Plasmonic field effects of silver nanoparticle monolayers on poly(phenylene ethynylene) fluorescent polymers of different chain length
Poncheri, Adam James
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The literature on nanomaterials has been flooded with new shapes, sizes, and compositions of nanostructures. The process of developing and characterizing these particles has been broadly accomplished and many interesting and promising properties have been revealed for application in current and developing technologies. In particular, the phenomenon of surface plasmon resonance seen in metallic gold and silver nanoparticles has drawn substantial interest. It has been established that the electromagnetic fields surrounding plasmonic particle surfaces can influence the properties of nearby systems, causing them to experience effects such as enhanced absorption and emission of light or drastically increased conductivity. For this reason, plasmonic nanoparticles are being applied to an endless number of applications for new materials. This thesis investigated the effects of silver nanocube (AgNC) arrays on the photophysical properties of poly(paraphenyleneethynylene) (PPE) fluorescent polymers, a particularly relevant material to the applications of organic-electronics. AgNCs were selected because of their particularly strong plasmonic field, which is enhanced at the sharp features of the cubes. The PPE polymer is an exceptionally fluorescent conjugated polymer that often serves as a building block for polymer-based sensing applications. By monitoring the absorption and emission of the PPE polymer, a better understanding of plasmonic effects on this polymer system was obtained. Compression of the monolayer of AgNCs on the surface of a Langmuir-Blodgett trough can be used for control of interparticle distance and, thus, the plasmon field intensity felt by an adsorbed layer of PPE polymer. In the Chapter 4, PPE (n = 15) emission was monitored as a function of the AgNC plasmonic field. A two-photon process was found to explain the unusual increase then decrease of the fluorescence intensity. This observation was attributed to exciton-exciton annihilation processes within the polymer. The annihilation process is initiated by large enhancements of the polymer absorption rate when plasmonic fields are at their highest (when the AgNCs are compressed to short interparticle distances). In chapter 5, the optical properties of PPE polymers as a function of their chain length and the AgNC density were examined. A simple study was conducted to consider the conformational/geometrical effects on PPE that were caused by the deposition of PPE onto the AgNC topography. In this study, the structure of the absorption and emission profiles were evaluated and used as evidence of polymer interchain interactions, planarization, and even the potential generation of oligomeric species through breaking of conjugation. Fundamental interactions between materials must be evaluated and optimized prior to their use in devices. This thesis serves to shed a little bit of light on the interaction of a well-defined plasmonic particle with a conjugated polymer. The Langmuir-Blodgett technique serves as a critical tool in applying these colloidally produced nanoparticles to 2D arrays in practical applications. The observation of exciton-exciton annihilation at low-energy excitation is an entirely new phenomenon that was initiated by the plasmonic properties of metal nanoparticles. It is the hope of the author that the results contained herein can aide in the use of plasmonic nanoparticles in future devices.