Theoretical consideration on preparing silver particle films by adsorbing nanoparticles from bulk colloids to an air-water interface

In our previous paper, a method for preparing enormous surface-enhanced Raman scattering (SERS) active substrates through the aggregation of silver particles trapped at an air−water interface was reported. Here, further efforts were devoted to investigate the origin of assembling silver particle films by adsorbing nanoparticles from bulk colloids to the air−water interface. It was revealed that it is thermodynamically favorable for a colloidal particle in bulk colloids to adsorb to the air−water interface; however, a finite sorption barrier between it and the nearby particles usually restrains the adsorption process. When an electrolyte such as KCl, which is commonly used as an activating agent for additional SERS enhancement, was added into silver colloids, it largely reduced the sorption barrier. Thus, silver nanoparticles can break through the sorption barrier, pop up, and be trapped at the air−water interface. The trapped silver particles are more inclined to aggregate at the interface than those in b...