Valence changes associated with the metal-insulator transition in Bi$_{1-x}$La$_x$NiO$_3$

TL;DR

This study investigates how La doping in BiNiO$_3$ affects its electronic structure, revealing a valence change in Ni from 2+ to 3+ and a transition from insulating to metallic behavior.

Contribution

It provides detailed spectroscopic evidence of valence changes and electronic structure evolution in La-doped BiNiO$_3$, highlighting the charge redistribution mechanisms.

Findings

Ni valence increases from 2+ to 3+ with La doping

La substitution induces metallic behavior in the compound

Spectral analysis confirms gradual Ni valence change

Abstract

Perovskite-type BiNiO$_3$ is an insulating antiferromagnet in which a charge disproportionation occurs at the Bi site. La substitution for Bi suppresses the charge disproportionation and makes the system metallic. We have measured the photoemission and x-ray absorption (XAS) spectra of Bi$_{1-x}$La$_{x}$NiO$_{3}$ to investigate how the electronic structure changes with La doping. From Ni $2p$ XAS, we observed an increase of the valence of Ni from 2+ toward 3+. Combined with the core-level photoemission study, it was found that the average valence of Bi remains $\sim 4+$ and that the Ni valence behaves as $\sim (2+x)+$, that is, La substitution results in hole doping at the Ni sites. In the valence-band photoemission spectra, we observed a Fermi cutoff for $x>0$, consistent with the metallic behavior of the La-doped compounds. The Ni $2p$ XAS, Ni $2p$ core-level photoemission, and valence-band photoemission spectra were analyzed by configuration-interaction cluster-model calculation, and the spectral line shapes were found to be consistent with the gradual Ni$^{2+} \to$ Ni$^{3+}$ valence change.