Multiplet XPS analysis of the Mn 2pfor Mn₃O₄thin films

In this work, we performed a detailed analysis of the x-ray photoemission spectroscopy (XPS) of the Mn 2ppeak for Mn₃O₄(001) thin films. This is a challenging task since Mn₃O₄is composed of two different cations, Mn²⁺at tetrahedral and Mn³⁺at octahedral sites, which both contribute to the XPS spectra. The oxide spectra consist of many multiplets arising from the angular momentum coupling of the open Mn 2pand 3dshells, thus increasing the spectrums' complexity. Moreover, the energy spacing and intensities of the different multiplets also reflect the covalent mixing between Mn 3dand O 2pshells. However, we show that a detailed analysis, which provides relevant information about the cations in the oxide structure, is possible. We prepared experimentally different Mn₃O₄films on Au(111), and their structure was monitored with the diffraction pattern obtained with low-energy electron diffraction. The Mn 2pspectra were fit, guided by cluster model theoretical predictions, and checked for films prepared at different oxygen partial pressures. Therefore, we could observe the Mn²⁺and Mn³⁺cations' relative concentration in the Mn 2pmains peaks.