Macromolecules, Vol.34, No.15, 5238-5248, 2001
Interface thickness of a styrene-methyl methacrylate block copolymer in the lamella phase by direct nonradiative energy transfer
This paper examines the use of direct nonradiative energy transfer (DET) experiments to determine the interface thickness in films of symmetric poly(styrene-b-methyl methacrylate) (PS-PMMA) block copolymers. The films were prepared from mixtures of two polymers of identical length and compositions, labeled at their junctions with either a 9-phenanthryl or 2-anthryl group. The fluorescence decays were analyzed in terms of a model that takes account of the Helfand-Taganu distribution profile of polymer segments at the interface. Reliable data analysis required careful subtraction of a background fluorescence from the measured decay profiles. Unlike neutron reflectivity experiments. DET measurements are insensitive to capillary waves at the interface. This advantage is offset by a strong sensitivity to the characteristic distance for energy transfer R-0, which has to be determined separately. When we take R-0 = 2.3 nm, we recover an interface thickness of 4.8 nm. We obtain a theoretical value of 4.2 nm when using the Semenov's finite-chain correction to Helfand-Tagami prediction and the Flory-Huggins chi (FH) parameter recovered by Russell for partially deuterated d-PS-PMMA copolymer. When we employ the Callaghan and Paul chi (FH) value for undeuterated PS + PMMA blends, we obtain delta = 4.9 nm.