Local structure and redox state of copper in tellurite glasses

The local glass structure of tellurite glasses containing CuO with the nominal composition x(CuO) · (1−x)(TeO₂), where x=0.10, 0.20, 0.30, 0.40, and 0.50, as well as the valence state of the copper ions have been investigated by X-ray photoelectron spectroscopy (XPS) and magnetization measurements. The Te 3d core level spectra for all glass samples show symmetrical peaks (Te 3d_5/2 and Te 3d_3/2) at essentially the same binding energies as measured for TeO₂ indicating that the chemical environment of the Te atoms in the glasses does not vary significantly with the addition of CuO. The O 1s spectra, however, show slight asymmetry for all glass samples which results from two contributions, one from the presence of oxygen atoms in the Te-O-Te environment (bridging oxygen BO) and the other from oxygen atoms in an Te-O-Cu environment (non-bridging oxygen NBO). The ratio of NBO to total oxygen was found to increase with CuO content and to be in good agreement with calculated values for the TeO₄ trigonal bipyramid structure. Moreover, the appearance of a satellite peak in the Cu 2p spectra provides definitive evidence for the presence of Cu²⁺ ions in these glass samples where the asymmetry and broadening of the Cu 2p_3/2 and Cu 2p_1/2 peaks are indicative of the presence of both Cu²⁺ and Cu⁺ ions. The relative concentration Cu²⁺ determined from XPS is in good qualitative agreement with the determinations of Cu²⁺ from magnetic susceptibility measurements on the same glass samples. Furthermore the susceptibility data follow a Curie-Weiss temperature-dependent behavior (χ=C/(T−θ)) with negative Curie temperatures indicating that the predominant magnetic interactions between the Cu²⁺-Cu²⁺ exchange pairs are antiferromagnetic in nature.