Tetragonal BaCoO$_3$: A Co$^{4+}$ Ferromagnetic Mott Insulator with Inverted Spin Crossover

TL;DR

This paper reports the synthesis and characterization of a new tetragonal phase of BaCoO₃ with a rare Co⁴⁺ valence state, exhibiting an unusual inverted spin crossover and ferromagnetic order, advancing understanding of spin-state transitions in cobalt oxides.

Contribution

It introduces a novel high-pressure synthesized tetragonal BaCoO₃ phase with unique spin crossover behavior and detailed structural, electronic, and magnetic characterization.

Findings

Revealed a rare Co⁴⁺ valence state in BCT-BaCoO₃.

Observed an inverted spin crossover from low-spin to high-spin state.

Demonstrated ferromagnetic ordering below 107 K.

Abstract

The interplay between crystal electric field splitting of d states and Hund's rule exchange energy in cobalt-based perovskites offers a promising avenue for inducing spin-state transitions. This study reports a new body-centered tetragonal (BCT) phase of BaCoO$_3$ (BCT-BaCoO$_3$), synthesized under high pressure (15 GPa) and high temperature (1200 {\deg}C) conditions. BCT-BaCoO$_3$ adopts a double perovskite structure of EuTiO$_3$-type (space group I4/mcm, #140), confirmed by high-resolution scanning transmission electron microscopy. X-ray photoelectron spectroscopy reveals a rare Co$^{4+}$ valence state. Magnetization and X-ray absorption measurements reveal a low-spin to high-spin transition that takes place between 200 and 300 K. While spin crossovers are relatively common among common oxides, the one observed in BCT-BaCoO$_3$ is remarkable in that it proceeds in the opposite direction from conventional spin transitions. BCT-BaCoO$_3$ exhibits a low-spin (S = 1/2) state at high temperatures and transitions to a high-spin (S = 5/2) state at low temperatures. Within the high-spin state, hard ferromagnetic order onsets at T$_C$ = 107 K. Electrical resistivity indicates weak magnetoresistance and insulating behavior. Overall, BCT-BaCoO$_3$ presents an exceptional model for the exploration of spin-state transitions and the study of Co spin states in cobalt-based perovskites.