Photochemical process of divalent germanium responsible for photorefractive index change in GeO2-SiO2 glasses

The photoluminescence spectra of the divalent Ge (Ge2+) center in GeO2-SiO2 glasses with different photosensitivities were investigated by means of excitation-emission energy mapping. The ultraviolet light induced photorefractivity has been correlated with the local structure around the Ge2+ centers. The glasses with a larger photorefractivity tended to exhibit a greater band broadening of the singlet-singlet transition on the higher excitation energy side accompanied by an increase in the Stokes shifts. This strongly suggests the existence of highly photosensitive Ge2+ centers with higher excitation energies. It is also found that the introduction of a hydroxyl group or boron species in GeO2-SiO2 glasses under appropriate conditions modifies the local environment of Ge2+ leading to an enhanced photorefractivity.