Identifying silicides via plasmon loss satellites in photoemission of the Ru-Si system

The phase and composition of several transition metal silicides are challenging to identify with common surface analysis techniques such as X-ray photoelectron spectroscopy (XPS). While silicide formation is concomitant with a distinct change in electronic structure, only minute changes in the main spectral features are observed for example for the family of Ru silicides. Here, the authors combine XPS, grazing-incidence X-ray diffraction, and density functional theory calculations to demonstrate that the characteristic excitation energies of plasmons in Ru and its silicides are a sensitive and easily accessible descriptor that reflects the change in electronic structure upon the formation of specific silicides in the XPS spectra. Electron energy loss satellites are reported to shift by more than 4 eV upon the formation of Ru silicide, by 1.1 eV between RuSi and Ru₂Si₃ and by 1.9 eV across the measured range of silicide layers, making these changes accessible even for basic experimental equipment. In the context of literature on metal silicides and electron energy loss spectroscopy, this approach is considered promising as a general pathway to enhance the chemical sensitivity of surface spectroscopy methods.