Surface enhanced Raman scattering with metal nanoshells
Jackson, Joseph Bryan
Halas, Naomi J.
Doctor of Philosophy
A systematic investigation of surface enhanced Raman scattering (SERS) was performed using metal nanoshells as the substrate. Nanoshells are a dielectric sphere coated with a thin metal shell, which have a well understood, geometrically tunable plasmon resonance. This tunability allows for the engineering of the optical near field for SERS. A simple model connecting the nanoshell electromagnetic near field at the incident frequency to that at the Raman shifted frequency is discussed. This theory is compared to the measured SERS response of the nonresonant molecule para-mercaptoaniline (pMA) adsorbed on silver and gold nanoshells. Using a solution of silver nanoshells, at an excitation wavelength of 1064 nm enhancements on the order of 106 to 108 were observed. Accounting for reabsorption of the Raman scattered light as it traverses the solution suggests enhancements of 1012. To mitigate the reabsorption, film geometries were investigated. For film measurements a 782 nm excitation laser was used. The SERS response of a dense film of silver nanoshells followed the calculated single nanoshell response of the nanoshells whose plasmon resonance was tuned near the excitation wavelength. In contrast, for nanoshells blue shifted from the excitation laser, the film Raman response followed an estimated dimer response. The Raman response as a function of nanoshell density was studied using films of gold nanoshells dispersed on the surface of polyvinylpyridine (PVP) coated glass slides. A linear dependence of the Raman modes on the nanoshell density was observed confirming that the single nanoshell plasmon dominates the SERS response. The SERS enhancements for nanoshell films calculated by direct comparison to an unenhanced measurement were on the order of 10 10 to 1012. The Raman response as a function of incident intensity was measured for dense silver nanoshell films. An optical pumping model allowing for stimulation of the Raman emission is proposed. Using this model, an effective unenhanced Raman cross section of the order of 10-27 cm2 is found. This is comparable to cross sections obtained in unenhanced Raman measurements. Evidence for two photon photoluminescence by nanoshells is presented. It is proposed the Raman emission is stimulated by the two photon photoluminescence.
Biomedical engineering; Optics