Solid State Communications 133 (2005) 311314 www.elsevier.

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Domain structures in tetragonal Pb(Mg1/3Nb2/3)O3PbTiO3 single crystals studied by piezoresponse force microscopy
H.F. Yua,b,*, H.R. Zenga, H.X. Wanga,b, G.R. Lia, H.S. Luoa, Q.R. Yina
a

State Key Laboratory of High Performance Ceramics and Superne Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China b Graduate School of The Chinese Academy of Sciences, Beijing 100039, China Received 21 October 2004; accepted 8 November 2004 by A. Pinczuk Available online 24 November 2004

Abstract The domain structures in (001) surface of Pb(Mg1/3Nb2/3)O340% PbTiO3 single crystals were investigated by piezoresponse force microscopy. Both micron-sized ngerprint 1808 and parallel 908 domains were observed in the sample. Different sets of favourable {110} oriented domain patterns were found to meet, intersect or grow through each other. In addition, the piezoelectricity decreases sharply at the domain walls in 1808 structures, but does not in the 908 domain structures. q 2004 Elsevier Ltd. All rights reserved.
PACS: 77.80.Dj; 77.84.Ks; 07.79.Kv; 77.65.Kj Keywords: A. PMNPT single crystals; C. Piezoresponse force microscopy; D. Ferroelectric domains; D. Piezoelectricity

1. Introduction Relaxor ferroelectric single crystals (1Kx)Pb(Mg1/3Nb2/3)O3xPbTiO3 (PMNxPT), which have a broad composition range, are well known to possess excellent piezoelectric (d33w2500 pCNK1) and dielectric (3rw50005500) properties, as well as high electro-mechanical coupling coefcients (k33w94%) with composition near the morphotropic phase boundary, MPB (0.30%x%0.35) [13]. This is due to the complex microstructure related domain structure. X-ray and neutron diffraction investigations have veried a slightly distorted pseudocubic phase, X, for x!0.25, a rhombohedral ferroelectric phase for 0.25zx!0.35, and a tetragonal ferroelectric phase for xO0.35 [47]. Other study [8] also

has demonstrated that a monoclinic m phase, the third ferroelectric phase in PMN33% PT single crystals near their MPB composition, can appear at room temperature. Most of the research work concentrated on the growth and characterization the PMNPT ferroelectric single crystals with the composition near the MPB or in the rhombohedral side phase [913]. Less attention has been paid to study the PMNPT single crystals in the tetragonal phase. More recently, a set of physical property data of the tetragonal PMN42% PT single crystals has been reported [14]. However, the corresponding detailed domain information is needed for us to understand and apply these materials. Therefore, the purpose of this investigation was to study the domain structure in the tetragonal phase with the composition xZ0.40 by the newly developed piezoresponse force microcopy technique with high resolution.

* Corresponding author. Address: State Key Laboratory of High Performance Ceramics and Superne Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China. Tel.: C86 21 52411076; fax: C86 21 52413122. E-mail address: yuhanfeng@mail.sic.ac.cn (H.F. Yu). 0038-1098/$ - see front matter q 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.ssc.2004.11.012

2. Experimental method Pb(Mg1/3Nb2/3)O340% PbTiO3 single crystals were

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grown directly from the melt by a modied Bridgman technique. The details of preparation of PMNPT single crystals can be found elsewhere [15]. The crystal was cut into plates with (001) orientation, which were veried by an X-ray diffractometer. One of the surfaces was polished to optical quality, the [100] and [010] directions were also indicated with X-ray diffractometer technique on it, for investigation and the other was electroded by sliver paste and glued to the sample holder. The domain structures in the (001)-oriented PMN40% PT single crystals were examined by piezoresponse force microcopy. The investigation scale is in the range from several mm to several ten mm. A commercial atomic force microscope (SPA400/SPI3800N, Seiko Inc., Japan) was used in the experiment. All the operations were performed in atmosphere condition at room temperature with a conductive cantilever (NSC12-B, Micro Masch, Estonia). When an ac voltage Vac Z V0 sin ut is applied between the tip and the bottom electrode of the sample, in which the tip is also used as a top electrode, the alternating external electric eld gives rise to the piezoelectric vibration of the sample, or a change in the sample thickness due to the converse piezoelectric effect. The sign of the piezoelectric coefcient depends on the polarization orientation, thus the regions of sample with opposite polarization state will vibrate out of phase upon the action of the ac eld. The magnitude of the piezoelectric coefcient and the direction of local polarization are reected in the amplitude and phase of the vibration signal, respectively. In the experiment, an imaging ac voltage with 2.0Vpp and 8 kHz was applied.

roughly 908 in Fig. 1(b). In the tetragonal phase ferroelectrics, the {110} oriented domains are compatible with stresses formed in the course of phase transformation. So the different {110} oriented domains can coexist in the same surface and grow, respectively. While they meet, they can intersect and stop there (see the right side in Fig. 1(b)) or grow through each other (see the left side in Fig. 1(b)). Fig. 2 shows the topography, piezoresponse, phase and amplitude images obtained from the same region of the PMN40% PT single crystal. The domains are w0.7 mm in width, which are nearly equal to those of the miniature ngerprint domain displayed in Fig. 1(b). It is shown that they are continuous and oriented. From the linescan in the phase image, the adjacent domains have a w1808 change in the phase. So it can be identied that the domain patterns are 1808 structures. It is interesting to nd that the amplitude values in the adjacent domains are nearly equal, but it has a sharp decrease at the domain wall regions in the amplitude linescan image, shown in Fig. 2(e). This indicates that the piezoelectricities in the adjacent domains are almost equal but an obvious low in the domain wall.

3. Results and discussion Fig. 1 shows the typical topography and its corresponding domain structures on the (001) surface of PMN40% PT single crystal imaged simultaneously by piezoresponse force microscopy. In the topography (Fig. 1(a)), there is no additional information except for some surface scratches. The domain patterns are hierarchical. Two sets of {110}  oriented, e.g. (110) and 110, large domain structures are located in the miniature ngerprint domain structure. The angle between the two sets oriented domain structures is

Fig. 1. The typical topography (a) and the domain structures (b) at the same area in (001) surface of PMN40% PT single crystal. The angle between the two sets of oriented domain structures is roughly 908.

Fig. 2. The topography (a), the piezoresponse A cos F image (b), the phase (F) image (c) and the amplitude (A) image (d) of the 1808 domains at the same region in (001) surface of PMN40% PT single crystals. The linescans of the A cos F, F, A images in the same direction, which was marked in (b), is displayed in (e).

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However, Fig. 3 shows the sizes of the large domain structures at high resolution are w1.5 mm, which are similar to those in Fig. 1. This picture reveals that they are oriented and separated by the other oriented domains in the long direction. From the linescan in the amplitude image, shown in Fig. 3(e), it can be seen that the difference between the amplitude values in the adjacent domains are obvious. It reects that the piezoelectricities in the adjacent domains are different. And from the phase image, the adjacent domains mostly have a 908 shift in the phase. So it can be conrmed that the domain patterns are 908 structures. But the obvious decrease of the value in the amplitude linescan image at the domain wall region has not been found in the 908 domain pattern. The study also obtained the other two domain pattern structures as shown in Fig. 4. The sizes of the domains in Fig. 4(a) are nearly equal to those in Fig. 2(b). It is reasonable to form the unoriented 1808 domains because it only to be compatible for charges. However, the non-1808 domains should be compatible not only for charges but also for stresses [16]. In Fig. 4(b) the domains are nearly continuous and the widths are in agreement with those in

Fig. 4. The unoriented piezoresponse images in (001) surface of PMN40% PT single crystals. The domain sizes are w0.7 mm (a) and w1.5 mm (b), respectively.

Fig. 3. The orientation of the domains is obvious, but the domain walls become coarseness and saw-toothed morphology [17]. In fact, the domain structures in Figs. 3(b) and 4(b) are two effective ways to lengthen the domain walls or to resume the head-to-tail arrangement locally in domain wall to stabilize the domain structures.

4. Conclusions Both micron-sized ngerprint 1808 and parallel 908 domain structures in (001) surface of Pb(Mg1/3Nb2/3)O3 40% PbTiO3 single crystals were clearly imaged by piezoresponse force microscopy. Different sets of favourable {110} oriented domain patterns were found to meet, intersect or grow through the each other. Furthermore, it was found that the piezoelectricity decreased sharply at the domain walls in 1808 structures, but such phenomenon didnt appear at the 908 domain structures.

Acknowledgements This work is supported by National Key Development Program for Basic Research of China (Grant No. 2002CB613307).

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Fig. 3. The topography (a), the piezoresponse A cos F image (b), the phase (F) image (c) and the amplitude (A) image (d) of the 908 domains at the same region in (001) surface of PMN40% PT single crystals. The linescans of the A cos F, F, A images in the same direction, which was marked in (b), is displayed in (e).

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