Takanori Matsuda

Enhancement of tetragonal anisotropy and stabilisation of the tetragonal phase by Bi/Mn-double-doping in BaTiO 3 ferroelectric ceramics

To stabilise ferroelectric-tetragonal phase of BaTiO3, the double-doping of Bi and Mn up to 0.5 mol% was studied. Upon increasing the Bi content in BaTiO3:Mn:Bi, the tetragonal crystal-lattice-constants a and c shrank and elongated, respectively, resulting in an enhancement of tetragonal anisotropy, and the temperature-range of the ferroelectric tetragonal phase expanded. X-ray absorption fine structure measurements confirmed that Bi and Mn were located at the A(Ba)-site and B(Ti)-site, respectively, and Bi was markedly displaced from the centrosymmetric position in the BiO12 cluster. This A-site substitution of Bi also caused fluctuations of B-site atoms. Magnetic susceptibility measurements revealed a change in the Mn valence from +4 to +3 upon addition of the same molar amount of Bi as Mn, probably resulting from a compensating behaviour of the Mn at Ti4+ sites for donor doping of Bi3+ into the Ba2+ site. Because addition of La3+ instead of Bi3+ showed neither the enhancement of the tetragonal anisotropy nor the stabilisation of the tetragonal phase, these phenomena in BaTiO3:Mn:Bi were not caused by the Jahn-Teller effect of Mn3+ in the MnO6 octahedron, but caused by the Bi-displacement, probably resulting from the effect of the 6 s lone-pair electrons in Bi3+.

Effects of poling termination and aging process on piezoelectric properties of Mn-doped BaTi0.96Zr0.04O3 ceramics

The effects of poling termination and aging process on the piezoelectric properties at room temperature of 1 mol % Mn-doped Ba(Ti0.96Zr0.04)O3 ceramics with orthorhombic structure have been investigated. It is expected that the substitution of accepter Mn into the Ti0.96Zr0.04 site will result in a defect dipole with an oxygen vacancy and generate an internal field (Ed) in 1 mol % Mn-doped Ba(Ti0.96Zr0.04)O3 ceramics. In order to investigate the effect of the rearrangement of defect dipoles on the piezoelectric properties, the following two investigations have been performed. One is on the relationship between the piezoelectric properties and the change in the poling-termination temperature (TP) around the orthorhombic–tetragonal temperature (TOT). The result shows that piezoelectric properties are related to spontaneous polarizations, and that the rearrangement of defect dipoles is small. The other is on the influence of aging treatment at 70 °C for 24 h on the piezoelectric properties. Above TOT, the piezoelectric properties are almost the same, independent of the TP of the specimen. This result suggests that the change in piezoelectric properties is due to a change in the domain in spontaneous polarizations and that the rearrangement of defect dipoles is also small. The result of domain observation reflection electron microscopy supports the rearrangement of spontaneous polarizations during the aging process.