The femtosecond laser ablation of a gold target in aqueous solutions has been used to produce colloidal Au nanoparticles with controlled surface chemistry. A detailed chemical analysis showed that the nanoparticles formed were partially oxidized by the oxygen present in solution. The hydroxylation of these Au-O compounds, followed by a proton loss to give surface Au-O -, resulted in the negative charging of the nanoparticles. The partial oxidation of the gold nanoparticle surface enhances its chemical reactivity and consequently has a strong impact on its growth. In particular, the oxidized surface reacted efficiently with Cland OHto augment its net surface charge. This limited the coalescence of the particles, due to electrostatic repulsion, and led to a significant reduction of their size. Taking advantage of the repulsion effect, efficient size control was achieved using different salts (7 ( 5 nm for 10 mM KCl, 5.5 ( 4 nm for 10 mM NaCl, 8 ( 5 nm for NaOH, pH 9.4), a considerable improvement comparatively to particles prepared in deionized water, using identical ablation conditions, where particles of 1-250 nm were produced. The partially oxidized gold surface was also suitable for surface modification through both covalent and electrostatic interactions during particle formation. Using solutions of N-propylamine, we showed an efficient control of nanoparticle size (5-8 ( 4-7 nm) by the involvement of these interactions. The results obtained help to develop methodologies for the control of laser-ablation-based nanoparticle growth and the functionalization of nanoparticle surfaces by specific interactions.

The diffusion and coalescence of metal nanoparticles play important roles in many phenomena. Here, we offer a new integrated overview of the main factors that control the nanoparticle coalescence process. Three factors are considered in our description of the coalescence process: nanoparticle diffusion across the surface, their physical and thermodynamic properties, and the mechanism of coalescence. We demonstrate that the liquid-like properties of the surface layers of the nanoparticles play an essential role in this process. We present experimental evidence for our opinion, based on the high-resolution electron microscopic analysis of several different types of nanoparticles.

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