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Theoretical Investigation of The Cubic and Tetragonal Phases of The Pbtio Material
Theoretical Investigation of The Cubic and Tetragonal Phases of The Pbtio Material
Theoretical Investigation of The Cubic and Tetragonal Phases of The Pbtio Material
the PbTiO3 material
Ribeiro, R. A. P.1, R. F. Penteado1, S. R. Lázaro1, S. M. Tebcherani1
1
Universidade Estadual de Ponta Grossa, Campus Ponta Grossa, PR, Brazil
Materials with perovskita type crystalline structure are used on several technologies
applications. In particular, the PbTiO3 material has piezoelectric and ferroelectric proprierties
at room temperature with bandgap of 3.4 eV, in the tetragonal symmetry, spacial group
P4mm and lattice parameters a = 3.904 Å and c = 4.152 Å (c/a = 1.064), however there is a
tetragonal – cubic phase transition at 500oC, which change the piezoelectric and ferroelectric
properties. In the cubic phase the PbTiO3 material has spacial group Pm3m with lattice
parameter a = 3.865 Å. The present work show a theoretical investigation about structural
properties for PbTiO3 material in the tetragonal and cubic phases. This investigation was
carried out by Density Functional Theory (DFT) with B3LYP functional included in the
CRYSTAL06. Lead, titanium and oxygen atoms were described using [DB]31G, 86411
d(41) and 631(d) basis set, respectively. Theoretical results for lattice parameters in the
tetragonal phase were a = 3.805 Å and c = 4.361 Å , whereas for cubic phase the theoretical
lattice parameter found was a = 3.904 Å . All lattice parameters calculated are in according
with experimental results. From analysis of the theoretical results of density of states (DOS)
were obtained bandgap values of 3.613 eV and 3.045 eV for tetragonal and cubic phases,
respectively. Experimental bandgap results for these phases are found around 3.6 eV and 3.4
eV. This difference between theoretical and experimental results is consequence of the
methodology employed, the DFT methodology underestimates bandgap results. It is
observed that in both phases (tetragonal and cubic) the conduction band is dominated for the
Ti4+ cation, whereas the valence band is formed mainly for the oxygen atoms. Charge map
obtained for the tetragonal phase showed that there is more concentration of charges on
oxygen and lead atoms. To cubic phase also was observed more concentration of charges in
the oxygen atoms. This behavior show the difference of electronegativity among atoms.
Tetragonal volume is about 6% larger than cubic volume indicating that piezoelectric and
ferroelectric properties are influenced for the cell unit volume. It is possible conclued that the
structural change caused alteration in the energy levels modifying the bandgap of the PbTiO 3
material.
Keywords: PbTiO3, DFT, gap, perovskita, ferroelectricity, simulation.
Work supported by Cnpq and Araucária Fundation.
[1] S. Piskunov, E. Heifets, R. I. Eglits, G. Borstel, Comp. Mat. Sc. 29, Phys. Rev. Lett. 68,
(2004).
[2] S. M. Hosseini, T. Movlarooy, A. Kompany, Physica B. 391, (2007).
[3] P. Hermet, M. Veithen, Ph. Ghosez, Journal Phys. Cond. Matter, 21, (2009).
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