Real-Time Dark-Field Scattering Microscopic Monitoring of the in Situ Growth of Single Ag@Hg Nanoalloys

A comprehensive understanding of the growth mechanism of nanoalloys is beneficial in designing and synthesizing nanoalloys with precisely tailored properties to extend their applications. Herein, we present the investigation in this aspect by real-time monitoring of the in situ growth of single Ag@Hg nanoalloys, through direct amalgamation of Ag nanoparticles with elemental mercury, by dark-field scattering microscopy. Four typically shaped Ag nanoparticles, such as rods, triangular bipyramids, cubes, and spheres, were used as seeds for studying the growth of Ag@Hg nanoalloys. The scattered light of Ag nanoparticles of different shapes, on exposure to the growth solution, exhibited a noticeable blue-shift followed by a red-shift, suggesting the growth of Ag@Hg nanoalloys. The formation of Ag@Hg nanoalloys was confirmed by scanning electron microscopy, high-resolution transmit electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, and elemental mapping and line scanning. Further analysis of the time-dependent spectral data and morphological change of single nanoparticles during the growth led to the visual identification of the growth mechanism of single Ag@Hg nanoalloys. Three important steps were involved: first, rapid adsorption of Hg atoms onto Ag nanoparticles; second, initial diffusion of Hg atoms into Ag nanoparticles, rounding or shortening the particles; third, further diffusion of Hg atoms leading to the formation of spherical Ag@Hg nanoalloys. On the basis of these results, Ag@Hg nanoalloys with given optical properties can be synthesized. Moreover, dark-field scattering microscopy is expected to be a powerful tool used for real-time monitoring of the in situ growth of other metal nanoparticles.