Dynamic structure factor for large aggregate clusters with internal motions: a self-consistent light-scattering study on conjugated polymer solutions.

The aggregation properties of a standard conjugated polymer, poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), in two distinct solvents (chloroform and toluene) and a range of polymer concentrations (c = 0.1-3 mg/mL) have been unequivocally resolved using combined dynamic and static light scatterings (DLS/SLS). The prime challenges for analyzing this peculiar, practically important, solution system arise from the wide size distribution and unknown aggregate morphology, as well as pronounced interferences between translational and internal motions of aggregate clusters of considerably varying size. To cope with these central difficulties, we propose a self-consistent formulation for analyzing the dynamic structure factor in DLS experiment by extending an existing theory on free-draining bead-spring chains that explicitly accounts for internal fluctuations, along with two candidate form factors on Gaussian coil and rigid sphere, respectively, serving as two limiting cases to be discriminated in combined DLS and SLS measurements. Given that no accessibility to ultrasmall angular resolutions is a prerequisite, the suggested protocol can readily be carried out in conventional light-scattering apparatus. The present analyses unanimously support the rigid-sphere form factor in describing the entire set of light-scattering data on MEH-PPV solutions, differing from early small-angle neutron/X-ray scattering interpretations suggesting certain 2D fractal structures for the aggregation network. Scrutiny into the interior dynamics of aggregate clusters further disclosed that the segmental motions are noticeably more suppressed than for usual, nonaggregated polymer solutions, and no existing theories based on the bead-spring picture can yet capture the observed scaling behavior as manifested by the present data. Accordingly, we report several first-revealed properties of MEH-PPV solutions on the aggregate morphology, the size distribution (and mean size), mean aggregation number, and interior segmental dynamics, which serve as valuable information for linking solution properties with those for dried thin films in contemporary applications with conducting conjugated polymers.