Proceedings of Asian Physics Symposium 2005 December 7-8, 2005, Bandung, Indonesia

Atomic Simulations of Five Layer Aurivillius Oxides: A2Bi4Ti5O18 (A = Ba, Ca, Pb)
Afifah Rosyidaha, Djulia Onggoa, Khairurrijalb, and Ismunandara* Departemen Kimia Institut Teknologi Bandung, Jl. Ganesha 10 Bandung 40132 b Departemen Fisika Institut Teknologi Bandung, Jl. Ganesha 10 Bandung 40132 * Corresponding author e-mail address: ismu@chem.itb.ac.id (Fax. 022-250 4154)
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Abstract Aurivillius oxides are very important technologically, for example as an FeRAM materials. Atomistic simulation methods has been caried out for A2Bi4Ti5O18 (A = Ba, Ca, Pb) to determine the lowest energy configuration of the crystal structure by employing efficient energy minimisation procedures and compare the obtained values to those obtained from diffraction studies. The calculations rest upon the specification of an interatomic potential model, which expresses the total energy of the system as a function of the nuclear co-ordinates. The Born model frame-work, which partitions the total energy into long-range Coulombic interactions, and a short-range term to model the repulsions and van der Waals forces between electron charge clouds, is employed. This is embodied in the GULP simulation code. The simulation resulted in cell parameters for A2Bi4Ti5O18 (A = Ba, Ca, Pb) are of a = 5.494684 b =5.494564 c = 48.578937 , a = 5.402632 b =5.414576 c = 47.476578 and a = 5.471453 b = 5.445314 c = 49.563431 ; the lattice energy are 2428.067 eV; -2450.132 eV and -2487.437 eV. Structure refinements from powder neutron diffraction data using the Rietveld method resulted in orthorhombic (space group B2cb) with cell parameters for A2Bi4Ti5O18 (A = Ba, Ca, Pb) are of a = 5.4988(3) b =5.4980(4) c = 50.352(1) , a = 5.4251(2) b =5.4034(1) c = 48.486(1) and a = 5.4704(2)b = 5.4577(2) c = 49.643(1) . Thus it could be concluded that the atomic simulation reproduce well the obtained structural parameters from diffraction experiments. Keywords: Aurivillius phase; Atomic simulation; Ba2Bi4Ti5O18; Ca2Bi4Ti5O18; Pb2Bi4Ti5O18 1. Introduction Layered bismuth oxides commonly referred to as the Aurivillius phases have been known over a long period when he was studying the Bi2O3TiO2 system1). Recently, there has been renewed interest in the ferroelectric properties of the Aurivillius phases due to their potential application in nonvolatile computer memories2). The Aurivillius phases, which have the general formula Bi2An1BnO3n+3; n = 1; 2; 3; . . . can be described as resulting from the regular stacking of [Bi2O2]2+ slabs and perovskite-like [An-1BnO3n+3]2- blocks. The integer, n, describes the number of sheets of cornersharing BO6 octahedra forming the ABO3-type perovskite blocks. The 12-coordinate perovskitelike A-site is typically occupied by a large cation such as Na+, K+, Ca2+, Sr2+, Ba2+, Pb2+, Bi3+ or Ln3+ and the 6-coordinate perovskite-like B-site by smaller cations such as Fe3+, Cr3+, Ti4+, Nb5+ or W6+. Whereas the perovskite blocks offer large possibilities in terms of compositional flexibility, with numerous combinations of A and B cations observed, the cation sites in the [Bi2O2]2+ layers are almost exclusively occupied by Bi3+. In comparison to the n = 2 and 3 oxides, which have been extensively studied35), very little is known about the higher order n = 4 or 5 oxides. The synthesis of the n = 5 oxides A2Bi4Ti5O18 (A = Ba and Pb) were first reported in 196268). There were conflicting reports about the existence of single phase samples of Ba2Bi4Ti5O18; Subbarao reported that this is, in fact, a mixture of the four layer oxide BaBi4Ti4O15 and BaTiO3 while Aurivillius claimed that Ba2Bi4Ti5O18 could be obtained as a single phase. Recently, Irie et al. reported the preparation and ferro-electric properties of single crystals of A2Bi4Ti5O18 (A = Ba and Pb)9). They indexed the patterns of both compounds in B2ab with a b 5 and c 50 ; no other structural parameters were reported. Recent work has resolved this controversies, by determining the precise and accurate structure of these compounds.10-11) High resolution diffraction studies have demonstrated that the majority of Aurivillius phases

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do not adopt the prototype tetragonal structure at room temperature, rather tilting of the perovskitelike BO6 octahedra, together with displacement of the cations relative to the Bi2O2 layers, lowers the symmetry to either orthorhombic or monoclinic. Indeed the main structural basis for the ferroelectricity is the displacement of the perovskite A-type cations within the perovskite-like layers, along the crystallographic a-axis with respect to the chains of corner sharing BO6 octahedra. This corresponds to a [110] displacement referred to the parent I4/mmm. In order to retain the unit cell, with the c-axis perpendicular to the structural layers, it has been customary to select the direction of spontaneous polarization along the a-axis. This results in the widespread use of non-standard settings of the space groups with an A-centered lattice for compounds with even values of n and a B-centered lattice for compounds with n odd. The aim of the present work is to apply atomistic simulation techniques, to the study of the archetypal Aurivillius phase A2Bi4Ti5O18 (A = Ba, Ca and Pb). Atomistic simulation techniques are now established tools for the investigation of structures and energetics of materials. 2. Simulation methods The simulation techniques used in this work, embodied in the GULP code12,13), are based upon lattice energy minimization procedures; detailed reviews have already been given elsewhere14), so only a brief account will be presented here. The basis of the simulation is the specification of a potential model which describes the energy of the system as a function of the atomic coordinates and allows the modelling of perfect and defective lattices. The interactions between ions are partitioned in terms of long range Coulombic forces and short range interactions which account for electron cloud overlap (Pauli repulsion) and dispersion (Van der Waals) interactions. An analytical function of the Buckingham form contains the short-range potential parameters which are usually empirically derived values: V(r)=Ae
r /

Polarisability of the ions, which is an important parameter especially for a lone-pair cation, is incorporated by means of the DickOverhauser shell model. This model treats such effects such effects in terms of a shell with charge Y connected to a core with charge Z-Y (where Z is the formal charge of the ion) by an isotropic harmonic spring of force constant k. The shell nominally represents the valence electron cloud, and the core represents the nucleus plus core electrons. During the energy minimization procedure, the core and the shell of each ion are allowed to relax independently and, thereby, displacement of the shell relative to the core affects the ionic polarization within the lattice. It should be emphasized that employing such a potential model does not necessarily mean that the electron distribution corresponds to a fully ionic system, and that the general validity of the model is assessed mainly by its ability to reproduce experimental crystal properties. Energy minimization methods lend themselves to the modeling of complex inorganic structures, in that a minimum energy structure is calculated from a specified initial configuration (typically the observed crystal structure). The minimization procedure is of the Newton-Raphson type which employs information on the second derivatives of the energy with respect to atomic positions, and is found to be particularly efficient. 3. Results And Discussion We study A2Bi4Ti5O18 (A = Ba, Ca and Pb) which can be considered as the simplest representative compound as a preliminary study to do systematic and more complex composition.

where A, and C are empirically derived parameter for each ion-ion interaction. The lattice energy calculations employ the now standard Ewald summation procedures for the Coulombic interactions.

C r6

(1)

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Table 1 Interatomic potentials for A2Bi4Ti5O18 (A = Ba, Ca and Pb). All except, Ti-O interaction were obtained from 13) A (eV) a) Short-range Buckingham Bi3+.. Bi3+ 24244.50 Bi3+.. O249529.35 4818.416 Ba2+.. O2Ca2+.. O21614.6 72276.42 Pb2+.. O2Ti4+.. O22549.4 9547.96 O2-.. O2b) Shell model Species Bi3+ Ba2+ Ca2+ Pb2+ Ti4+ O2K (eV 2) 395.55 34.05 34.05 172.7 39.5 6.3 () 0.3284 0.2223 0.3067 0.2981 0.2223 0.2989 0.2192 C (eV 6) 0.0 0.0 0.0 0.0 8.0 0.0 32

Shell(e) -5.51 1.831 1.281 -4.00 2.89 -2.04

Figure 1 Structure of Ca2Bi4Ti5O18 (left) and Ba2Bi4Ti5O18 (right). The Bi atoms are represented by the small shaded sphere. Note the difference in the rotations of the octahedral

Table 2 Calculated and experimental lattice parameter for A2Bi4Ti5O18 (A = Ba, Ca and Pb) Parameter Calculated Exp10,11) (expcalc)% A = Ba A () 5.494684 5.4988(3) -0.07 B () 5.494564 5.4980(4) -0.06 C () 48.578937 50.352(1) -3.52 90 90 = = (deg) Lattice energy -2428.067 (eV) A = Ca A () B () C () = = (deg) Lattice energy (eV) A = Pb a () b () c () = = () Lattice energy (eV)

The core-shell was introduced using the parameter reported in Table 1. The initial interatomic potentials were those derived by Pirovano et al.13) to describe Aurivillius phases. Due to the importance of the octahedral distortions the effect of various Ti-O potentials on the calculated structural model was examined. To determine whether the model provided a good reproduction of the experimental data, the lattice parameters were examined. The result of these calculations is the final set of interatomic potentials used in the calculations given in Table 1. The calculated lattice parameters are listed in Table 2, which generally show good accord with experimental data with an average difference of 1.1% for a relatively complex structure. This provides a valid starting point for the next calculations, especially defect calculations.

5.402632 5.414276 47.476578 90 -2450.132

5.4251(2) 5.4034(1) 48.486(1) 90

-0.41 0.20 -2.12

5.471453 5.445314 49.563431 90 -2487.437

5.4701(2) 5.4577(2) 49.643(1) 90

0.02 -0.2 -0.16

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Table 3 Atomic coordinates parameters of A2Bi4Ti5O18 (A = Ba, Ca and Pb) Atom A = Ba Bi(1)/A(1) Bi(2) Bi(3)/A(2) Ti(1) Ti(2) Ti(3) O(1) O(2) O(3) O(4) O(5) O(6) O(7) O(8) O(9) A = Ca Bi(1)/A(1) Bi(2) Bi(3)/A(2) Ti(1) Ti(2) Ti(3) O(1) O(2) O(3) O(4) O(5) O(6) O(7) O(8) O(9) A = Pb Bi(1)/A(1) Bi(2) Bi(3)/A(2) Ti(1) Ti(2) Ti(3) O(1) O(2) O(3) O(4) O(5) O(6) O(7) Calculated Y 0.992985 0.000064 0.001033 0.00 0.001942 0.999326 0.252766 0.255142 0.985597 0.011208 0.997690 0.269488 0.243502 0.266980 0.261680 Experimental 10,11) Y Z 0.993(7) 0.0433(1) 0.00 0.22515(7) 1.001(6) 0.1306(1) 0.00 0.500 0.002(6) 0.4160(2) 0.999(7) 0.3300(2) 0.250(4) 0.0008(5) 0.255(5) 0.2508(4) 0.986(6) 0.2958(1) 0.011(5) 0.3801(1) 0.998(7) 0.4604(1) 0.269(3) 0.0802(4) 0.245(4) 0.9212(3) 0.265(3) 0.8373(3) 0.260(3) 0.1616(3)

X 0.000047 0.993016 0.995778 0.991686 0.996745 0.994343 0.250596 0.259550 0.980592 0.008340 0.020744 0.273132 0.246930 0.270747 0.267402

Z 0.039701 0.213322 0.120060 0.500000 0.410513 0.318691 0.000576 0.251027 0.305079 0.387320 0.462131 0.076508 0.924988 0.845530 0.153235

X 0.000 0.993(4) -0.004(4) -0.008(6) -0.003(5) -0.006(4) 0.250(4) 0.259(5) -0.019(4) 0.008(4) 0.020(4) 0.272(4) 0.247(4) 0.269(4) 0.266(4)

0.999803 0.097892 0.976785 0.986981 0.004634 0.996848 0.163534 0.275360 0.952057 0.967373 0.957917 0.236032 0.181248 0.219810 0.245471

0.994937 0.981779 0.005688 0.00 0.000258 0.006625 0.209672 0.243603 0.043778 0.947553 0.071886 0.256320 0.201950 0.248019 0.284164

0.038490 0.214628 0.115478 0.500000 0.414794 0.331763 0.006273 0.248880 0.303369 0.388294 0.462618 0.071743 0.918333 0.846023 0.160650

0 0.98(4) -0.022(7) 0.010(7) 0.004(6) -0.002(5) 0.197(2) 0.237(5) -0.048(4) 0.969(4) 0.953(4) 0.236(5) 0.177(4) 0.220(5) 0.250(6)

0.995(3) -0.018(2) 0.006(3) 0 0.001(6) 0.006(4) 0.224(3) 0.244(3) 0.044(3) 0.944(2) 0.067(2) 0.256(3) 0.200(2) 0.243(3) 0.269(3)

0.0425(2) 0.2238(1) 0.1278(2) 0.5 0.4191(3) 0.3342(2) 0.0062(2) 0.2489(2) 0.2973(2) 0.3804(1) 0.4586(2) 0.0754(3) 0.9145(2) 0.8453(2) 0.1619(2)

0.0000001 0.015396 0 0.029303 0.023362 0.012839 0.313805 0.273960 0.060675 0.020744 0.035435 0.282544 0.316770

0.99800 0.993786 0.002000 0.00 0.978297 0.005409 0.410385 0.246698 0.007492 0.985144 0.074232 0.199749 0.207552

0.04314 0.226119 0.130000 0.5000 0.419483 0.339853 0.001553 0.249823 0.317882 0.511295 0.398871 0.082793 0.914350

0 0.016(2) 0 0.025(6) 0.020(3) 0.014(3) 0.304(3) 0.268(3) 0.046(2) 0.028(3) 0.041(2) 0.270(2) 0.320(3)

0.998 (2) -0.006 (1) 0.002 (2) 0 0.997 (3) 0.004 (3) 0.264 (2) 0.248 (3) 0.010 (2) 0.983 (2) 0.044 (2) 0.232 (2) 0.284 (2)

0.0431 (6) 0.2248 (6) 0.13000 (6) 0.5 0.4164 (1) 0.3305 (1) 0.0015 (3) 0.2497 (2) 0.2961 (1) 0.3796 (1) 0.4601 (1) 0.0775 (2) 0.9194 (2)

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O(8) 0.280365 0.208306 0.829890 O(9) 0.296736 0.212959 0.172973 The observed structural parameters are in good agreement with values from difraction studies reported previously Tabel 2 and 3.10,11) Fig. 1 compares the structures of Ca2Bi4Ti5O18 and Ba2Bi4Ti5O18. It is immediately apparent from this figure that the structure of Ba2Bi4Ti5O18 is much less distorted that of Ca2Bi4Ti5O18, consistent with those observed from diffraction studies 13,14). 4. Conclusion Atomistic simulation techniques have been employed to investigate the the 5-layer Aurivillius phase A2Bi4Ti5O18 (A = Ba, Ca and Pb) that are relevant to potential ferroelectric applications. The simulation resulted in cell parameters for A2Bi4Ti5O18 (A = Ba, Ca, Pb) are of a = 5.494684 b = 5.494564 c = 48.578937 , a = 5.402632 b = 5.414576 c = 47.476578 and a = 5.471453 b = 5.445314 c = 49.563431 ; the lattice energy are 2428.067 eV; -2450.132 eV and -2487.437 eV. These paramteres agree well with those obtained from structure refinements from powder neutron diffraction data using the Rietveld method, which resulted in orthorhombic (space group B2cb) with cell parameters for A2Bi4Ti5O18 (A = Ba, Ca, Pb) are of a = 5.4988(3) b =5.4980(4) c = 50.352(1) , a = 5.4251(2) b = 5.4034(1) c = 48.486(1) and a = 5.4704(2)b = 5.4577(2) c = 49.643(1) . References 1. Aurivillius, B., Mixed Oxides With Layer Lattices, Ark. Kemi. 1, 499, 1949. 2. de Araujo, C.A.P., Cuchlaro, J.D., McMillan, L.D., Scott, M. and Scott, J.F., Fatigue-free ferroelectric capacitors with platinum electrodes, Nature (Lond.) 374, 627, 1995. 3. Ismunandar, Hunter, B.A. and Kennedy, B.J., Cation Disorder In The Ferroelectric Aurivillius Phase PbBi2Nb2O9: An Anomalous Dispersion X-Ray Diffraction Study, Solid State Ionics 112, 281, 1998. 4. Macquart, R., Kennedy, B.J., Hunter, B.A., Howard, C.J. and Shimakawa, Y., Structural

0.272(2) 0.246 (2) 0.8399 (2) 0.281(2) 0.247 (2) 0.1624 (2) Phase Transitions In The Ferroelectric Oxide SrBi2Ta2O9, Integrated Ferroelectric 44, 101, 2002. 5. Hervoches, C.H. and Lightfoot, P., Cation Disorder In Three-Layer Aurivillius Phases: Structural Studies Of Bi2-XSr2+XTi1-XNb2+XO12 (0 < X < 0.8) and Bi4-XLaxTi3O12 (X = 1 And 2), J. Solid State Chem. 153, 66, 2000. 6. Subbarao, E.C., Ferroelectric of PbBi2Nb2O9, SrBi2Nb2O9, BaBi2Nb2O9, J. Am. Ceram. Soc. 45, 564, 1962. 7. Subbarao, E.C., Crystal chemistry of mixed bismuth oxides with layer-type structure, J. Am. Ceram. Soc. 45, 166, 1962. 8. Aurivillius, B. and Fang, P.H., Ferroelectricity In The Compound Ba2Bi4Ti5O18, Phys. Rev. 126, 893, 1962. 9. Irie, H., Miyayama,M. and Kudo, T., Structure Dependence of Ferroelectric Properties of Bismuth Layer Structured Ferroelectric Single Crystals, J. Appl. Phys. 90, 4089, 2001. 10. Ismunandar, Kamiyama T, Hoshikawa A, Zhou Q, Kennedy B.J, Kubota Yand Kato K., Structural Studies of Five Layer Aurivillius Oxides: A2Bi4Ti5O18 (A = Ca, Sr, Ba and Pb), J. Solid State Chem. 177, 4188, 2004. 11. Ismunandar, Kamiyama T, Hoshikawa A, Zhou Q and Kennedy B.J, Structural Studies of Five Layer Aurivillius Oxides: A2Bi4Ti5O18 (A = Ca, Sr, Ba and Pb), J. Neutron Res. 13, 183, 2005. 12. Gale, J. D., GULP: A Computer Program for the Symmetry-Adapted Simulation, J. Chem. Soc., Faraday Trans., 93, 4, 629-637, 1997. 13. Pirovano, C., Islam, M.S., Vannier, R., Nomogrocki, G., Mairesse, G., Modelling the Crystal Structures of Aurivillius phases, Solid State Ionics, 140, 115-123, 2001. 14. Catlow C.R.A, in: Cheetham A.K, Day,P (Eds), Solid State Chemistry-Techniques, vol. 7; Clarendon Press, Oxford, Chap. 7, p.231, 1987.