Antiferromagnetic defect structure in LaNiO3−δ single crystals

Abstract

The origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, R${\mathrm{NiO}}_{3}$ (where $R$ is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of ${\mathrm{LaNiO}}_{3}$, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced $\mathrm{LaNi}{\mathrm{O}}_{3\ensuremath{-}\ensuremath{\delta}}$ crystals, we show that both antiferromagnetic and ferromagnetic phases with a N\'eel temperature of \ensuremath{\sim}152 K and a Curie temperature of \ensuremath{\sim}225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of $\mathrm{LaNi}{\mathrm{O}}_{3\ensuremath{-}\ensuremath{\delta}}$ single crystals; accordingly, the implications of our results for putative oxygen-stoichiometric ${\mathrm{LaNiO}}_{3}$ are discussed.