Complex Structural Phase Transitions of the Hybrid Improper Polar Dion–Jacobson Oxides RbNdM₂O₇ and CsNdM₂O₇ (M = Nb, Ta)

Recently, there has
been much interest in hybrid improper ferroelectrics
materials that adopt polar, ferroelectric structures due to a complex
tilting and twisting of the MO6 octahedra which constitute
perovskite and related structures. Using a combination of synchrotron
X-ray powder diffraction (XRD) and high-resolution neutron powder
diffraction data, the temperature-dependent phase transitions of a
series of n = 2 Dion–Jacobson oxides have been investigated. RbNdM2O7 undergoes a transition from a polar, a–a–c+/–(a–a–c+) distorted I2cm phase to an antipolar, a–b0c–/–(a–b0)c– distorted Cmca phase at T = 790
and 500 K for M = Nb and Ta, respectively. There is a subsequent transition
to an a0a0c–/a0a0–c– distorted I4/mcm structure at
865 and 950 K for M = Nb and Ta, respectively, before a transition
to the undistorted P4/mmm aristotype
structure. In contrast, CsNdM2O7 undergoes a
transition from a polar, a–a–c+ distorted P21am structure to an antipolar, a–b0c– distorted C2/m phase at T = 625 and 330 K for M = Nb
and Ta, respectively, with a subsequent phase transition to the undistorted P4/mmm aristotype structure at 800 and
820 K for M = Nb and Ta, respectively. A plot of Tc against the relative stability of the 4 polar Dion–Jacobson
phases compared to the corresponding aristotype P4/mmm structures (calculated from first-principles
density functional theory (DFT)) yields a strong linear relation,
suggesting that Tc is not proportional
to the enthalpy change at the ferroelectric phase transition.