Pressure Tuning the Jahn-Teller Transition Temperature in NaNiO2.

Abstract

NaNiO2 is a layered material consisting of alternating layers of NaO6 and Jahn–Teller-active NiO6 edge-sharing octahedra. At ambient pressure, it undergoes a broad phase transition from a monoclinic to rhombohedral structure between 465 and 495 K, associated with the loss of long-range orbital ordering. In this work, we present the results of a neutron powder diffraction study on powdered NaNiO2 as a function of pressure and temperature from ambient pressure to ∼5 GPa between 290 and 490 K. The 290 and 460 K isothermal compressions remained in the monoclinic phase up to the maximum pressures studied, whereas the 490 K isotherm was mixed-phase throughout. The unit-cell volume was fitted to a second-order Birch–Murnaghan equation of state, where B = 119.6(5) GPa at 290 K. We observe at 490 K that the fraction of the Jahn–Teller-distorted phase increases with pressure, from 67.8(6)% at 0.71(2) GPa to 80.2(9)% at 4.20(6) GPa. Using this observation, in conjunction with neutron diffraction measurements at 490 K on removing pressure from 5.46(9) to 0.342(13) GPa, we show that the Jahn–Teller transition temperature increases with pressure. Our results are used to present a structural pressure–temperature phase diagram for NaNiO2. To the best of our knowledge, this is the first diffraction study of the effect of pressure on the Jahn–Teller transition temperature in materials with edge-sharing Jahn–Teller-distorted octahedra and the first variable-pressure study focusing on the Jahn–Teller distortion in a nickelate.