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Journal of the Korean Physical Society, Vol. 56, No. 1, January 2010, pp.

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Alkali Metal Non-Stoichiometric Eects in (K0.5 Na0.5 )NbO3 Based Piezoelectric Ceramics
S. C. Lee, H-G. Yeo, J. H. Cho, Y. S. Sung, M-H. Kim and T. K. Song
School of Nano and Advanced Materials Engineering, Changwon National University, Changwon 641-773

S. S. Kim
Department of Physics, Changwon National University, Changwon 641-773

B. C. Choi
Department of Physics, Pukyung National University, Busan 608-737

K-S. Choi
Department of Physics, Sunchon National University, Sunchon, Chonnam 540-742 (Received 17 March 2009, in nal form 22 June 2009) Alkali-metal-excess lead-free 0.93(K0.5 Na0.5 )(1+x) NbO3 -0.07LiNbO3 (KNNL) piezoelectric ceramics were prepared by using a solid state reaction. The contents of both K and Na were simultaneously controlled to 4 mol% excess. From X-ray diraction and temperature-dependent dielectric constant measurements, a polymorphic phase transition (PPT) between the tetragonal and orthorhombic phases was observed by changing the stoichiometry of x. With increasing (K+Na) content, the PPT temperature increased, but the Curie temperature decreased. The highest piezoelectric constant was 189 pC/N for x = 0.01, where the PPT temperature was around room temperature.
PACS numbers: 77.65.-j, 77.80.Bh, 77.84.Dy, 77.80.-e Keywords: Lead-free, Piezoelectric, Stoichiometry, Phase transition DOI: 10.3938/jkps.56.453

I. INTRODUCTION Alkali metal niobate, (K0.5 Na0.5 )NbO3 (KNN) ceramics have been studied for lead-free piezoelectric ceramics because of their good piezoelectric properties and high Curie temperatures [14]. Pure KNN ceramics have, however, diculties such as densication when the conventional solid state reaction method and poling process are used [57]. As a result, their piezoelectric properties are not good enough for applications. To improve the piezoelectric properties of KNN ceramics, various doping elements, such as KNN-BaTiO3 [8], KNN-SrTiO3 [9], KNN-LiSbO3 [10], and KNN-LiTaO3 [11], have been investigated. Due to the phase transition between the tetragonal and the orthorhombic phases, the so-called polymorphic phase transition (PPT) with doping, the piezoelectric properties in these KNN-based ceramics are much improved [12]. These results are similar to the improvements in the piezoelectric properties near mor E-mail:

photropic phase boundaries in the Pb(Zr,Ti)O3 piezoelectric system [13]. In the KNN-LiNbO3 system [1420], the PPT was introduced by LiNbO3 doping [14,16] or by changing the sintering temperature [18]. It is not easy to control the exact compositions of KNN systems because the starting materials of alkali-metal carbonates, such as K2 CO3 and Na2 CO3 powders, are hygroscopic and because alkali metals are very volatile during heat treatments. The improvement in the piezoelectric properties was investigated for nominal compositions, so it is important to control the stoichiometry of alkali metals and to study the eects of non-stoichiometry in KNN. We report A-site non-stoichiometric eects in 0.93(K0.5 Na0.5 )(1+x) NbO3 0.07LiNbO3 (KNNL) piezoelectric ceramics with a nominal alkali-metal excess.

tksong@changwon.ac.kr; Fax: +82-55-262-6486

II. EXPERIMENTAL
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Journal of the Korean Physical Society, Vol. 56, No. 1, January 2010

KNNL piezoelectric ceramics with 0.00 x 0.04 were prepared by using a conventional solid state reaction method from component oxides powders of K2 CO3 (99.7%), Na2 CO3 (99.95%), Li2 CO3 (99.99%), and Nb2 O5 (99.9%). These carbonate powders were dried at 200 C for 3 hours to remove water molecules absorbed from air; then, the powders were weighed and mixed by ball milling in anhydrous alcohol for 3 hours. After having been dried at 90 C, the powders were calcined at 850 C 900 C for 3 hours twice. The calcined powders were re-milled in anhydrous alcohol and dried, and they were mixed with 5 wt% polyvinyl alcohol as a binder. The powders were pressed into pellets with 10mm diameters and 1-mm thicknesses. The pellets were sintered at 1,050 C for 2 hours in air [17]. The shrunk sintered ceramics were ground to a 0.5-mm thickness before applying electrodes. X-ray diraction (XRD, XPert, Philips) was used to determine the crystalline phases. For the ferroelectric properties measurement, electrodes were applied to the sintered ceramics by using silver paste on both surfaces and were cured at 650 C for 30 min. Dielectric constants were measured by using an impedance analyzer (HP4192A) at 10 kHz in the temperature range from room temperature to 650 C. For the piezoelectric property measurements, samples were poled by using a dc electric eld of 20 kV/cm for 30 min in silicone oil at room temperature. After having been aged for 24 hours, the value of the piezoelectric coecient d33 were measured by using a quasi-static d33 meter (ZJ-6B, HC Materials). Ferroelectric hysteresis loops were measured at 11 Hz by using a Sawyer-Tower circuit with function generator (FG300, Yokogawa), a voltage amplier (610E, Trek), and a digital oscilloscope (DL7100, Yokogawa) at room temperature.

Fig. 1. (Color online) X-ray diraction patterns of 0.93(K0.5 Na0.5 )(1+x) NbO3 -0.07LiNbO3 ceramics in the 2 range (a) from 20 to 60 and (b) from 31 to 32.5 .

Fig. 2. (Color online) Lattice constants as functions of x. Polymorphic phase transitions were observed for 0.01 x 0.02.

III. RESULTS The densities of the sintered ceramics were measured by using the method of Archimedes to be about 4.2 g/cm3 and did not change much with alkali metal excess. The size of the grains, about 10 m, increased a little with alkali metal excess, but the microstructure did not change signicantly. Figure 1(a) shows the XRD patterns of KNNL ceramics with 0.00 x 0.04. The crystal structure is pure perovskite without any secondary phases. Figure 1(b) shows the magnied XRD in the 2 range from 31 to 32.5 . When x < 0.01, the tetragonal phase was observed, but the phase starts to change to the orthorhombic phase at x = 0.01, and the phase change is complete at x = 0.02, where XRD peaks of both phases coexist. The peak indexing of the orthorhombic phase was based on the JCPDS le for orthorhombic KNbO3 (32-0822), which is dierent from the indexing based on monoclinic symmetry [20]. The polymorphic phase transition (PPT), between the tetragonal and the

orthorhombic phases coexist corresponds to the composition of 0.01 x 0.02. The change of lattice constant and the phase transformation are summarized in Fig. 2. In the tetragonal phase, a increased, but c decreased with increasing x, and the tetragonality c/a decreased from 1.024 to 1.013 [14]. The lattice constants do not change much with x in the orthorhombic phase. In the PPT region, the lattice constants were not well dened due to the mixing of peaks of both phases. Figure 3(a) shows the temperature dependence of the dielectric constant, (T ), of KNNL ceramics at a frequency of 10 kHz on the cooling run. Even though not shown in gure, dielectric anomalies in (T ) were observed in poled ceramics on the heating run at temperatures between room temperature and the ferroelectric transition temperature (TC ). These results may be due to ferroelectric domain dynamics. A high temperature TC with very large dielectric constant peaks, was observed at around 450 C. For x = 0.01, the PPT was observed at around room temperature. This result is consistent with the X-ray study shown in Fig. 2. The

Alkali Metal Non-Stoichiometric Eects in in (K0.5 Na0.5 )NbO3 S. C. Lee et al.

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Fig. 4. (Color online) Ferroelectric polarization hysteresis loops. The inset shows the piezoelectric constant (d33 ) of 0.93(K0.5 Na0.5 )(1+x) NbO3 -0.07LiNbO3 ceramics as a function of x.

IV. DISCUSSION In comparison to the report on the LiNbO3 doping effect in [Liy (K0.5 Na0.5 )(1y) ]NbO3 by Guo et al. [14], the ratio r = Li/(K+Na) is not so much changed in our work. When y = 0.07, r = 0.0753, and r decreased to 0.0683 with y = 0.06, where the PPT was observed. In our 0.93(K0.5 Na0.5 )(1+x) NbO3 -0.07LiNbO3 system, r varied from 0.0753 with x = 0.00 to 0.0724 with x = 0.04. For the case of the ratio = (Li+K+Na)/Nb, is always 1.000 in [Liy (K0.5 Na0.5 )(1y) ]NbO3 , but was varied from 1.000 with x = 0.00 to 1.037 with x = 0.04 in our 0.93(K0.5 Na0.5 )(1+x) NbO3 -0.07LiNbO3 system. From these calculations, the observed PPT in our work is due to the alkali-metal non-stoichiometric eects of rather than r. One of the reasons a 1-mol%-excess KNNL ceramic showed the best piezoelectric properties is the fact that a nominal 1-mol%-excess system could be the most stoichiometric composition of KNNL ceramics after the sintering process because alkali-metal oxides are hygroscopic and are volatile during heat treatments. We could, however, hardly measure the exact compositions of the KNNL ceramics by using energy dispersive Xray spectroscopy. The improvements in the piezoelectric properties in the 1-mol%-excess system are attributed not only to the exact composition but also to the PPT, caused by variations in the stoichiometry because the piezoelectric properties are strongly correlated with the PPT temperature. The large decrease of d33 with increasing x in the 2-mol%-excess system may be due to defects induced by the non-stoichiometry of KNNL ceramics. In summary, a polymorphic phase transition was observed by using X-ray diraction and temperature-dependent dielectric constant studies on 0.93(K0.5 Na0.5 )(1+x) NbO3 -0.07LiNbO3 ceramics by changing the alkali-metal stoichiometry only. Improve-

Fig. 3. (Color online) (a) Temperature dependencies of the dielectric constant, (T ), at 10 kHz for 0.93(K0.5 Na0.5 )(1+x) NbO3 -0.07LiNbO3 ceramics. Insets are magnied gures around the phase transition temperatures. (b) Temperature (T )-composition (x) phase diagram of 0.93(K0.5 Na0.5 )(1+x) NbO3 -0.07LiNbO3 ceramics.

temperature-composition phase diagram deduced from (T ) is shown in Fig. 3(b). Ferroelectric cubic to tetragonal phase transition temperature, TC , decreased from 470 C for x = 0.00 to 443 C for x = 0.04. The PPT temperature increased with x from room temperature for x = 0.01 to 149 C for x = 0.04. The tetragonal phase region is reduced with increasing x. In the KNN-LiNbO3 ceramic system, TC was reported to increase with increasing Li doping [14]. Similarly TC decreased with increasing x in our system because the ratio Li/(K+Na) decreased. Ferroelectric hysteresis loops are shown in Fig. 4. The remanent polarization increased from 2.1 C/cm2 for x = 0.00 to 4.9 C/cm2 for x = 0.02 and then decreased. Coercive elds around 8.3 9.6 kV/cm were almost independent of x [19]. The highest d33 of 189 pC/N was observed for x = 0.01, as shown in the inset of Fig. 4 [14]. The highest d33 was observed in the KNNL ceramic with its PPT region at room temperature, as observed in the X-ray and (T ) studies.

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Journal of the Korean Physical Society, Vol. 56, No. 1, January 2010 [7] L. Egerton and D. M. Dillon, J. Am. Ceram. Soc. 45, 438 (1959); R. E. Jaeger and L. Egerton, J. Am. Ceram. Soc. 45, 209 (1962). [8] H. Y. Park, C. W. Ahn, H. C. Song, J. H. Lee, S. Nahm, K. Uchino and H. J. Lee, Appl. Phys. Lett. 89, 062906 (2006). [9] V. Bobnar, J. Bernard and M. Kosec, Appl. Phys. Lett. 85, 994 (2004). [10] S. Zhang, R. Xia, T. R. Shout, G. Zang and J. Wang, J. Appl. Phys. 100, 104108 (2006). [11] Y. Dai, X. Zhang and G. Zhou, Appl. Phys. Lett. 90, 262903 (2007). [12] T. R. Shrout and S. J. Zhang, J. Electroceram. 19, 113 (2007). [13] B. Jae, W. Cook and H. Jae, P iezoelectric Ceramics (Academic, New York, 1971), p. 136. [14] Y. Guo, K. Kakimoto and H. Ohsato, Appl. Phys. Lett. 85, 4121 (2004). [15] E. Hollenstein, M. Davis, D. Damjanovic and N. Setter, Appl. Phys. Lett. 87, 182905 (2005). [16] H. L. Du, W. C. Zhou, F. Luo, D. M. Zhu, S. B. Qu and Z. B. Pei, Appl. Phys. Lett. 91, 202907 (2007). [17] H. C. Song, K. H. Cho, H. Y. Park, C. W. Ahn, S. Nahm, K. Uchino, S. H. Park and H. G. Lee, J. Am. Ceram. Soc. 90, 1812 (2007). [18] P. Zhao, B.-P. Zhang and J.-F. Li, Appl. Phys. Lett. 90, 242909 (2007). [19] P. Zhao, B.-P. Zhang and J.-F. Li, Appl. Phys. Lett. 91, 172901 (2007). [20] K. Wang and J.-F. Li, Appl. Phys. Lett. 91, 262903 (2007).

ments in the piezoelectric properties were observed at the transition composition, x = 0.01, at room temperature. The ferroelectric transition temperature decreased, but the polymorphic phase transition temperature increased with increasing x.

ACKNOWLEDGMENTS This work was supported by the Korean Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007-412-J00901).

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