Strong coupling of localized surface plasmons and ensembles of dye molecules.

We have studied strong exciton-plasmon coupling in the films of Ag nanoislands as well as in the layer-by-layer (LBL) deposited films of Au nanoparticles (NPs) coated with highly concentrated rhodamine 6G (R6G) dye. Their absorbance and the reflectance spectra featured the peaks or dips, which were not characteristic of dye or NPs/nanoislands taken separately. The positions of the spectral maxima (or minima) in the dye-doped films, plotted against those in pristine Ag nanoislands films, resulted in the dispersion curves comprised of three branches. They could be described by the analytical model based on the Hamiltonian accounting for the unperturbed energies of the surface plasmon (SP) resonance, the two bands composing the absorption spectrum of R6G dye, and the exciton-plasmon coupling energy Δ. Its value was larger in Ag nanoislands films deposited on hyperbolic metamaterials (0.221 eV) than on glass (0.165 eV). The minimal gap between the upper and the lower branches was equal to ≈3Δ. The dispersion curves in the Au NPs LBL films could be described with the Hamiltonian equation at relatively small dye concentrations. At larger concentrations of R6G molecules, the spectral peaks shifted and became more pronounced. The corresponding dispersion curve could not be described in terms of the existing model, indicating the need for further theoretical studies.

Study of the effect of excited state concentration on photodegradation of the p3ht polymer.

We have studied photoinduced reduction of absorption and emission in p3ht, a semiconducting polymer, and found that the rate of photodegradation (destruction of the constituent thiophene rings) does not correlate with the luminescence intensity and, correspondingly, does not depend on the excited state concentration. This conclusion rules out Purcell enhancement of radiative decay rate as a possible explanation of the recently discovered reduction of the p3ht photodegradation rate in the vicinity of metallic substrates and lamellar metal-dielectric metamaterials.

Control of a chemical reaction (photodegradation of the p3ht polymer) with nonlocal dielectric environments.

Proximity to metallic surfaces, plasmonic structures, cavities and other inhomogeneous dielectric environments is known to control spontaneous emission, energy transfer, scattering, and many other phenomena of practical importance. The aim of the present study was to demonstrate that, in spirit of the Marcus theory, the rates of chemical reactions can, too, be influenced by nonlocal dielectric environments, such as metallic films and metal/dielectric bilayer or multilayer structures. We have experimentally shown that metallic, composite metal/dielectric substrates can, indeed, control ordering as well as photodegradation of thin poly-3-hexylthiophene (p3ht) films. In many particular experiments, p3ht films were separated from metal by a dielectric spacer, excluding conventional catalysis facilitated by metals and making modification of the nonlocal dielectric environment a plausible explanation for the observed phenomena. This first step toward understanding of a complex relationship between chemical reactions and nonlocal dielectric environments is to be followed by the theory development and a broader scope of thorough experimental studies.