Playing with Plasmons: Tuning the Optical Resonant Properties of Metallic Nanoshells

Abstract

Nanoshells, concentric nanoparticles consisting of a dielectric core and a metallic shell, are simple spherical nanostructures with unique, geometrically tunable optical resonances. As with all metallic nanostructures, their optical properties are controlled by the collective electronic resonance, or plasmon resonance, of the constituent metal, typically silver or gold. In striking contrast to the resonant properties of solid metallic nanostructures, which exhibit only a weak tunability with size or aspect ratio, the optical resonance of a nanoshell is extraordinarily sensitive to the inner and outer dimensions of the metallic shell layer. The underlying reason for this lies beyond classical electromagnetic theory, where plasmon-resonant nanoparticles follow a mesoscale analogue of molecular orbital theory, hybridizing in precisely the same manner as the individual atomic wave functions in simple molecules. This plasmon hybridization picture provides an essential “design rule” for metallic nanostructures that can allow us to effectively predict their optical resonant properties. Such a systematic control of the far-field optical resonances of metallic nanostructures is accomplished simultaneously with control of the field at the surface of the nanostructure. The nanoshell geometry is ideal for tuning and optimizing the near-field response as a stand-alone surface-enhanced Raman spectroscopy (SERS) nanosensor substrate and as a surface-plasmon-resonant nanosensor.Tuning the plasmon resonance of nanoshells into the near-infrared region of the spectrum has enabled a variety of biomedical applications that exploit the strong optical contrast available with nanoshells in a spectral region where blood and tissue are optimally transparent.