent grade NaNO3 , Bi(NO3 )3 5H2 O, Ba(NO3 )2 , tetrabutyl titanate, Mn(NO3 )2 aqueous solution (50 wt.%) and citric acid were used as starting materials. Tetrabutyl titanate was rst dissolved into a citric acid solution and various nitrates were then added, followed by a stirring to yield a transparent aqueous solution. The mole ratio of citric acid to the total metal cation content was 1.25. The precursor solution was heated to form a sol and subsequently a

Fig. 1. XRD patterns of the powders with various MnO contents.

gel. The gel was calcined at 600 C for 1 h in air. The detail of the synthesis process has been described elsewhere [16]. The calcined powders were pressed into discs of 19 mm in diameter and 1 mm in thickness, and then sintered at 1150 C for 2 h in air.

Fig. 2. SEM micrographs of the powders with (a) x = 0, (b) x = 0.4, and (c) x = 0.6.

96

Q. Xu et al. / Materials Science and Engineering B 130 (2006) 94100

The crystal structure of calcined powders and ceramic specimens was examined by a Rigaku D/MAX-RB X-ray diffractometer using Cu K radiation. The morphology of calcined powders and microstructure of ceramic specimens were investigated by a Jeol JSM-5610LV scanning electron microscope (SEM). For ceramic specimens, thermally etched surfaces were used for SEM observation. The ceramic specimens were polished to ensure surface atness and painted with silver paste on both surfaces as electrodes. The dielectric properties were measured using a HP4294 impedance analyzer at 1 kHz. The specimens for measuring piezoelectric properties were poled in a silicon oil bath at 80 C under 3.0 kV/mm for 15 min. The piezoelectric constant (d33 ) was measured using a quasistatic d33 meter based on the Berlincourt method at 110 Hz. The electromechanical coupling factor (kp ), mechanical quality factor (Qm ) and frequency constant (Np ) were measured by the resonanceantiresonance method using the HP4294 impedance analyzer. The polarization-eld (PE) hysteresis loop was measured at room temperature by a Radiant precision workstation based on a standard SawyerTower circuit at 50 Hz. 3. Results and discussion Fig. 1 shows the X-ray diffraction (XRD) patterns of the powders with various MnO contents. A perovskite structure was

certied for the powders together with a trace amount of intermediate phase (Bi4 Ti3 O12 ). Fig. 2 shows the SEM micrographs of the powders with various MnO contents. It can be seen that the powders have similar morphology, consisting of homogeneous and ne particles of 100200 nm. A pure perovskite structure was identied for the resulting ceramic specimens. It was noticed that the color of the specimen with x = 0 is yellowish, whereas that of the specimens added with MnO became black and got darker with increasing MnO content. Considering the very small addition amount of MnO, the color change with MnO addition infers the incorporation of Mn into the lattice [12]. Fig. 3 shows the XRD patterns in the 2 ranges of 3842 and 4548 , respectively, for the ceramic specimens with various MnO contents. A (0 0 3)/(0 2 1) peak splitting, corresponding to a rhombohedral symmetry, and a (0 0 2)/(2 0 0) peak splitting, corresponding to a tetragonal symmetry, were detected for the specimen with x = 0. It characterizes a coexistence of rhombohedral and tetragonal phases, which is consistent with the nature of the specimen with a composition near the MPB [2,6]. The specimens added with MnO maintain the coexistence of the two phases. It indicates that the addition of small amounts of MnO did not give rise to an obvious change in crystal structure. Fig. 4 shows the SEM micrographs of the ceramic specimens with various MnO contents. There is a monotonic increase in grain

Fig. 3. XRD patterns of the ceramic specimens with various MnO contents in the 2 ranges of (a) 3842 and (b) 4548 .

Q. Xu et al. / Materials Science and Engineering B 130 (2006) 94100

97

Fig. 4. SEM micrographs of the ceramic specimens with (a) x = 0, (b) x = 0.2, (c) x = 0.5, and (d) x = 0.8.

size with enhancing MnO content. This implies that within the amount range of MnO addition in the present work, Mn mainly dissolved into the perovskite structure, because the accumulation of Mn at the grain boundaries would inhibit grain growth [17]. Moreover, it can be observed that distinct pores appeared in the triangle regions formed by the grains in the specimens with relatively high MnO contents (Fig. 4(c) and (d)). These results reveal that the MnO addition caused a signicant evolution in microstructure. Fig. 5 shows typical PE hysteresis loops of the ceramic specimens with various MnO contents. A well-saturated PE hysteresis loop was obtained for the specimen with x = 0 under an electrical eld of 100 kV/cm, showing a relatively large remanent polarization (Pr ) of 37.1 C/cm2 and a relatively low coercive eld (Ec ) of 42.7 kV/cm. For the specimens added with MnO, the values of applicable electrical eld decline to 5070 kV/cm due to an increase in leakage current. Applying a higher electrical eld resulted in an electrical breakdown of the specimens or an obvious distortion of measured loops. As a result, the PE hysteresis loops of the specimens added with MnO are not fully saturated, making it unavailable in determining the real values of remanent polarization and coercive eld for these specimens. Moreover, for the specimens added with MnO,

several scattered points deviating form the normal locus of the loops (Fig. 5(b) and (c)) and obvious asymmetry of the measured loop (Fig. 5(c)) can be distinguished. It suggests that even under relatively low electrical led, the contribution of leakage current is still evident for the MnO added specimens. Hence, it can be deduced that the MnO addition led to a reduction in resistivity. Fig. 6 shows the dielectric and piezoelectric properties of the ceramic specimens as a function of MnO content. The dielectric constant (r ) and piezoelectric constant (d33 ) display a similar change, rapidly decreasing with MnO content over the range of x = 00.4 and then slightly varying with further increased MnO content. The variation trend of dissipation factor (tan ) with MnO content is inverse to that of mechanical quality factor (Qm ), which attain a minimum value of 1.5% at x = 0.4 and a maximum value of 304 at x = 0.5, respectively. A rather similar result has been previously reported for MnCO3 added (Na0.5 Bi0.5 )0.94 Ba0.06 TiO3 ceramics prepared by the conventional solid state method, with the peak value of the mechanical quality factor (Qm 370) occurring when 0.5 wt.% MnCO3 was added [9]. Comparatively, no considerable inuence of the MnO addition on the electromechanical coupling factor (kp ) and frequency constant (Np ) were found, with the electromechanical coupling factor and frequency constant slightly changing in the

98

Q. Xu et al. / Materials Science and Engineering B 130 (2006) 94100

Fig. 5. PE hysteresis loops of the ceramic specimens with (a) x = 0, (b) x = 0.4, and (c) x = 0.6.

ranges of 0.250.28 and 29603100 Hz m, respectively. In Ref. [9], it has been revealed that the addition of moderate amount of Mn (0.5 wt.% MnCO3 ) into (Na0.5 Bi0.5 )0.94 Ba0.06 TiO3 resulted in a reduced dissipation factor, an obviously enhanced mechanical quality factor and a slightly increased frequency constant while maintaining a high electromechanical coupling factor. The results of the present work are generally consistent with the early research. It has been reported that Mn can be present in perovskite materials with multiple valence states [11]. Some recent results suggested that Mn coexists mainly in Mn2+ and Mn3+ states in the perovskite structure piezoelectric ceramics such as PZTbased system [17,18]. In this research, Mn was introduced into (Na0.5 Bi0.5 )0.94 Ba0.06 TiO3 composition in the form of Mn2+ . Considering the versatility of Mn in valence state as a transitional metal element, the oxidization of partial Mn2+ to Mn3+ during the sintering in air can be expected. Mn2+ and Mn3+ have

cationic radii of 0.80 A and 0.66 A, respectively, close to that of Ti4+ (0.68 A). Thus, Mn2+ and Mn3+ can enter into the octahedral site of the perovskite structure to substitute for Ti4+ because of radius matching. Accompanying this occurrence, oxygen vacancies were created to maintain electrical neutrality. Similar to the case of PZT-based piezoelectric ceramics, the incorporation of Mn into the perovskite structure as an acceptor can generate a hard effect on the electrical properties. On the other hand, the formation of oxygen vacancies is benecial for the mass transport during sintering. This is presumably responsible for the promoted grain growth with the MnO addition. The variation of the electrical properties with the addition of MnO can be tentatively interpreted with respect to the doping effect and microstructural evolution. When the addition amount of MnO is relatively low (x 0.4), the hard doping effect on the electrical properties appears to be predominant. In the low MnO content region (x 0.4), the decrease of resistivity, dielectric

Q. Xu et al. / Materials Science and Engineering B 130 (2006) 94100

99

Fig. 6. Dielectric and piezoelectric properties of the ceramic specimens as a function of MnO content.

constant, dissipation factor and piezoelectric constant together with the enhancement of mechanical quality factor correspond well to the feature of a hard doping effect on the electrical properties. In the case of relatively high MnO content (x > 0.4), the grain growth became remarkable. The increase of grain size favors improving piezoelectric properties, which is known as grain size effect [8,19]. The grain size effect compensates the decrease of piezoelectric constant due to the hard doping effect. This is assumedly responsible for the slight fall of piezoelectric constant when x > 0.4. The signicant rise of dissipation factor and degradation of mechanical quality factor in the high MnO content region may be attributed to the appearance of distinct pores in the microstructure [18]. Therefore, it is likely that the doping and microstructural effects contribute to the electrical properties of the ceramics in a cooperative way. 4. Conclusions (Na0.5 Bi0.5 )0.94 Ba0.06 TiO3 powders added with various amounts of MnO (x = 00.8 wt.%) have been synthesized by a citrate method. The powders show a ne and uniform morphology, consisting of particles of 100200 nm. The structure and electrical properties of the resulting ceramic specimens have been investigated. It was found that the addition of small amounts of MnO did not cause an obvious change in crystal structure, but

led to a signicant evolution in microstructure. A considerable inuence of the MnO addition on the ferroelectric, dielectric and piezoelectric properties was detected for the ceramics. It was considered that the variation of the electrical properties with the MnO addition may be attributed to a joint contribution of doping effect and microstructural evolution. Acknowledgements This work was nancially supported by the Natural Science Foundation of China (grant no. 50272044). It is grateful to the Natural Science Foundation of China (grant no. 50410529) and Korea Science and Engineering Foundation (grant no. F012004-000-10084-0) for jointly supporting the research. One of the authors (Q. Xu) expresses sincere acknowledgement to Professor Kohji Toda of the Department of Electrical and Electronic Engineering, National Defense Academy of Japan, for his kind help in providing an important reference. References
[1] G.A. Smolenskii, V.A. Isupov, A.I. Agranovskaya, N.N. Krainik, Sov. Phys. Solid State (Engl. Transl.) 2 (1961) 26512654. [2] T. Takenaka, K. Maruyama, K. Sakata, Jpn. J. Appl. Phys. 30 (1991) 22362239. [3] N. Ichinose, K. Udagawa, Ferroelectrics 169 (1995) 317325.

100

Q. Xu et al. / Materials Science and Engineering B 130 (2006) 94100 [12] H. Nagata, T. Takenaka, J. Eur. Ceram. Soc. 21 (2001) 1299 1302. [13] D.L. West, D.A. Payne, J. Am. Ceram. Soc. 86 (2003) 192194. [14] P. Pookmanee, G. Rujijanagul, S. Ananta, R.B. Heimann, S. Phanichphant, J. Eur. Ceram. Soc. 24 (2002) 517520. [15] J.J. Hao, X.H. Wang, R.Z. Chen, L.T. Li, Mater. Chem. Phys. 90 (2005) 282285. [16] Q. Xu, S.T. Chen, W. Chen, S.J. Wu, J. Zhou, H.J. Sun, Y.M. Li, Mater. Chem. Phys. 90 (2005) 111115. [17] L.X. He, C.E. Li, J. Mater. Sci. 35 (2000) 24772480. [18] Y.D. Hou, M.K. Zhu, F. Gao, H. Wang, B. Wang, H. Yan, C.S. Tian, J. Am. Ceram. Soc. 87 (2004) 847850. [19] Y.D. Hou, P.X. Lu, M.K. Zhu, X.M. Song, J.L. Tang, B. Wang, H. Yan, Mater. Sci. Eng. B 116 (2005) 104108.

[4] T. Takenaka, T. Okuda, K. Takegahara, Ferroelectrics 196 (1997) 175178. [5] T. Takenaka, Ferroelectrics 230 (1999) 8798. [6] B.J. Chu, D.R. Chen, G.R. Li, Q.R. Yin, J. Eur. Ceram. Soc. 22 (2002) 21152121. [7] X.X. Wang, H.L.W. Chan, C.L. Choy, Solid State Commun. 125 (2003) 395399. [8] H.D. Li, C.D. Feng, W.L. Yao, Mater. Lett. 58 (2004) 11941198. [9] N. Kaewkamnerd, T. Takenaka, K. Sakata, K. Toda, Sensor. Mater. 9 (1997) 4755. [10] X.Y. Zhou, H.S. Gu, Y. Wang, W.Y. Li, T.S. Zhou, Mater. Lett. 59 (2005) 16491652. [11] T. kamiya, T. Suzuki, T. Tsurumi, M. Daimon, Jpn. J. Appl. Phys. 31 (1992) 30583060.