Correlation between dielectric constant and chemical structure of sodium silicate glasses

The chemical structure of sodium aluminosilicate glasses is determined by high resolution x-ray photoelectron spectroscopy ~XPS! as silicon is gradually replaced by aluminum. A well-defined chemical state is found for silicon, aluminum, and sodium atoms, while three different environments are identified for oxygen atoms corresponding to Si–O–Si, Si–O–Al, and Si–O–Na bonds. The binding energy of Na 1s photoelectrons increases significantly with increasing aluminum substitution while that of Al 2p and components of O 1s photoelectrons remains approximately constant. Thus, the ionicity of sodium increases with aluminum amount, but the over all electron density around silicon, aluminum, and different types of oxygen atoms remains unchanged. The dielectric constant of the glasses increases with increasing aluminum substitution. It is analyzed in terms of the polarizabilities of constituent structural units, viz., silicon tetrahedra, nonbridging oxygen–sodium ion pairs, and aluminum tetrahedron–sodium ion pairs. The electronic polarizability of oxygen ions depends linearly on their negative charge and can be correlated to the O 1s XPS binding energy. The ionic polarizability of sodium ions increases with an increasing aluminum amount, and correlates directly with the Na 1s XPS binding energy. © 1996 American Institute of Physics. @S0021-8979~96!06015-X#