The synthesis of Ag nanoclusters in sodalime silicate glasses and silica was
studied by optical absorption (OA) and electron spin resonance (ESR)
experiments under both low (gamma-ray) and high (MeV ion) deposited energy
density irradiation conditions. Both types of irradiation create electrons and
holes whose density and thermal evolution - notably via their interaction with
defects - are shown to determine the clustering and growth rates of Ag
nanocrystals. We thus establish the influence of redox interactions of defects
and silver (poly)ions. The mechanisms are similar to the latent image formation
in photography: irradiation-induced photoelectrons are trapped within the glass
matrix, notably on dissolved noble metal ions and defects, which are thus
neutralized (reverse oxidation reactions are also shown to exist). Annealing
promotes metal atom diffusion, which in turn leads to cluster nuclei formation.
The cluster density depends not only on the irradiation fluence, but also - and
primarily - on the density of deposited energy and the redox properties of the
glass. Ion irradiation (i.e., large deposited energy density) is far more
effective in cluster formation, despite its lower neutralization efficiency
(from Ag+ to Ag0) as compared to gamma photon irradiation.Comment: 48 pages, 18 figures, revised version publ. in Phys. Rev. B, pdf fil