Solid-State Electronics 47 (2003) 22952298 www.elsevier.

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The syntheses and microstructures of tabular SrTiO3 crystal

Hanxing Liu *, Xiaoqin Sun, Qinglin Zhao, Jing Xiao, Shixi Ouyang
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, PR China Received 10 January 2003; received in revised form 3 March 2003; accepted 12 May 2003

Abstract In the present paper, the microstructures of SrTiO3 particles obtained in two dierent methods were examined by scanning electron microscopy (SEM) and X-ray diraction pattern (XRD). The two synthesis techniques included a conventional mixed solid method and a molten salt synthesis method (MSS), which proceeded through two steps. In the rst, precursor Sr3 Ti2 O7 particles were synthesized. Tabular SrTiO3 crystals were synthesized via the superposition of the SrTiO3 basic cell on the interface of Sr3 Ti2 O7 particles. The microstructures of SrTiO3 particles synthesis in those two ways were quite dierent. The microstructures of SrTiO3 obtained by MSS method were high purity and obviously tabular in structure. Oriented growth faces included typical (0 0 1), (1 0 0), (1 1 0), etc. The mechanism of the oriented growth of tabular SrTiO3 could be considered as the superposition of coordination polyhedron TiO6 octahedron basic cell on the interface of Sr3 Ti2 O7 particles. 2003 Elsevier Ltd. All rights reserved.
Keywords: SrTiO3 ; Microstructures; Molten salt synthesis; Oriented growth

1. Introduction Among the class of electroceramics exhibiting novel properties, SrTiO3 is a technologically important functional electroceramics. SrTiO3 is a multifunctional perovskite structure compound, having a high dielectric constant, a low dielectric loss, etc., which has been applied in capacitors, and other electronic applications [15]. With the development and application of microelectronics conventional material process can not meet the demand for both properties [69]. There were many synthesis methods applied to SrTiO3 including conventional mixture oxides, microwave synthesis [10], coprecipitation [11], hydrothermal synthesis [12], alkoxide hydrolysis [13], and metallo organic processing [14]. The microstructure and the processing for each are quite dierent.

Corresponding author. Fax: +86-27-8787-9468. E-mail address: lhxhp@mail.whut.edu.cn (H. Liu).

Synthesis of SrTiO3 with a tabular crystal microstructure attracts special attention. Tabular particles can yield thinner coatings. It can be used when multiplayer capacitors require thinner layers of ceramic powders for improved properties. Tabular or plate-like single crystal particles can be used to modify available substrates to control the orientation in deposited thin lms. For example, tabular PbTiO3 particles can be used to grow ber-textured PbTiO3 thin lms. Tabular or plate-like SrTiO3 provide template to grain growth of textured polycrystalline structural ceramics. In order to obtain excellent piezoelectric properties lead-based relax ferroelectric materials oriented growth is needed. In PMNPT, PZNPT, etc., tabular SrTiO3 is useful as a template to texture PMNPT because it has virtually the same lattice parameter as PMNPT at room temperature. With the addition of tabular SrTiO3 , oriented PMNPT and PZNPT is possible with a high increase of piezoelectric coecients and a possible decrease of dielectric loss, as compared to that of common ceramics. Thus the synthesis of tabular SrTiO3 and the study of an oriented growth mechanism would be important. Molten salt

0038-1101/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0038-1101(03)00215-6

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H. Liu et al. / Solid-State Electronics 47 (2003) 22952298

synthesis (MSS) [1518] is a possible way to obtain tabular SrTiO3 .

3. Results and discussion 3.1. The microstructures of the reaction products

2. Experimental procedure Two synthesis methods namely MSS method and conventional solid reaction method, were employed to produce SrTiO3 particles in this paper. The raw materials for the synthesis included analytically pure SrCO3 , TiO2 , and KCl along with ethyl alcohol. In the conventional method, SrCO3 and TiO2 powders were mixed in a 1:1 ratio for 10 h. The samples were pressed into discs after the reactant slurry dried. The mixture was calcined at 1200 C for 4 h to obtain the products (the sample A2 in Table 1). MSS method included two steps. In the rst, precursor Sr3 Ti2 O7 particles were synthesized, then tabular SrTiO3 crystal was synthesized via the superposition of the SrTiO3 basic cell on the interface of Sr3 Ti2 O7 particles. In MSS method, SrCO3 and TiO2 powders were mixed by ball milling for 8 h in ethanol according to a 3.1:2.0 molar ratio. Potassium chloride was added to the slurry in the amount of 50 wt% of the total dry solid powder. The mixture was milled for further times. The milled slurry was dried in an oven above the melting point of KCl (780 C) at 1300 C for 4 h. The solid reactions occur in the dry powder. The reaction product was separated from the solidied mass by repeated washing with hot deionized water to dissolve the KCl. The powders were dried (the sample A0 in Table 1). Due to the high ratio of Sr, Sr3 Ti2 O7 would react with TiO2 to produced SrTiO3 . Therefore Sr3 Ti2 O7 and TiO2 were gently mixed in ethanol in the second step. Potassium chloride was added to the suspension in a 1:1 weight ratio with respect to the reactants. The slurry was dried, and subsequently reacted in a covered alumina crucible at 1200 C for 4 h (the sample A1 in Table 1). The detail reaction conditions for three kinds of samples obtained by the two methods shown above are presented in Table 1. To check the amounts of perovskite phase, the calcined powder or the pellets were analyzed using Japan D/MAX-YB X-ray diraction (XRD). Microstructure of powders were analyzed by Japan JSM-5610 scanning electron microscopy (SEM).

Following the experiments in Section 2, the microstructures for dierent samples were examined. Fig. 1 shows the XRD pattern for three samples. The XRD pattern of the precursor Sr3 Ti2 O7 prepared by MSS in the initial stage is shown in Fig. 1(a), where the SrTiO3 phase also appeared along with the Sr3 Ti2 O7 phase. The two phases coexist in the precursor. The XRD pattern of SrTiO3 prepared by MSS in 1200 C for 4 h is presented in Fig. 1(b). The relative intensity I=I0 of SrTiO3 was in agreement with the standard pattern of SrTiO3 , indicating the formation of a single perovskite cubic phase. From Fig. 1(c), we could nd diraction peaks of other phase besides SrTiO3 , which illustrated that some uncertainly exists in the products synthesized by the conventional solid reaction method. From SEM pictures presented in Fig. 2(c), the size of particles for SrTiO3 powder prepared by the conventional solid method, were <3 lm. The shapes were cubic without preferred orientation. In Fig. 2(a) and (b), Sr3 Ti2 O7 and SrTiO3 particles prepared by MSS took on obvious tabular structure, with a thickness of 25 lm and an edge length of 1040 lm.

Table 1 Synthesis method and heat treatment Samples A0 A1 A2 Reactant Sr3 Ti2 O7 SrTiO3 SrTiO3 Synthesis method MSS MSS Conventional solid method Heat-treatment 1300 C, 4 h 1200 C, 4 h 1200 C, 4 h Fig. 1. XRD pattern for the sample A0 (a), A1 (b), A2 (c).

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between the crystallographic orientation and the crystal conguration. The unveiling of each family of crystal plane with crystal conguration is intimately correlated to the crystallographic orientation of the negative ion coordination polyhedron. According to the Pauling Rule, the stability of the negative ion coordination polyhedron is maximized when the atoms (or ions) are connected by the vertex angle. The stability worsens when they are connected by edge or face. The crystal planes with the fastest growth rate were mostly connected by the vertex angle, whereas the crystal planes connected by face had the slowest growth rate. Those connected by edge had intermediate properties. Actually, crystal growth had dierent crystals conguration in dierent physical and chemical conditions. This is because the coordination polyhedron growth basic cell in solutions and melts can be connected to form basic cells with dierent forms of construction and dimensionalities, whereas the superposition of growth basic cells with dierent dimensionalities on each family of crystal planes have dierent stability. This inuences directly the growth rate percentage of each family of crystal planes, because its change reects the crystal conguration. SrTiO3 crystal prepared by solution method was cubic phase. It is tetragonal at low temperature and cubic phase at high temperature. Its change from cubic to tetragonal corresponds with the change from paraelectric phase to ferroelectric phase. As shown in Fig. 3, TiO6 octahedron was the major structure basic cell. A lattice cell is formed by eight TiO6 octahedrons, with Sr2 lying in the center, connected with O2 in eight octahedrons around, which form a SrO8 cube. The TiO6 octahedron basic cell is connected with each other by vertex angle in crystal. It can form dierent basic cells such as monomer, chain, reticulation and carcass according to the way of connection. The best orientation growth of Sr3 Ti2 O7 crystal provided an advantageous interface for SrTiO3 s further tabular growth. When a tabular seed crystal was selected, the (0 0 1) seed exhibited tetragonal structure in the initial stage. When the crystal grew, (0 1 1) and (1 1 0) faces began to

Fig. 2. SEM micrographs of sample A0 (a), A1 (b), A2 (c).

3.2. Mechanism analysis of tabular SrTiO3 crystal oriented growth In order to show the growth mechanism of SrTiO3 in the uxing agent KCl, we applied the coordination polyhedron growth model. From crystal chemistry theory, the basic cell growth of the crystal involves coordinated polyhedron according to the relationship

Fig. 3. Diagram of crystal structure for SrTiO3 .

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H. Liu et al. / Solid-State Electronics 47 (2003) 22952298 solution-deposited BaTiO3 and SrTiO3 thin lms. J Am Ceram Soc 1999;82(9):235967. Ardila DR, Andreeta MRB, Cuni SL, Hernandes AC, Andreeta JP, Mascarenhas YP. Single-crystal SrTiO3 ber grown by laser heated pedestal growth method: inuence of ceramic feed rod preparation in ber quality. Mater Res 1998;1(1):117. Liu HX, Liu ZJ, Ouyang SX. Study on the microstructure and properties of SrTiO3 synthesized by microwave heating. Acta Phys-Chi Sinica 1998;14(7):6249. Richard PR, Chang HJ, Ellis DE, Dravid VP. Electronic structure of pristine and solute-incorporated SrTiO3 . J Am Ceram Soc 1999;82(9):237384. Sabolsky EM, Jame AR, Kwon S, Trolier-McKinstry S, Messing GL. Piezoelectric properties of h0 0 1i textured Pb (Mg1=3 Nb2=3 )O3 PbTiO3 . App Phys Lett 2001;78(17): 25513. Liu HX, Liu ZJ, Ouyang SX. The mechanism of microwave synthesis for SrTiO3 . Aata Chim Sinica 1999;57: 4727. Chang Y, Hou D, Shi D. Single crystal growth of SrTiO3 by TSSG method. Phys Lett 1981;3:1922. Kim NK, Yoon S-G. Electrical and structural properties of SrTiO3 thin lms deposited by plasma-enhanced metalorganic chemical vapor deposition. J Mater Res 1997; 12(4):11603. Hong S-H, Messing GL. Development of textured mullite by templated grain growth. J Am Ceram Soc 1999;82(4): 86772. Liu HX, Li YW, Ouyang SX. Heating eect in microwave eld and microstructure of BaTiO3 . Sci China (Ser A) 1997;40:77984. Lee J, Shin HC, Choi JC, Choi SC. The electric properties of SrTiO3 varistor prepared by co-precipitation process. J Micro Packaging Soc 2000;7(3):711. Kalender N, Kartal M. Preparation of ba-hexaferrite powders using the hydrothermal process. Inter Ceram 1998;47(2):10811. Ziolli RL, Jardim WF. Photocatalytic decomposition of seawater-soluble crude oil fractions using high surface area colloid nanoparticles of TiO2 . J Photochem Photobio Chem 2002;A147:20512. Chatterjee S, Samanta SK, Bankerjee HD, MaiTi CK. Metalloorganic compound-based plasma enhanced CVD of ZrO2 lms for microelectronic applications. Bull Mater Sci 2001;24(6):57982. McCarthy TJ, Ngeyi S-P, Liao J-H, DeGroot DC, Schindler J, Kannewurf CR, et al. Molten salt synthesis and properties of three new solid-state ternary bismuth chalcogenides, b-CsBiS2 , c-CsBiS2 , and K2 Bi8 Sel3 . Chem Mater 1993;5:33140. Liao JH, Tsai MC. Synthesis and crystal growth of two novel layered structures NaKLaNbO5 and Na2 K2 Gd4 Nb2 O13 in molten hydroxide salts. Growth Des 2002; 2(2):835. Keiichi K, Yasuo A, Yutaka T. Molten salt synthesis of single-phase BaNd2 Ti4O12 powder. J Mat Sci 1999;34: 3015. Wang J, Fang J, Ng S-C, Gan L-M, Chew C-H, Wang X, et al. Ultrane barium titanate powders via microemulsion processing routes. J Am Ceram Soc 1999;82(4):87381.

appear. In the anaphase, (1 0 0), (1 0 1) and (1 1 1) faces began to appear during the reaction. Due to the TiO6 octahedron of SrTiO3 basic cell, the stabilization energy varied with dierent basic cell shape (such as monometer, chain, reticulation, carcass). The stabilization energy increased with the increasing content of Sr2 . During superposition of the SrTiO3 , the solution super saturation degree is high, the dominant basic cells are reticulation and carcass, with Sr2 lying in the center, and the crystal is tetragonal, As the crystal grew, it is obvious that TiO6 octahedron or reticulation and carcass basic cell laminate upon the (1 0 0) and (0 1 0) two faces. In the anaphase, the amount of reticulation and carcass basic cell decreased with the decreasing content of Sr2 in solution, thus the solution was dominated by monomer or chain basic cells. The stability of superposition of monomer on (1 0 0), (0 1 0) faces increased from the edge to the center. Thus (1 0 0), (0 1 0) faces grew faster in the center than in the edge, which spur (1 1 0), (1 1 1) and (2 1 0) faces to unfurl. From the crystallographic orientation of octahedron in the crystal and the unfurling in each family of crystal planes, it can be concluded that the octahedron unfurls upon (1 1 1) faces by face, upon (1 1 0) and (2 1 0) faces by edges. When TiO6 octahedron laminated upon these faces, three vertex angles were connected upon (1 1 1) and two upon (1 0 0), (1 1 0). Thus (1 1 1), (1 1 0) faces grow faster. In the anaphase, the content of Sr2 decreased and it concentrated on the (1 0 0) faces, which were unfurling faces of TiO6 octahedron vertex angle, where O2 concentrated. TiO6 octahedron laminated upon (1 0 0) faces rst. Thus (1 0 0) faces grew fast and the unfurling area decreased gradually in the anaphase. The (1 1 1), (1 1 0) faces then unfurl. 4. Conclusions Tabular SrTiO3 prepared by MSS was studied. The microstructure study show that the size was 1040 lm edge length and 25 lm thickness. Oriented growth of tabular SrTiO3 could be considered as the superposition of coordination polyhedron TiO6 octahedron on the Sr3 Ti2 O7 interface, whose oriented unfurling faces were (0 0 1), (1 0 0), (1 1 0), (1 1 1), (2 1 0), etc. Acknowledgements

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The research was supported by Natural Science Foundation of China (NSFC) and Ministry of Education of China.
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