The origin of ferroelectricity, polarization and high resistivity in Aurivillius CaBi2B2O9 (B = Ta, Nb)

Abstract

Aurivillius layered oxides are important candidates for high-temperature ferroelectric and piezoelectric application. In this work, we combine group theoretic analysis with first-principles calculations to systematically investigate the origin of ferroelectric phase transition, polarization, piezoelectric response, and intrinsic electrical insulation of the two-layer Aurivillius ferroelectrics CaBi$_{2}$B$_{2}$O$_{9}$ (B = Ta, Nb). The results show that the \textit{A2$_1$am} ferroelectric phase arises from the cooperative condensation of a polar mode and nonpolar oxygen octahedral rotation/tilting modes, whose the $Γ_5^-$X$_2^+$X$_3^-$ trilinear coupling substantially lowers the total energy and deepens the ferroelectric potential well. The spontaneous polarization and anisotropic piezoelectric response are governed primarily by the cooperative displacements of the Bi$_{2}$O$_{2}$ layers and Ta/NbO$_{6}$ octahedra, with Bi ions providing an indispensable contribution to both responses. More importantly, the polar distortion can be traced to the relative in-plane displacement between adjacent the Bi$_{2}$O$_{2}$ layer and the perovskite-like block. Because this displacement is intrinsic to the alternating Bi$_{2}$O$_{2}$/perovskite-block stacking topology and is independent of the number of perovskite layers, we identify interlayer sliding as a general, layer-number-independent structural mechanism for ferroelectricity in Aurivillius oxides. Our findings establish a unified microscopic picture linking structural distortions, ferroelectric polarization, piezoelectric response, and electronic insulation in CaBi$_{2}$B$_{2}$O$_{9}$ (B = Ta, Nb), and provide theoretical guidance for designing layered ferroelectric oxides with high Curie temperatures and robust insulating behavior.