Spin-state responses to light impurity doping in low-spin perovskite LaCoO$_{3}$

TL;DR

This study investigates how light impurity doping affects the spin states in low-spin LaCoO3, revealing that Ni doping induces a spin-state change and magnetic anisotropy, linked to chemical potential and Jahn-Teller activity.

Contribution

It demonstrates that Ni doping uniquely alters the spin state in LaCoO3 and proposes a model connecting chemical potential to spin-state changes, expanding understanding of impurity effects.

Findings

Ni doping induces a spin-state change and magnetic anisotropy.

Chemical potential influences the spin-state response to doping.

Jahn-Teller activity in Ni3+ contributes to magnetic cluster formation.

Abstract

We studied the spin-state responses to light impurity doping in low-spin perovskite LaCoO$_{3}$ (Co^3+: d^6) through magnetization and X-ray fluorescence measurements of single-crystal LaCo$_{0.99}$$M_{0.01}$O$_{3}$ ($M$ = Cr, Mn, Fe, Ni). In the magnetization curves measured at 1.8 K, a change in the spin-state was not observed for Cr, Mn, or Fe doping but was observed for Ni doping. Strong magnetic anisotropy along the [100] easy axis was also found in the Ni-doped sample. The fluorescence measurements revealed that the valences were roughly estimated to be Cr^3+, Mn^4+, Fe^(3+delta)+, and Ni^3+. From the observed chemical trends, we propose that the chemical potential is a key factor in inducing the change of the low-spin state. By expanding a model of the ferromagnetic spin-state heptamer generated by hole doping, we discuss the emergence of highly anisotropic ferromagnetic spin-state clusters induced by low-spin Ni^3+ with Jahn-Teller activity. We also discuss applicability of the present results to mantle materials and impurity-doped pyrites with Fe (d^6).