  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.

Strongly Correlated Electrons;Materials Science