XPS investigation of Mn valence in lanthanum manganite thin films under variation of oxygen content

The question whether LaMnO3 accepts doping with tetravalent cations such as cerium and thus allows the preparation of electron-doped mixed-valent lanthanum manganites has been discussed controversially so far. Against the background of this problem, we present a comparative x-ray photoemission (XPS) study of epitaxial La0.7Ce0.3MnO3 (LCeMO) and La0.7Ca0.3MnO3 (LCMO) thin films. We focus on the exchange splitting of the Mn 3s core level peak, which is a direct indicator of the Mn valence and allows us to quantify the Mn valence in the outermost 3 nm of the films. We demonstrate that, depending on the oxygen content, the Mn valence can be tuned between a mixed Mn3+/4+ state and a mixed Mn2+/3+ state in both the LCeMO and the LCMO film. The oxygen content was varied by heating in ultrahigh vacuum for deoxygenation and in an oxygen atmosphere for reoxidation. In the LCeMO film, the deoxygenation not only changes the Mn valence, but also the Ce valence is driven from the 4+ towards the 3+ state.