Plasmonics Tutorial

Noble metal nanoparticles support surface plasmons (oscillations of the conduction electrons at the nanoparticle surface) that result in extraordinary optical properties that are not exhibited by any other class of material. The basis for the effect is the plasmon resonance of the free electrons in the metal nanoparticle, which can be understood by studying the polarizability (the ease with which charges, such as the conduction electrons on the metal nanoparticle surface, undergo charge distribution and form partial dipoles). For a spherical nanoparticle, the quasistatic polarizability of the nanoparticle is given by:

Where 1 is the wavelength dependent dielectric function of the nanoparticle and 2 is the dielectric function of the medium which remains roughly constant regardless of wavelength. When the condition Re{ 1} = -22 is satisfied, the particle is driven into resonance resulting in a strong increase in the absorption and/or scattering at that wavelength. The resonance condition depends on the wavelength dependent dielectric function of the nanoparticle as well as the dielectric function of the medium. Consequently, the nanoparticle optical properties are highly dependent on material composition, size, and the medium in which the particles are embedded. Both the shape and peak resonance wavelength of the nanoparticle plasmon resonance is influenced by the local refractive index. When particles are in water (n=1.33) the peak resonance of 80 nm Ag particles predicted by Mie Theory is ~445 nm. In air (n=1.00) the peak wavelength of the plasmon resonance is predicted to be ~380 nm, a blue-shift of 65 nm. However, if the silver particle is coated with a shell of a material that has the same refractive index as water, the peak Plasmon wavelength will be restored to ~445 nm. By adjusting the thickness of the shell, the peak resonance of coated nanoparticles can be tuned to any wavelength between these two extremes. To observe this effect for other particle sizes, compositions and refractive indices, see our Online Mie Theory Simulator (OMTS) which allows you to calculate and view the theoretical optical response of gold and silver nanoparticles. Nanoparticle optical properties are also sensitive to the proximity of other plasmonic materials. When two or more plasmonic nanoparticles are near each other (with edge-to-edge separations of one particle diameter or less) their surface plasmons couple as the conduction electrons on each particle surface collectively oscillate. This effect is similar to molecular orbital theory in that plasmon coupling results in the oscillating electrons assuming the lowest energy state, causing the plasmon resonance wavelength of the coupled particles to red-shift to longer wavelengths (lower energies). This coupling effect is responsible for the dramatic changes in the visible color of plasmonic nanoparticle solution when nanoparticles aggregate and also the basis of many different types of plasmonic nanoparticle sensors.