Properties of BaTiO3/BaZrO3 ferroelectric superlattices with competing instabilities

Abstract

Properties of (BaTiO3)1/(BaZrO3)n ferroelectric superlattices (SLs) with n = 1-7 grown in the [001] direction are calculated from first principles within the density functional theory. It is revealed that the quasi-two-dimensional ferroelectricity occurs in these SLs in the barium titanate layers with a thickness of one unit cell; the polarization is oriented in the layer plane and weakly interacts with the polarization in neighboring layers. The ferroelectric ordering energy and the height of the barrier separating different orientational states of polarization in these SLs are sufficiently large to provide the formation of an array of independent polarized planes at 300 K. The effect of the structural instability on the properties of SLs is considered. It is shown that the ground state is a result of simultaneous condensation of the Γ15 polar phonon and phonons at the M point (for SLs with even period) or at the A point (for SLs with odd period); it is a polar structure with out-of-phase rotations of the octahedra in neighboring layers, in which highly polarized layers are spatially separated from the layers with strong rotations. The competition between the ferroelectric and structural instabilities in biaxially compressed SLs manifests itself in that the switching on of the octahedra rotations leads to an abrupt change of the polarization direction and can cause an improper ferroelectric phase transition to occur. It was shown that the experimentally observed zcomponent of polarization in the SLs can appear only as a result of the mechanical stress relaxation.

Piezoelectric properties of II–IV/I–V and II–IV/III–III ferroelectric perovskite superlattices

“…It can be seen that in addition to the instability at the Γ point, the instabilities also appear at the X, R, and Z points of the Brillouin zone. We have already encountered a similar situation in KNbO 3 /KTaO 3 [7] and BaTiO 3 /BaZrO 3 [9] SLs.…”

Piezoelectric properties of ferroelectric perovskite superlattices with polar discontinuity

“…It is seen that in addition to the instability at the Γ point, the instabilities also appear at the X, R, and Z points of the Brillouin zone. We have already encountered a similar situation in KNbO 3 /KTaO 3 [42] and BaTiO 3 /BaZrO 3 [44] SLs. xy-polarized displacements of Bi and oxygen atoms lying in the same xy plane are stronger; this displacement pattern is characteristic of BiScO 3 .…”

Repolarization of Ferroelectric Superlattices BaZrO3/BaTiO3

“…The main factors determining the properties of ferroelectric superlattices and the possibility of their change are mechanical stresses caused by the mismatch of sizes of the elementary cells of components of the superlattice which are in contact with each other and with the substrate. The stretching of BaTiO 3 layers in BaTiO 3 /BaZrO 3 superlattices due to epitaxial conjugation with BaZrO 3 layers, having a higher lattice parameter, should stabilize polarization in BaTiO 3 along the substrate.However, as shown in 25 , the presence of structural instability in BaZrO 3 under rotations of octahedra and its competition with ferroelectric instability qualitatively change the situation.…”