Spectroscopic investigations on trivalent ruthenium ions in ruthenium perovskite oxide thin films

Abstract

The $d^5$ electron configurations under the crystal field, spin-orbit coupling, and Coulomb interaction give rise to a plethora of profound ground states. Ruthenium perovskite oxides exhibit a number of unconventional properties yet the Ru$^{4+}$ state ($4d^4$) is usually stable in these materials. In this regard, Ru$^{3+}$ ions in perovskite materials are expected to be a mesmerising playground of $4d^5$ electron configurations. Here, we report measurements of x-ray photoemission spectroscopy on recently synthesized perovskite ruthenium oxide thin films, LaRuO$_3$ and NdRuO$_3$, whose valence state of the ruthenium ions is trivalent. We discuss correlation and spin-orbit effects from the valence-band spectra, in particular an additional peak structure around 3-5 eV, reminiscent of the so-called 3 eV peak observed in Sr$_2$RuO$_4$. Moreover, we find that the core-level spectra of these materials are quantitatively different from those in other ruthenates which possess Ru$^{4+}$ ions, e.g., SrRuO$_3$. We therefore argue that the core level spectra of LaRuO$_3$ and NdRuO$_3$ are peculiar to the Ru$^{3+}$ states.