Nonlinear Optical Properties of TeO2-Based Glasses: MOx-TeO2 (M = Sc, Ti, V, Nb, Mo, Ta, and W) Binary Glasses

The third-order nonlinear optical susceptibilities, X⁽³⁾, of TeO₂-based glasses containing transition metal oxides (M = Sc₂O₃, TiO₂, V₂O₅, Nb₂O₅, MoO₃, Ta₂O₅, and WO₃) glasses have been measured by the third harmonic generation (THG) method in order to investigate the effect of the empty d-orbital contributions to the third-order nonlinear optical susceptibilities. It is found that the addition of TiO₂, Nb₂O₅, and WO₃ to TeO₂ glass increases the X⁽³⁾ value as well as the refractive index, while others decrease both of them. The positive effect of the TiO₂, Nb₂O₅, or WO₃, on the X⁽³⁾ of TeO₂ glass was interpreted in terms of the cationic empty d-orbital contribution. There is an almost linear relation between the X⁽³⁾ and the term (n²_ω+ 2)³.(n²_ω -1).E_d/E²₀ containing three measurable parameters only, irrespective of the kinds of MO, which was derived based on the bond orbital theory developed by M. E. Lines. The largest X⁽³⁾ value obtained is 1.69 × 10^?12 esu for 30NbO_2.5.70TeO₂ glass, about 60 times larger than that of pure fused silica glass.