Controlled joining of Ag nanoparticles with femtosecond laser radiation

We show that it is possible to tailor the gap separation and interface geometry between adjacent Ag nanoparticles (NPs) by controlling fluence when irradiating with pulses from a fs laser. Unirradiated samples extracted from aqueous solution consist of networks of Ag NPs coated with polyvinylpyrrolidone (PVP). At low laser fluence, bonding between NPs occurs via the formation of an intervening hydrogenated amorphous carbon (α-C:H) layer resulting from the laser-induced decomposition of PVP. This occurs when electrons are emitted at hot-spots created by the trapping of plasmons. The thickness of the α-C:H layer determines the minimum separation between NPs. Ag NPs with different contact geometries can be produced by irradiation of the networks in solution at fluences exceeding the threshold for the formation of α-C:H. At fluences between 200 and 380 μJ/cm2, the α-C:H interface layer is replaced with a metallic neck. Surface enhanced Raman scattering (SERS) has been used to quantify the electromagnetic field enhancement in joined NP samples. We find that Ag NPs bonded by α-C:H and exhibiting a narrow gap possess the highest SERS enhancement.