Structural Distortions and Uniaxial Negative Thermal Expansion in the Polar Dion–Jacobson Oxide RbNdTa₂O₇

We provide deeper insight into the crystal structures, sequential structural phase transitions (I2cm → Cmce → I4/mcm → P4/mmm), thermal expansion, and electronic properties of the n = 2 Dion–Jacobson polar oxide RbNdTa₂O₇, through X-ray powder diffraction, neutron powder diffraction, Raman studies, and density functional theory calculations. We observed a uniaxial negative thermal expansion (NTE) across the first-order transition, I2cm → Cmce, where the unit cell contracts along the c-axis, which is driven by a contraction of the NdTa₂O₆layer. This NTE occurs within the temperature range of the first-order phase transition and contrasts with the corkscrew mechanism typically observed in Ruddlesden–Popper phases. In RbNdTa₂O₇, the I2cm (hybrid improper ferroelectric) → Cmce (antipolar) transition involves crucial changes in the bond lengths of Nd and Ta polyhedra, coupled with polar to antipolar displacement of the Nd ions, leading to a net contraction in the NdTa₂O₆layer along the c-axis, while preserving the overall octahedral tilting magnitude. This transition highlights the intricate interplay between the Nd and Ta coordination and the associated TaO₆distortions. Temperature-dependent Raman spectra analysis further confirms the first-order structural transition and associated NTE, providing evidence for increased bond stiffness across this transition. Additionally, using neutron powder diffraction, we have determined that the transition I4/mcm → P4/mmm occurs at approximately 1150 K. Finally, we have calculated from DFT + U, the partial density of states, the energy bandgaps, and effective masses of the charge carriers of the polar ground structure.