Chemical Shifts of Silicon X‐ray Photoelectron Spectra by Polymerization Structures of Silicates

The binding energy of Si 2 p electrons and the kinetic energy of the Si(KLL) X‐ray‐excited state were measured by using X‐ray photoelectron spectroscopy (XPS) and X‐ray Auger electron spectroscopy (XAES), respectively, for silicates with SiO 4 tetrahedra of various polymerization types. The resulting Si 2 p XPS binding energies varied from 101.3 eV in merwinite (monomeric structure) to 103.4 eV in quartz and cristobalite (three‐dimensional framework structure). A clear chemical‐shift relation was observed, relating the polymerization structures of SiO 4 tetrahedra to the plots of their Si 2 p XPS binding energy versus the kinetic energy of their Si(KLL) XAES spectra. Thus, the structural state of the surface silicates in various substances can be deduced from this chemical‐shift relationship.