Ion exchange is largely used to dope surface layer of glass with metal ions so inducing a modification of the optical properties of the doped layer, useful to fabricate low-loss optical waveguides. Post-exchange treatments, such as annealing in selected atmospheres and irradiation with light ions can induce the dopant aggregation in metallic clusters; laser irradiation can be further used to reduce the cluster size. These facts spread the possible application of ion-exchanged glasses as non-linear optical materials for optoelectronics.

I will present recent and new experimental results on glasses doped with metal atoms (Cu, Ag, Tl) by ion exchange from molten salt baths. X-ray absorption spectroscopy (XAS) allowed the investigation of the site of the metal ions dispersed into the matrix and of the metal aggregates induced by the post-exchange treatments, such as thermal annealing, laser or ion irradiation. Moreover, in presence of metal ions of different oxidation states diffusing into the matrix, XAS in grazing incidence geometry allowed to measure the depth profile of each species, giving the basic information to model the ion diffusion process. The experimental results indicate that the site of the dopant ion is different from that of that one of the replaced alkali ion (Na or K) and strongly depends on the glass used; moreover, the dopant-matrix correlation (i.e. the metal-oxygen distance) depends critically on the dopant concentration, suggesting that structural changes occur into the glass, caused by the ion-exchange process; about the aggregation of dispersed ions into metallic clusters, suitable post-exchange treatments can be exploited to tailor the cluster size, even towards the formation of small (~1 nm) aggregates.

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