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

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

2005-05-26

arxiv.org/abs/cond-mat/0505646v1

Phys. Rev. B 72, 155103 (2005)

Physics

Condensed Matter

Strongly Correlated Electrons

6 pages, 7 figures

Scientific paper

10.1103/PhysRevB.72.155103

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.

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