Journal of the Korean Physical Society, Vol. 57, No. 4, October 2010, pp.

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Eect of Domain Size on the Coercive Field of Orthorhombic (Li, K, Na)NbO3 Ceramics
Jeong-Ho Cho, Yong-Hyun Lee, Kyu-Suk Han, Myoung-Pyo Chun, Joong-Hee Nam and Byung-Ik Kim
Advanced Materials Laboratory, Korea Institute of Ceramic Engineering and Technology, Seoul 153-023, Korea (Received 15 January 2010, in nal form 5 July 2010) Li0.02 (K0.45 Na0.55 )0.98 NbO3 [Li0.02 KNN] ceramics were prepared by using the conventional solid state reaction method. The domain structures of orthorhombic Li0.02 KNN ceramics were observed using a piezoelectric force microscope (PFM). A highly complicated conguration of domains was observed in grains with sizes over 15 m, where all types of domains exist together. In order to evaluate the domain size, we only considered 90 domains in simple lamellar twinning. In grains with sizes of 3 15 m, the simple lamellar twinning was observed and domain widths were about 275 300 nm. In smaller grains with sizes below 3 m, the domain width was wider than it was for larger grains (>3 m). The coercive eld signicantly decreased with decreasing domain size.
PACS numbers: 61.16.Ch, 61.66.Fn, 61.72.Mm Keywords: Orthorhombic, KNN ceramics, Grain size, Domain, Coercive eld DOI: 10.3938/jkps.57.971

I. INTRODUCTION

During the past 50 years, perovskite compounds [ABO3 ] , especially those exhibiting piezoelectricity and ferroelectricity, have attracted much interest for use in electronic devices such as actuators, sound transducers, sensors, etc. [1]. The lead zirconate titanate [PZT] family of materials has served as the cornerstone for these applications thus far. A critical drawback of this material, however, is the presence of lead and the recent concerns about the toxicity of lead-containing devices. Recently, lead-free ferroelectrics (K, Na)NbO3 [KNN] has attracted a great deal of attention because of its superior ferroelectric properties, which are comparable to those of PZT systems [26]. When a ferroelectric crystal is cooled below its Curie temperature, in the absence of external electrical and mechanical stresses, it generally breaks into domains, the directions of polar axes in the neighboring domains being dierent. Intrinsically, most electrical properties are primarily determined by the ferroelectric domain structure and by the domain-wall mobility. If the changes in these electrical properties are to be understood, it is of vital importance to study the relation between the domain structure, the domain size, and the grain size [7]. Numerous polycrystalline ceramics, which undergo ferroelectric phase transitions, have a simple lamellar twinning or a banded twin structure. In ne-grained ceramics, the deformed grains adjust in two dimensions by simple lamel E-mail:

lar twinning. In coarse-grained ceramics, twinning with a band structure allows for grain adjustment in the third dimension. The banded twin structure can transform into the simple lamellar twin structure by stress relief. The banded twin structure is understood to contain a higher elastic energy than a simple lamellar twin structure because the absolute strain energy increases with increasing grain size, g as g3 . Furthermore, Arlt et al. [8] have shown that the equilibrium domain width depends on the grain size, decreases for grain sizes, a, <10 m, and is eectively constant for grain sizes, a, >10 m. They explained that the eects of domain size gave rise to a high dielectric constant for ne-grained BaTiO3 . Recently, in the tetragonal BaTiO3 crystals with the engineered domain congurations, the piezoelectric properties have been found to be signicantly improved with decreasing domain sizes and were larger than those of PZT ceramics [911], which agree with previous reports [12,13]. These results suggest that domain size control could lead to remarkable improvements in the piezoelectric properties. In this study, the domain structures of orthorhombic Li0.02 KNN ceramics were observed, and the eect of the domain size on the coercive eld was investigated.

II. EXPERIMENTAL K2 CO3 , Na2 CO3 , Nb2 O5 , and Li2 CO3 of high purity (>99.0% purity) were used as the starting materials. Li0.02 (K0.45 Na0.55 )0.98 NbO3 [Li0.02 KNN] ceramics
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goedc@kicet.re.kr; Fax: +82-2-3282-2424

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were prepared using the conventional solid-state synthesis. The starting materials were prepared after completely removing absorbed water at 200 C for one hour; special care was taken so that K2 CO3 did not to absorb water during the manufacturing process. The powders were mixed in a polyethylene (HDPE) bottle for 24 h using ZrO2 balls in ethyl alcohol. The mixed powders were calcined at 850 C for 5 h in air. These powders, milled with a 5 wt% polyvinyl alcohol (PVA) aqueous solution, were uniaxially pressed into disks with a 10 mm diameter at a pressure of 100 Mpa and were subsequently sintered at 1050 C for 5 h in air. A commercial PFM (PucoTech, PICOStation) was used to observe surface domain structures and measure the electrical properties on polished samples by using contact topography and piezoresponse modes. The scanned head allowed a maximum scan area of 40 m 40 m. Commercially available Pt-coated conductive silicon cantilevers with a tip radius of 40 nm were used. Their spring constants lie between 1.0 and 5.0 N/m with a resonance frequency of approximately 50 - 70 kHz.

Fig. 1. (a) Topograph and (b) PFM image of Li0.02 KNN ceramics with large grain sizes above 15 m, showing the orientations of domain walls with {100} grain boundaries.

III. RESULTS AND DISCUSSION Li0.02 (K0.45 Na0.55 )0.98 NbO3 [Li0.02 KNN] ceramics have the orthorhombic perovskite structure (Bmm2), which is completely isomorphous with KNbO3 . The orthorhombic structure leads to patterns of the domain distribution that are more complicated than those of tetragonal structures composed of only two types of domain walls (90 and 180 ). The orthorhombic unit cell of Bmm2 can be considered as a distortion of the original cubic cell, that distortion being caused by elongating one of the face diagonals of the original cube, which becomes the orthorhombic a direction (polar) and by compressing the other face diagonal, which becomes the orthorhombic b direction. The lattice distortion can then be described in terms of a slight change in the length of the original cube edges and a shear in one of the cubic (001) planes. In this case, pseudocubic {100} planes and pseudocubic {011} planes serve as domain walls [14]. Four types of domain walls (90 , 60 , 120 , and 180 ) may be allowed in the Bmm2 structure. Figure 1 shows the typical domain pattern of Li0.02 KNN ceramics with large grain sizes above 15 m. A highly complicated conguration of domains was observed in which all types of domains existed together in a grain. Domain walls, 60 and 90 , may be identied by using the angle between the domain wall and the grain boundary because 60 and 90 domain walls intersect the grain boundaries ({100} planes) with an incline of 0 or 90 and 45 , respectively [3]. In addition to these commonly observed walls, an S-wall can appear in a Bmm2 crystal structure such as KNbO3 and KNN [14,15]. They are irrational planes and permissible walls for 60 and 120 domains. In a single crystal, 60 domains cut the

corner formed by two {100} and a (101) facet. An orientation of (0.30/1/1) is obtained for the walls. Thereby, a domain wall with an angle of 18.4 to the {110} (equal to cubic {100} planes) was assigned to the S-wall [3,16]. Ceramics, however, make the domain patterns extremely complicated, so the domain structure of orthorhombic ceramics has not been suciently interpreted so far. If the eect of domain size on the coercive eld is therefore to be investigated, it is necessary to choose grains exhibiting a simple domain pattern and to evaluate the domain size exactly. As is well known, numerous polycrystalline ceramics, which undergo ferroelectric phase transitions, have a simple lamellar twinning or a banded twin structure, depending on the grain size [12]. These domain structures are also observed in Li0.02 KNN ceramics. In ne-grained ceramics, the deformed grains adjust in two dimensions by simple lamellar twinning; in coarse-grained ceramics, the twinning with a band structure allows for grain adjustment in the third dimension. As shown in Fig. 1, highly complicated patterns of domains were observed in coarse-grained ceramics with a banded twin structure. In contrast, the domain patterns of grains exhibiting simple lamellar twinning, which consisted of 90 domains, were relatively simple. A 60 domain could be easily moved under very low stress [17], so most 60 domains, except for wedge-shaped domains, could be removed by internal stresses. Generally, no 90 wedges were formed in the orthorhombic phase of KNbO3 because there were no alternative position for the twin plane to pass through the body of the crystal. All the wedges observed were 60 wedges [14]. Thus, only considering 90 domains in simple lamellar twinning to estimate the eect of domain size is valid. Figures 2(a) and 2(c) show atomic force microscope (AFM) topographs of grains with sizes of 6.3 4.2 m and 2.0 6.2 m, respectively, and the corresponding piezoelectric force microscope (PFM) images are shown in Figs. 2(b) and 2(d). The simple lamellar twinning, which is predominantly distributed in Li0.02 KNN ceramics with grain sizes of 3 15 m, is observed in the PFM images. We can conrm that the domain walls, constituting a simple lamellar twinning, are 90 domain

Eect of Domain Size on the Coercive Field of Orthorhombic (Li, K, Na)NbO3 Jeong-Ho Cho et al.

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Fig. 4. Grain size dependence of the domain width for 90 domains.

Fig. 2. Topographs (a and c) and corresponding PFM images (b and d). PFM images show simple lamellar twinning.

Fig. 3. Topographs (a and c) and corresponding PFM images (b and d) of grains with sizes below 3 m.

walls because these walls intersect grain boundaries at an incline of 45 . In these cases, the domain widths are about 275 300 nm, which is evaluated from two layers composed of a polarization set of upward and downward directions. In small grains below 3 m, on the other hand, it is dicult to dene the domain structures as simple lamellar twinning. Figure 3 shows AFM topographs and cor-

responding PFM images of grains smaller than 3 m. In such cases, the domain width is wider than those of large grains (>3 m), even though the grain sizes are still small. The domain size in ferroelectric materials is a state of equilibrium between the energy of the domain walls and the energy of the electric and elastic elds created by the spontaneous polarization and strain. Arlt [12] suggested that the twin width (d) depended on the grain size (g), d g1/2 . This relationship holds for all types of simple lamellar twinning in ceramics, in which the twin wall energy and the elastic deformation energy determine the minimum. This relationship was conrmed in Li0.02 KNN ceramics for grain sizes of 3-15 m and only for 90 domains. Figure 4 shows the domain width of a simple lamellar twinning as a function of the grain size. It is obvious that the domain width decreases with decreasing grain size in Li0.02 KNN ceramics, as in the results for BaTiO3 or PbTiO3 [7,8]. For grains with <3 m, however, this result does not coincide with the grain size dependence on domain size. It is dicult to explain why the domain size increases as the grain size decreases for small grains (<3 um). Although several researchers have discussed the domain sizes of BaTiO3 or PbTiO3 , the results of those studies have not yet been clearly interpreted. Figure 5 shows PFM phases as a function of applied bias. These gures describe the eect of domain size on the coercive eld. As the polarization directions of the dipoles are reversed by using an applied voltage, the PFM phase changes abruptly and exhibits a hysteresis loop during a cycle of applied bias. A small electric eld leads to the nucleation of domains at the soft spot, and these domains quickly grow at the cost of the original domain. As the electric eld is increased, a new domain nucleates and grows through sidewise domain-wall motion until it lls the entire specimen. Nucleation is enabled by introducing defects or a soft spot with low barriers. Thus, the domain walls of a crystal play an important role in nucleation processes [1821]. As the domain size

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Journal of the Korean Physical Society, Vol. 57, No. 4, October 2010

Fig. 5. PFM phases as a function of applied bias for dierent domain sizes: (a) 480 nm, (b) 420 nm, and (c) 260 nm.

decreases, the domain wall density increases, providing many nucleation sites. Therefore, the coercive eld signicantly decreases with decreasing domain size.

REFERENCES

IV. CONCLUSION Li0.02 (K0.45 Na0.55 )0.98 NbO3 [Li0.02 KNN] ceramics were prepared by using conventional solid state synthesis. A highly complicated conguration of domains was observed in grains with sizes over 15 m, where all types of domains existed together. Domain walls, 60 and 90 , domain walls were identied by using the angle between the domain wall and the grain boundary. In order to evaluate the domain size, we considered only the 90 domains in simple lamellar twinning. In grains with sizes of 3 15 m, simple lamellar twinning was observed, and the domain widths were about 275 300 nm. In small grains below 3 m, the domain width was wider than those of large grains (>3 m), even though the grain sizes were still small. A large number of nucleation sites could be provided by decreasing domain size, and so the coercive eld could be signicantly decreased.

ACKNOWLEDGMENTS This work was nancially supported by the Fundamental R&D Program for Core Technology of Materials funded by the Ministry of Knowledge Economy, Republic of Korea.

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