Glass layers for planar light waveguides prepared by Ag-Na ion exchange of different silicate glasses in molten salt baths are annealed and/or irradiated with a laser beam in the UV region, with different energy density values and total pulse numbers. The samples are mainly characterized by optical absorption spectroscopy, luminescence spectroscopy, and Rutherford backscattering spectrometry, in order to determine the role of irradiation parameters and of the host matrix structure in the aggregation phenomena. Photoluminescence spectroscopy gave information regarding the presence of Ag multimeric aggregates, the primal seeds for the growing (nano) crystals. The appearance of the plasmon resonance band in the optical absorption spectra proved the formation of Ag clusters and allowed the evolution steps of the clusterization process to be followed as a function of the energy deposited during the laser irradiation. (C) 2010 Elsevier B.V. All rights reserved.