Prolonged exposure to X-rays of HAuCl4 deposited from an aqueous solution onto a SiO2/Si substrate or into a poly(methyl methacrylate) (PMMA) matrix induces reduction of the Au 3+ ions to Au 0 and subsequent nucleation to gold nanoclusters as recorded by X-ray photoelectron spectroscopy. The corresponding major oxidation product is determined as chlorine {HAuCl 4(ads) + X-rays f Au(ads) + (3/2)Cl2(ads) + HCl(ads)}, which is initially adsorbed onto the surface but eventually diffuses out of the system into the vacuum. The reduced gold atoms aggregate (three-dimensionally) into gold nanoclusters as evidenced by the variation in the binding energy during X-ray exposure, which starts as 1.3 eV but approaches a value that is 0.5 eV higher than that of the bulk gold. The disappearance of the oxidation product (Cl2p signal) and the growth of the nanoclusters (related to the measured binding energy difference between the Si2p of the oxide and Au4f of the reduced gold) exhibit first-order kinetics which is approximately 3 times slower than the reduction of Au 3+ , indicating that both of the former processes are diffusion controlled. Similarly, gold ions incorporated into PMMA can also be reduced and aggregated to gold nanoclusters using 254 nm deep UV irradiation in air evidenced by UV-vis-NIR absorption spectrocopy.

a b s t r a c tAu and Au-Pt alloy nanoparticles are prepared and patterned at room temperature within the PMMA polymer matrix by the action of 254 nm UV light or X-rays. The polymer matrix enables us to entangle the kinetics of the photochemical reduction from the nucleation and growth processes, when monitored by UV-vis spectroscopy. Accordingly, increase of the temperature to 50 C of the reaction medium increases the nucleation and growth rates of the nanoparticle formation by more than one order of magnitude, due to enhanced diffusion and nucleation at the higher temperature, but has no effect on the photochemical reduction process. Presence of Pt ions also increases the same rate, but by a factor two only. Similar photochemical reduction and particle growth take also place within the PMMA matrix, when these metal ions are subjected to prolonged exposure to X-rays, as evidenced by XPS analysis. Both angle-resolved and charge-contrast measurements using XPS reveal that the resultant Au and Pt species are in close proximity to each other, indicating the Au-Pt alloy formation to be the most likely case.

Prolonged exposure to X-rays of HAuCl 4 , PtCl 4 and their mixtures, deposited from an aqueous solution onto a silicon substrate, causes chemical reduction of the metal ions to their metallic states. The corresponding oxidation reaction is the conversion of chloride ions to chlorine. The resultant metal atoms aggregate to form metallic/bimetallic nanoclusters as evidenced from their XPS chemical shifts. Hence, X-rays are usable for in-situ nanoparticle production or for direct-writing applications on silicon substrates.