Photophysics of bis(diarylamino)biphenyl dyes adsorbed on silver nanoparticles

This dissertation investigates the photophysics of bis(diarylamino)biphenyl (TPD) and silver nanoparticles (AgNP). A main goal of this work was to develop an understanding of the relaxation pathways involved in the deactivation of photoexcited TPD chromophores in close proximity to silver nanoparticles. The TPD chromophores were attached to the silver nanoparticle core via an alkylthiol group. The TPD-AgNP systems were synthesized and characterized using Transmission Electron Microscopy (TEM), UV-visible absorption, infrared spectroscopy, and Nuclear Magnetic Resonance (NMR) spectroscopy, Inductively Coupled Plasma - Emission Spectroscopy (ICP-ES) and Thermogravimetric Analysis (TGA). Time-resolved photophysical processes in these systems were studied using femtosecond transient absorption spectroscopy. Initial studies of the interaction of the TPD and AgNP addressed the linker length dependence of the dye excited state decay kinetics, wherein alkyl linker chains of 3, 4, 8 and 12 carbon atoms were used. These results showed that an ultrafast deactivation of the excited state of the TPD chromophore, which is three orders of magnitude faster than that of the free chromophore in solution, occurred in all of the systems. However, an unexpected new transient species was observed for the systems with three and four carbon linker chains. Further studies showed this species to be spectroscopically very similar to the TPD radical cation, suggesting a charge separation pathway in the excited state relaxation. Possible pathways for formation of the cation-like state were examined through comparisons to the photophysics of alkyl substituted TPD in solution and in solid films, investigation of the pulse energy and TPD surface coverage dependence of the yield of the cation-like TPD species, transient absorption anisotropy decay dynamics, and kinetic modeling studies. Taken together, these investigations provide support for exciton-exciton annihilation being responsible for the formation of cation-like species. The packing of the TPD chromophores is concluded to be of critical importance in the generation of the cation like species but it is also possible that proximity to the silver nanoparticle plays a role in facilitating charge separation as well.Ph.D