The morphology regulation and plasmonic spectral properties of Au@AuAg yolk-shell nanorods with controlled interior gap.

Au@AuAg yolk-shell nanorods with tunable and uniform interior gap were synthesized through galvanic replacement reaction, where Au@Ag core-shell nanorods served as sacrificial templates and HAuCl4 solution served as reductant. The effects of HAuCl4, Ag shell thickness and aspect ratio (AR) of Au nanorods on the morphology of Au@AuAg yolk-shell nanorods had been investigated systemically. The results clearly indicated that AuAg alloy shell thickness of Au@AuAg yolk-shell nanorods could be increased from 3.6 to 10.0 nm by varying the amount of HAuCl4. Meanwhile, the shape of AuAg alloy shell could be tuned by changing the shape of Ag coating. With the increasing of Ag coating thickness, the interior gap could be finely tuned in the range from 2.6 to 8.1 nm. The uniformity of interior gap could be improved by increasing the AR of Au nanorods. All these tunable geometries can further affect the plasmonic spectral properties of Au@AuAg yolk-shell nanorods. Because of the appearance of interior gap, the longitudinal localized surface plasmon resonance (LSPR) peak of Au@AuAg yolk-shell nanorods was located between that of bare Au nanorods and Au@Ag core-shell nanorods without interior gap. The increase of outer AuAg shell thickness can weaken the coupling between the inner and outer surface of the AuAg shell and lead to the decrease of AR, so the transverse and longitudinal LSPR bands gather together. The decrease of Ag coating thickness can enhance the coupling between inner Au nanorod and outer AuAg shell, which results in the red shift of the longitudinal LSPR band. This paper provides a method for studying the plasmonic coupling between two metal surfaces with a metal layer or a dielectric layer, which is also a new approach for regulating the plasmonic spectral properties of bimetallic nanoparticles. The controllability of Au@AuAg yolk-shell nanorods in both the interior gap and outer alloy shells makes them have potential applications in biomedicine, catalysis, nanoreactors, and energy storage.