Antiferroelectric and antiferrodistortive phase transitions in Ruddlesden-Popper Pb2TiO4 from First-Principles

  • Xu, Tao ;
  • Shimada, Takahiro ;
  • Wang, Jie ;
  • Kitamura, Takayuki
  • Received : 2016.01.24
  • Accepted : 2016.03.08
  • Published : 2016.07.25


This work employed density functional theory to investigate the structural and ferroelectric properties of the Ruddlesden-Popper (RP) phase of lead titanate, $Pb_2TiO_4$, as well as its phase transitions with epitaxial strain. A wealth of novel structural instabilities, which are absent in the host $PbTiO_3$ material, were identified in the RP phase through phonon soft-mode analysis. Our calculations showed that the ground state of $Pb_2TiO_4$ is antiferroelectric, distinct from the dominant ferroelectric phase in the corresponding host material. In addition, applied epitaxial strain was found to play a key role in the interactions among the instabilities. The induction of a sequence of antiferroelectric and antiferrodistortive (AFD) phase transitions by epitaxial strain was demonstrated, in which the ferroic instability and AFD distortion were cooperative rather than competitive, as is the case in the host $PbTiO_3$. The RP phase in conjunction with strain engineering thus represents a new approach to creating ferroic orders and modifying the interplay among structural instabilities in the same constituent materials, enabling us to tailor the functionality of perovskite oxides for novel device applications.


ferroelectrics;Ruddllesden-Popper phase;antiferroelectricity;strain;first-principles


  1. Benedek, N.A. and Fennie, C.J. (2011), "Hybrid improper ferroelectricity: a mechanism for controllable polarization-magnetization coupling", Phys. Rev. Lett., 106, 107204.
  2. Benedek, N.A. and Fennie, C.J. (2013), "Why are there so few Perovskite Ferroelectrics?", J. Phys. Chem. C., 117, 13339-13349.
  3. Birol, T., Benedek N.A. and Fennie C.J. (2011) "Interface control of mergent Ferroic order in Ruddlesden-Popper Srn+1TinO3n+1", Phys. Rev. Lett., 107, 257602.
  4. Blochl, P.E. (1994), "Projector augmented-wave method", Phys. Rev. B., 50, 17953.
  5. Ceperley, D.M. and Alder, B.J. (1980), "Ground state of the Electron Gas by a Stochastic method", Phys. Rev. Lett., 45, 566.
  6. Fennie, C. J. and Rabe, K. M. (2005) "First-principles investigation of ferroelectricity in epitaxially strained Pb2TiO4", Phys. Rev. B., 71, 100102.
  7. Fobes, D., Yu, M.H., Zhou, M., Hooper, J., O'Connor, C.J., Rosario, M. and Mao, Z.Q. (2007), "Phase diagram of the electronic states of trilayered ruthenate Sr4Ru3O10", Phys. Rev. B., 75, 094429.
  8. Glazer, A.M. (1972), "The classification of tilted octahedra in perovskites", Acta Crystallogr. B., 28, 3384-3392.
  9. Harris, A.B. (2011), "Symmetry analysis for the Ruddlesden-Popper systems Ca3Mn2O7and Ca3Ti2O7", Phys. Rev. B., 84, 064116.
  10. Kresse, G. and Hafner, J. (1993), "Ab initio molecular dynamics for liquid metals", Phys. Rev. B., 47, 558.
  11. Lines, M.E. and Glass, A.M. (1997), "Principles and applications of Ferroelectrics and related materials", (Oxford University Press, New York).
  12. Mabud, S.A. and Glazer, A.M. (1979), "Lattice parameters and birefringence in PbTiO3 single crystals", J. Appl. Crystallogr., 12, 49-53.
  13. Maeno,Y., Hashimoto, H., Yoshida, K., Nishizaki, S., Fujita, T., Bednorz, J.G. and Lichtenberg, F. (1994), "Superconductivity in a layered perovskite without copper", Nature (London), 372, 532-534.
  14. Monkhorst, H.J. and Pack, J.D. (1976), "Special points for Brillouin-zone integrations", Phys. Rev. B., 13, 5188.
  15. Nakhmanson, S.M., Rabe, K.M. and Vanderbilt, D. (2005), "Polarization enhancement in two-and three-component ferroelectric superlattices," Appl. Phys. Lett., 87, 102906.
  16. Oh, Y.S., Luo, X., Huang, F.T., Wang, Y., Cheong, S.W. (2015), "Experimental demonstration of hybrid improper ferroelectricity and the presence of abundant charged walls in (Ca, Sr)3Ti2O7 crystals", Nat. Mater., 14, 407-413.
  17. Perdew, J.P., Ruzsinszky, A., Csonka, G.I., Vydrov, O.A., Scuseria, G.E., Constantin, L.A., Zhou, X. and Burke, K. (2008), "Restoring the Density-Gradient Expansion for exchange in solids and surfaces", Phys. Rev. Lett., 100, 136406.
  18. Perry, R.S., Galvin, L.M., Grigera, S.A., Capogna, L., Schofield, A.J., Mackenzie, A.P., Chiao, M., Julian, S.R., Ikeda, S.I., Nakatsuji, S., Maeno, Y. and Pfleiderer, C. (2001), "Metamagnetism and critical fluctuations in high quality single crystals of the Bilayer Ruthenate Sr3Ru2O7", Phys. Rev. Lett., 86, 2661.
  19. Schaak, R.E. and Mallouk, T.E. (2002), "Perovskites by design: a toolbox of solid-state reactions", Chem. Mater., 14, 1455-1471.
  20. Shimada, T., Ueda, T., Wang, J. and Kitamura, T. (2013), "Hybrid Hartree-Fock density functional study of charged point defects in ferroelectric PbTiO3", Phys. Rev. B., 87, 174111.
  21. Shimada, T., Wang, J., Ueda, T., Uratani, Y., Arisue, K., Mrovec, M., Elsasser, C. and Kitamura, T. (2015), "Multiferroic grain boundaries in oxygen-deficient Ferroelectric lead Titanate", Nano Lett., 15, 27-33.
  22. Xu, T., Shimada, T., Araki, Y., Wang, J. and Kitamura, T. (2016), "Multiferroic domain walls in ferroelectric PbTiO3 with oxygen deficiency", Nano Lett., 16, 454-458.


Supported by : JSPS