Properties of pi-Conjugated Fluorescence Polymer-Plasmonic Nanoparticles Hybrid Materials

Recently, great interest has risen in studying and using hybrid material made by mixing polymeric materials with plasmonic nanoparticles. In the present work, the photophysical properties of two poly(p-phenyleneethynylene) fluorescent polymers, varying in chain length, were studied as a function of (1) pure polymer surface compression after deposition from a Langmuir-Blodgett trough onto a substrate and (2) deposition of a constant amount of polymer onto the surface of silver nanocube arrays of varying particle densities. The results are discussed in terms of the surface pressure and nanoparticle topography effects on conformation of the fluorescent polymer. It was found that the short polymer is much less affected by increased surface pressure, remaining isolated from interchain interaction. The long polymer exhibits signs of conjugation breaking, presumably due to compression of its longer, "tangled", structure. The two polymer chains in the nanoparticle/polymer series of experiments exhibited a blue-shift and a substantial narrowing of their emission spectra when deposited onto the lowest surface pressure nanoparticle sample. With increasing nanoparticle density, the spectra continue to blue-shift and narrow. This effect is presumably a combined effect of conformational changes that shift the emission to higher energy (blue-shift) and plasmonic effects that result in enhancement of primary emission of the polymer (emission from the 0-0 and 1-0 transitions), thus narrowing the emission.