Formation and migration of cation defects in the perovskite oxide LaMnO₃

Abstract

Atomistic simulation techniques have been employed to investigate the energetics of cation formation and migration in cubic, rhombohedral and orthorhombic LaMnO₃. The calculations suggest that for rhombohedral and orthorhombic lanthanum manganite, oxidative nonstoichiometry leads to the formation of cation vacancies on both La and Mn sites, though tending towards more La vacancies. The activation energy for lanthanum vacancy migration was found to increase with departure from cubic perovskite symmetry in the order: cubic<rhombohedral<orthorhombic. A number of different pathways for manganese vacancy migration were examined. The lowest energy pathway was found to be a curved path between Mn sites that are adjacent along the <100>_cubic directions. Calculated migration energies for this path also increased with distortion from the cubic form. The effect of composition on cation migration energies was also examined.

References

1. G. H. Jonker and J. H. Van Santen, Physica, 1950, 16, 337.
2. N. Q. Minh, J. Am. Ceram. Soc., 1993, 76, 563.
3. R. M. von Helmholt, J. Wecker, B. Holzapfel, L. Schultz and K. Samwer, Phys. Rev. Lett., 1993, 71, 2331.
4. S. Jin, T. H. Tiefel, M. McCormack, R. A. Fastnacht, R. Ramesh and L. H. Chen, Science, 1994, 264, 413.
5. J. H. Kuo, H. U. Anderson and D. M. Sparlin, J. Solid State Chem., 1989, 83, 52.
6. H. Tagawa, J. Mizusaki, H. Nambu, C. Nakao, H. Takai and H. Minamiue, in Ceramic Oxygen Ion Conductors and Their Technological Applications, British Ceramic Proc. vol. 56, The Institute of Materials, London, 1996, p. 113.
7. B. C. Tofield and W. R. Scott, J. Solid State Chem., 1974, 10, 183.
8. J. A. M. van Roosmalen, E. H. P. Cordfunke, R. B. Helmholdt and H. W. Zandberg, J. Solid State Chem., 1994, 110, 100.
9. J. F. Mitchell, D. N. Argyriou, C. D. Potter, D. G. Hinks, J. D. Jorgensen and S. D. Bader, Phys. Rev. B, 1996, 54, 6172.
10. J. A. Alonso, M. J. Martínez-Lope, M. T. Casais, J. L. MacManus-Driscoll, P. S. I. P. N. de Silva, L. F. Cohen and M. T. Fernández-Díaz, J. Mater. Chem., 1997, 7, 2139.
11. Q. Huang, A. Santoro, J. W. Lynn, R. W. Erwin, J. A. Borchers, J. L. Peng and R. L. Greene, Phys. Rev. B, 1997, 55, 14987.
12. K. Katayama, T. Ishihara, H. Ohta, S. Takeuchi, Y. Esaki and E. Inukai, J. Ceram. Soc. Jpn. Int. Ed., 1989, 97, 1324.
13. A. Hammouche, E. Siebert and A. Hammou, Mater. Res. Bull., 1989, 24, 367.
14. J. A. M. van Roosmalen, E. H. P. Cordfunke and J. P. P. Huijsmans, Solid State Ionics, 1993, 66, 285.
15. J. W. Stevenson, P. F. Hallman, T. R. Armstrong and L. A. Chick, J. Am. Ceram. Soc., 1995, 78, 507.
16. J. Wolfenstine, K. C. Goretta, R. E. Cook and J. L. Routbort, Solid State Ionics, 1996, 92, 75.
17. A. Weber, R. Männer, B. Jobst, M. Schiele, H. Cerva, R. Waser and E. Ivers-Tiffée, in Proc. 17th Risø Int. Symp. Mater. Sci., High Temperature Electrochemistry: Ceramics and Metals, ed. F. W. Poulsen, N. Bonanos, S. Linderoth, M. Mogensen, and B. Zacharau-Christiansen, Risø National Laboratory, Roskilde, Denmark, 1996, p. 473.
18. J. D. Gale, J. Chem. Soc., Faraday Trans., 1997, 93, 629.
19. Computer Simulation of Solids, ed. C. R. A. Catlow and W. C. Mackrodt, Lecture Notes in Physics 166, Springer-Verlag, Berlin, 1982.
20. C. R. A. Catlow, in Solid State Chemistry—Techniques, ed. A. K. Cheetham and P. Day, Clarendon Press, Oxford, 1987, p. 231.
21. B. G. Dick and A. W. Overhauser, Phys. Rev., 1958, 112, 603.
22. M. Cherry, M. S. Islam and C. R. A. Catlow, J. Solid State Chem., 1995, 118, 125.
23. B. Ammundsen, J. Rozière and M. S. Islam, J. Phys. Chem., B, 1997, 101, 8156.
24. A. Wold and R. J. Arnott, J. Phys. Chem. Solids, 1959, 9, 176.
25. J. Rodríguez-Carvajal, M. Hennion, F. Moussa, A. H. Moudden, L. Pinsard and A. Revcolevschi, Phys. Rev. B, 1998, 57, R3189.
26. M. S. Islam and L. J. Winch, Phys. Rev. B, 1995, 52, 10510.
27. A. Chainani, M. Mathew and D. D. Sarma, Phys. Rev. B, 1993, 47, 15397.
28. CRC Handbook of Chemistry and Physics, ed. R. C. Weast, M. J. Astle and W. H. Beyer, CRC Press, Boca Raton, Florida, 64th edn., 1983–1984.
29. J. H. Harding and N. J. Pyper, Philos. Mag. Lett., 1995, 71, 113.
30. S. D'Arco and M. S. Islam, Phys. Rev. B, 1997, 55, 3141.
31. J. A. M. van Roosmalen, P. van Vlaanderen, E. H. P. Cordfunke, W. L. IJdo and D. J. W. IJdo, J. Solid State Chem., 1995, 114, 516.
32. J. A. Kilner and R. J. Brook, Solid State Ionics, 1982, 6, 237.
33. H. W. King, K. M. Castelliz, G. J. Murphy and W. Manuel, J. Can. Ceram. Soc., 1982, 51, 1 Quoted by van Roosmalen et al.³¹.
34. R. D. Shannon, Acta Crystallogr., Sect. A, 1976, 32, 751.
35. T. Akashi, M. Nanko, T. Maruyama, Y. Shiraishi and J. Tanabe, J. Electrochem. Soc., 1998, 145, 2090.
36. T. Horita, M. Ishikawa, K. Yamaji, N. Sakai, H. Yokokawa and M. Dokiya, Solid State Ionics, 1998, 108, 383.
37. H. Schmalzried, Chemical Kinetics of Solids, VCH, Weinheim, 1995, p. 183.
38. R. A. De Souza and J. A. Kilner, Solid State Ionics, 1998, 106, 175.