First-principles lattice dynamics and thermodynamic properties of pre-perovskite PbTiO 3

Meng Jun Zhou, Yi Wang, Yanzhou Ji, Zi Kui Liu, Long Qing Chen, Ce Wen Nan

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7 Scopus citations


It was recently found that nanowires of PbTiO 3 synthesized through an intermediate pre-perovskite phase exhibit enhanced spontaneous polarization. Here we investigated the pre-perovskite PbTiO 3 (PP-PTO) nanowire phase at finite temperatures employing first-principles quasiharmonic calculations. We calculated its band gap, phonon dispersions, phonon density of states, Debye temperature, and thermodynamic properties. The corresponding calculations for cubic and tetragonal PbTiO 3 were also carried out for comparison. In the current calculations, the amount of imaginary frequencies associated with the ideal cubic PTO structure, i.e., a cubic cell shape with ion positions at the ideal cubic perovskite lattice sites, was decreased to a negligible level by employing a constrained cubic structure, a structure with the same cubic cell shape as the ideal cubic PTO structure but allowing the ion positions to relax to thermodynamically more stable tetragonal positions at 0 K. In contrast to the general observation that a higher volume phase would have relatively higher entropy, it is found that the PP-PTO phase possesses the lowest entropy while having the largest volume compared to cubic and tetragonal PbTiO 3 phases. Furthermore, the temperature-pressure phase diagram for the three PbTiO 3 phases was obtained, which demonstrates that PP-PTO could be stabilized under a large volume or a negative pressure. This study provides insights to experimentally synthesizing the PP-PTO phase and to better understanding its phase transition into the converted tetragonal PbTiO 3 nanowires with enhanced piezoelectric and ferroelectric properties.

Original languageEnglish (US)
Pages (from-to)146-153
Number of pages8
JournalActa Materialia
StatePublished - Jun 1 2019

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Polymers and Plastics
  • Metals and Alloys


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