First-principles study of PbTiO$_3$ under uniaxial strains and stresses

Abstract

The behavior of PbTiO$_3$ under uniaxial strains and stresses is investigated from first-principles calculations within density functional theory. We show that irrespectively of the uniaxial mechanical constraint applied, the system keeps a purely ferroelectric ground-state, with the polarization aligned either along the constraint direction ($FE_z$ phase) or along one of the pseudo-cubic axis perpendicular to it ($FE_x$ phase). This contrasts with the cases of isotropic or biaxial mechanical constraints for which novel phases combining ferroelectic and antiferrodistortive motions have been previously reported. Under uniaxial strain, PbTiO$_3$ switched from a $FE_x$ ground state under compressive strain to $FE_z$ ground-state under tensile strain, beyond a critical strain $\eta_{zz}^c \approx +1$\%. Under uniaxial stress, PbTiO$_3$ exhibits either a $FE_x$ ground state under compression ($\sigma_{zz} < 0$) or a $FE_z$ ground state under tension ($\sigma_{zz} > 0$). Here, however, an abrupt jump of the structural parameters is also predicted under both compressive and tensile stresses at critical values $\sigma_{zz} \approx$ $+2$ GPa and $- 8$ GPa. This behavior appears similar to that predicted under negative isotropic pressure and might reveal practically useful to enhance the piezoelectric response in nanodevices.