Multiple Roles of Polyethylenimine during Synthesis of 10 nm Thick Continuous Silver Nanoshells.

Silica@silver core-shell particles (silver nanoshells) present a wide range of applications, owing to their unique optical, chemical, and surface plasmon resonance (SPR) properties. Because SPR properties are mainly determined by shell thickness, precise shell thickness control is required. However, the synthesis of continuous nanoshells less than 10 nm thickness is still a challenge. In this study, we overcame this challenge by using polyethyleneimine (PEI) during the shell growth step of the seed-mediated growth method. We determined that the addition of PEI significantly slowed the shell growth reaction and facilitated the formation of uniform shells, which allowed us to synthesize 9.8 nm thick complete silver nanoshells. The SPR absorptions of the resultant nanoshell suspensions remained almost unchanged for 15 days. Therefore, we demonstrated that PEI molecules played three different roles during the shell growth process: reaction-rate regulators, shell growth facilitators, and resultant suspension stabilizers. The shell thickness was tuned from 9.8 to 29.5 nm by simply varying the silver-ion concentration. A key factor was the amount of added PEI because excess PEI would result in the formation of silver nanoparticles in the bulk solution phase, while too little PEI would produce incomplete shells. The optimum mass ratio of PEI-to-silica particles was determined to be 1.0 for the experimental conditions in this study. The mixing sequence of the reaction solutions was also important because PEI had to be mixed with silica particles first to ensure that the PEI molecules get adsorbed on the surface of silica and accommodated silver ions via the coordination interactions between the amine groups of the PEI molecules and silver ions. The reaction that involves the use of PEI could lead to establishing a simple and robust synthesis technique for silver nanoshells.