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Journal of Crystal Growth 259 (2003) 296301

Growth and characterization of KNbO3 by vertical Bridgman method

T. Takagi*, T. Fujii, Y. Sakabe
Murata Manufacturing Co., Ltd., 2-26-10 Tenjin, Nagaokakyo, Kyoto 617-8555, Japan Received 23 May 2003; accepted 11 July 2003 Communicated by T. Hibiya

Abstract Potassium niobate (KNbO3; KN) was grown from a K2O-Nb2O5 ux using the vertical Bridgman (VB) method. By optimizing a ux composition, soaking temperature, the pulling down rate of crucible, and temperature gradient, we were able to successfully grow a pale white and partially colorless KN crystal, 10 mm in diameter and 50 mm in length, without a seed crystal. Blue coloration occurred when the soaking temperature was too high and low soaking temperature resulted in red coloration. The crystal had almost no cracking under optimal temperature conditions and optimal pulling down rate of the crucible. The X-ray pole gures of (0 4 0) and (0 0 4) reections revealed that the white crystal had a so-called multi-domain structure. It is possible to obtain the high quality KN crystal using VB method. r 2003 Elsevier B.V. All rights reserved.
PACS: 81.10.fq; 81.10.h Keywords: A2. Bridgman technique; B1. Niobates; B2. Ferroelectric materials

1. Introduction Potassium niobate (KNbO3; KN) is a ferroelectric material with a perovskite structure (a 0:5721 nm, b 0:5695 nm, c 0:3973 nm at room temperature), and one of the most promising crystals for nonlinear-optical and electro-optical devices because of its large nonlinear susceptibility and high photorefractive coefcient [1]. Also KN has large piezoelectric constants [1], therefore it
*Corresponding author. Murata Manufacturing Co., Ltd., 2288 Oshinohara, Yasu, Shiga 520-2393, Japan. Tel.: +81-77586-8209; fax: +81-77-587-1923. E-mail address: takagisc@murata.co.jp (T. Takagi).

has large electromechanical coupling constants in bulk acoustic waves [2,3] and in surface acoustic wave [4,5]. This is why a great deal of attention has been directed toward this material for many years. In general, top-seeded solution growth (TSSG) is used to grow KN bulk crystal [68] and a 50 50 15 mm high quality crystal has been obtained [8]. However, it needs a crystal diameter control system with weight sensor to use the TSSG technique industrially, and this results in expensive apparatus. We chose vertical Bridgman (VB) method to grow KN crystal. The reasons are as follows: (1) it is possible to grow KN crystal at low cost because it does not have to control the crystal diameter and (2) it is known as one of the low

0022-0248/$ - see front matter r 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.jcrysgro.2003.07.022

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temperature gradient process. Moreover, It is said that growing below the melt result in good quality KN crystal [6]. This paper is the rst article of our study and reports on the inuence of ux composition, the soaking temperature, the pulling down rate of the crucible, and the temperature gradient on VB growth of KN crystal.

2. Experiments KN is an incongruent melting material [9] and has to be grown from K2O rich, non-stoichiometric solution. As the starting material 99% K2CO3 and 99.99% Nb2O5 raw powders (Kojundo Chemical Laboratory Co., Ltd.) were used, and mixed. The mixture was then calcined at 900 C or 850 C for 2 h in a platinum crucible. The calcined mixture was milled and put into a cylindrical platinum crucible, 10 mm in diameter, 100 mm in height, and 0.2 mm in thick. The crucible was surrounded by an alumina tube maintain the shape of the crucible. Fig. 1 has a cross-section of the VB apparatus. The cylindrical furnace was separated into two heat zones, upper and lower zones, so that temperature bias could be controlled. A set of

platinum plate reectors was positioned above the crucible to homogenize the thermal conditions at the top. The melt temperature was monitored by an R-type thermo-couple placed under the crucible. The temperature distributions are in Fig. 2. We examined three types of temperature distributions (Types 13). The maximum temperature gradients of these three distributions were 10 C/ cm, 16 C/cm, and 24 C/cm. The crucible was placed into the VB apparatus at a position where the temperature gradient was maximum, then heated at a rate of 300 C/h to the soaking temperature, and melted for 12 h. Examined conditions, such as the composition of the mixture, calcined and soaking temperatures, are in Table 1.

Fig. 1. Cross-section of VB apparatus.

Fig. 2. Temperature distributions.

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After soaking, the melt was cooled down to 1045 C at a rate of 30 C/h. Crystal growth began when the crucible was pulled down at a rate of 0.31.0 mm/h after the melt was maintained for 2 h at 1040 C. When the crucible bottom temperature fell below 800 C, pulling down was stopped. It was then cooled down to room temperature at a rate of 15 C/h. The platinum crucible was broken and stripped off from the solidied contents using nippers. The contents were rinsed in water at room temperature for several hours to wash away the ux. In these experiments, the crystal was grown in air without a seed crystal. The X-ray powder diffraction pattern was measured to check the crystal structure at 25 C,
Table 1 Typical melt composition Melt composition K2O/Nb2O5 molar ratio 52/48 54/46 56/44 Calcined temperature ( C) 900 850 850 Soaking temperature ( C) 1070, 1150, 1250 1070, 1150 1070

300 C, and 500 C. The crystal orientation was determined by measuring the X-ray pole gures of (0 4 0) and (0 0 4) reections. Inductively coupled plasma atomic-emission spectrometry (ICP-AES) was used to determine the chemical composition of the crystals.

3. Results and discussion Fig. 3 shows crystals grown from various melt compositions and soaking temperatures, when the moving rate of the crucible was 1.0 mm/h and the temperature distribution was Type 2. For the case that the K2O/Nb2O5 molar ratio of the melt was 52/48, the whole of crystal had been blue and cracked when the melt was soaked at 1250 C. And red coloration occurred at the beginning of crystallization when the melt was soaked at 1070 C. A pale white and slightly yellow crystal was obtained when the soaking temperature was 1150 C. At other melt compositions, red coloration did not occur, but blue coloration did at a lower soaking temperature with increased K2O concentration of the melt.

Fig. 3. KN crystals grown from various melt compositions and soaking temperatures.

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Fig. 4. X-ray powder diffraction patterns.

Table 2 Chemical compositions of KN crystal Crystal color White Molar ratio of K2O/Nb2O5 Na2O (wt%) Pt (wt%) 1.00 0.093 o0.005 Red 0.98 0.109 o0.005 Blue 1.00 0.096 o0.005

Table 3 Results of crystal growth under various conditions Temperature Pulling down condition rate (mm/h) Type 1 Type 2 Type 3 1.0 1.0 1.0 0.5 0.3 Color White, pale yellow White, pale yellow White, pale yellow White, colorless, and red in bottom part White, colorless, and red in bottom part Crack Much Much A few Almost no crack Much

X-ray powder diffraction patterns (Fig. 4) conrmed that these crystals were consisted only KN crystals and the crystal structures were orthorhombic at 25 C, tetragonal at 300 C, and cubic at 500 C. There were no differences in diffraction patterns at different colored crystals. The molar ratios of K2O/Nb2O5 and impurity concentrations measured by ICP-AES are in Table 2. The red colored crystal was slightly Nb2O5 rich and Na2O was detected for all crystals. Other impurities such as Pt or Al2O3 were not detected. It is thought that local melt composition became K2O poor due to low soaking temperature, and a Nb2O5 rich phase such as K4Nb6O7, though undetected by X-ray powder diffraction, caused red coloration. The reasons for blue coloration are not yet completely clear. However, considering one report that blue color is due to free carriers induced by oxygen vacancies [6], K2O evaporation or deformation induced by overheating may be related to this blue coloration. Crystal grown under various conditions are listed in Table 3, when the K2O/Nb2O5 molar ratio in the melt was 52/48. Type 3 was the best temperature distribution to reduce the number of cracks. At a pulling down rate of 1.0 mm/h, the

crystal was slightly pale yellow, while the others were a pale white and partially colorless. Considering KN is yellow at high temperature, this appears to be because a high temperature phase was pinned by pores or inclusions in the pale yellow crystal. The crystal grown at a rate of 0.5 mm/h has almost no cracks, except for the red coloration part at the bottom (Fig. 5). The colorless part, 5 mm thick, cut off this crystal is also in Fig. 5. It is surprising that such a large colorless crystal was able to be obtained without a seed crystal using the VB method. We expected that a slower pulling down rate would result in larger colorless crystals; however, many cracks occurred in crystals grown at a rate of 0.3 mm/h. The reasons for these cracks are currently being studied. Fig. 6 shows X-ray pole gures of (0 4 0) and (0 0 4) reections for a white sample cut vertical to the direction of growth, where (0 4 0) includes (4 0 0). There are six spots in the pole gure of the (0 4 0) reection, which we can divide into two groups (A and B) with the three spots in each group being at an angle of 60 to each other.

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Fig. 5. Crystals grown at a rate of 0.5 mm/h, when K2O/Nb2O5 of melt was 52/48, temperature condition was Type 3.

Fig. 6. X-ray pole gures of (0 4 0) and (0 0 4) reections for a white crystal.

different directed crystals, (a1; b1; c1), (a2; b2; c2), (a3; b3; c3), make an angle of 90 for three c-axis, and 60 for three a- and b-axis. Fig. 7 shows a scheme for this structure. Look at the a1 and b1; these axes are in a plane including the c2- and c3axis and at 45 to c2 and c3: Considering the /1 1 0S direction in the cubic phase is a /1 0 0S or /0 1 0S axis in the tetragonal phase and these axes are the a- or b-axis in the orthorhombic phase [10], we assume that this structure was formed through two phase transitions, i.e. cubic to tetragonal at 435 C and tetragonal to orthorhombic at 225 C during the cooling process. We think this structure has a so-called multi-domain structure and transforms a single-domain, colorless crystal by an electrical or mechanical poling process.
Fig. 7. Scheme of white crystal structure.

4. Conclusion Further, there are three pairs, one spot in group A and another in group B, are at an angle of 90 to each other. However, for (0 0 4) reection, three spots are at an angle of 90 to one another. These results indicate that the white crystal has three We successfully grew a pale white and partially colorless KN crystal from a K2O-Nb2O5 ux using the vertical Bridgman method, by optimizing ux composition, soaking temperature, the pulling

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down rate of the crucible, and the temperature gradient. Soaking temperature was important to avoid coloration, i.e. blue coloration occurred when the soaking temperature was too high and a low soaking temperature resulted in red coloration. A crystal grown under a temperature gradient of 24 C/cm had almost no cracks. At a pulling down rate of 1.0 mm/h, the crystal was slightly pale yellow, while a crystal grown at a rate of 0.5 mm/h was pale white and partially colorless. A slower pulling down rate (0.3 mm/h) caused many cracks. The X-ray pole gures of (0 4 0) and (0 0 4) reections revealed that white crystal had so-called multi-domain structure. It is supposed that white crystal transforms colorless by electrical or mechanical poling process. We believe it is possible to obtain high quality KN crystal using the VB method.

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