Abstract
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 RbNdTa(2)O(7), 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 NdTa(2)O(6) layer. 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 RbNdTa(2)O(7), 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 NdTa(2)O(6) layer 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 TaO(6) distortions. 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.