Spectroscopic monitoring on irradiation-induced formation of AuAg alloy nanoparticles by femtosecond laser

The interaction of an intense femtosecond laser pulses with a neat liquid solvent has been known to produce a number of highly reactive species that are useful to induce chemical reactions in the solution through the nonlinear absorption processes. When metal ions are present in the solution, they are assumed to readily reduce by ions, radicals, molecules or excited states generated photolytically from the solvent resulting in the formation of zerovalent metal nanoalloys. If two kinds of metal precursors are involved in a reduction process, the alloying process is expected. In this work, irradiation-induced synthesis of AuAg bimetallic nanoparticle at different laser-pulse energies was examined to investigate the formation mechanism in the presence of NH₄OH in the initial solution. At a given laser pulse energy (5.8 mJ/pulse), the time evolution of the UV-visible absorption spectra showed that the formation of AuAg nanoalloys most likely begin with the formation of Ag-riched alloy nanoparticles. As the reduction is started, the absorption spectrum of solution was closer to that of pure Ag nanoparticles. This indicates that the reduction rate of Ag is relatively greater than that of Au nanoparticle in the presence of ammonia. The single peak position then shifts to the red region as the irradiation time increases. After 10 min, the peak positions are between pure silver and gold peaks indicating the alloying process occurs at this stage. At low pulse energy (1.0 mJ/pulse), there was an induction time for several minutes before the absorption is detectable, and hence the alloying process is also delayed (after 20 minutes irradiation). While the formation rate of nanoparticles is more pronounced at high laser pulse energy, the formation yield is relatively the same for both laser pulse energies.