Effects of chromophore dissociation on the optical properties of rare-Earth-doped polymers.

The observed dissociation of tetrakis rare-earth chromophores in rare-earth-doped organic polymers is reported, and a time-resolved spectroscopic technique is presented to determine quantitatively the fractional concentrations of different chromophore species in various solvents. Based on this technique, the equilibrium constants of tetrakis rare-earth chromophores in rare-earth-doped polymers are determined. Thus, the equilibrium constants for tetrakis rare-earth compounds of benzoyltrifluoroacetonate (BTF), for example, Sm(BTF)(4)P and Eu(BTF)(4)P in methyl methacrylate monomer, are K = 4.7 ? 0.5 x 10(-4) M and K = 1.2 ? 0.5 x 10(-4) M, respectively. In contrast, the tetrakis rare-earth compounds of hexafluoroacetylacetonate (HFA), for example, Sm(HFA)(4)Net(4) and Eu(HFA)(4)Net(4), are quite stable and show no evidence of dissociation. We further characterize the dissociation of several chromophore systems and discuss the influence such dissociation has on overall optical performance. The results enable determination of optimal doping concentrations as well as preferred rare-earth chromophore preparation and doped polymer fabrication procedures.