Macroscopic Au@PANI Core/Shell Nanoparticle Superlattice Monolayer Film with Dual-Responsive Plasmonic Switches

The self-assembled gold nanoparticle (NP) superlattice displays unusual but distinctive features such as high mechanical and free-standing performance, electrical conductivity, and plasmonic properties, which are widely employed in various applications especially in biological diagnostics and optoelectronic devices. For a two-dimensional (2D) superlattice monolayer film composed of a given metal nanostructure, it is rather challenging to tune either its plasmonic properties or its optical properties in a reversible way, and it has not been reported. It is therefore of significant value to construct a free-standing 2D superlattice monolayer film of gold nanoparticles with an intelligent response and desired functions. Herein, we developed an easy and efficient approach to construct a gold nanoparticle superlattice film with a dual-responsive plasmonic switch. In this system, gold nanoparticles were coated by polyaniline (PANI) and then interracially self-assembled into a monolayer film at the air-liquid interface. The PANI shell plays two important roles in the superlattice monolayer film. First, the PANI shell acts as a physical spacer to provide a steric hindrance to counteract the van der Waals (vdW) attraction between densely packed nanoparticles (NPs), resulting in the formation of a superlattice by adjusting the thickness of the PANI shell. Second, the PANI shells provide the superlattice film with multiple stimuli such as electrical potential and pH change, leading to reversible optical and plasmonic responsiveness. The superlattice monolayer film can show a vivid color change from olive green to pink, or from olive green to violet by the change of the corresponding stimuli. Also, the localized surface plasmonic resonance (LSPR) of the superlattice monolayer film can be reversibly modulated by both by changing the local pH and applying an electric potential. Notably, a significant plasmonic shift of 157 nm can be achieved in the superlattice monolayer film when the PANI shell with a thickness of 35 nm and gold nanorods as a core were used. The superlattice monolayer film with dual-responsive plasmonic switches is promising for a range of potential applications in optoelectronic devices, plasmonic and colorimetric sensors, and surface-enhanced Raman scattering (SERS).