SPECTROSCOPIC ENHANCEMENT FROM NOBLE METALLIC NANOPARTICLES

Abstract

Resonant coupling of localized surface plasmon resonances (LSPRs) in noble metallic nanostructures to incident radiation and the related subject of localized behavior of electromagnetic waves are currently of great interest due to their potential application to sensors, biochemical assays, optical transmission, and photovoltaic devices.

My thesis research is made up of two related parts. In part one I examined enhanced fluorescence in dye molecules in proximity to Ag nanostructures. In part two I studied the effect of Au nanostructure arrays on the performance of poly(3-hexylthiophene-2,5-diyl) : [6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) bulk heterojunction (BHJ) organic solar cells (OSCs). Nanostructures were fabricated by two different methods: e-beam lithography (top down) and spray pyrolysis (bottom up). Using e-beam lithography, we produced arrays of nanostructures with well defined shapes, sizes, and spacings. By systematically varying these topographical parameters, we measured their effect on nanometer-sized metallic structure-enhanced fluorescence (nMEF) and on absorption and external quantum efficiency (EQE) in OSC devices as a function of optical wavelength.

In analyzing experimental results, we carried out numerical simulations of the local electric field under incident light, across plasmonic resonances. The comparison between the calculated local field squared and measured fluorescence/EQE provides physical insight on the configuration- dependence of these two processes. Our results indicate that local field enhancement near nanostructures is dominant in nMEF, and that the local field is strongly affected by the substrate and device architectures. For the OSCs, both measurements and calculations show that absorbance within the active layer is enhanced only in a narrow band of wavelengths (~640-720 nm) where the active layer is not very absorbing for our prototype nanopillar-patterned devices. The peak enhancement for 180 nm wide Au nanopillars was approximately 60% at 675nm. The corresponding resonance involves both localized surface plasmon excitation and multiple reflections/diffraction within the cavity formed by the electrodes. Finally, we explore the role of the size of the nanostructures in such a device on the optical absorption in the OSC active layer. We find that small Au nanopillars produce strong internal absorption resulting in Joule heating, and suppressing the desired enhancement in EQE in OSC devices.