Morphology-dependent photophysics in conjugated polymers

Summary form only given. We present evidence that the degree of inter-chain interactions and morphology in conjugated polymer films can be controlled by altering the chain conformation in the solution from which the film is cast. Light scattering experiments show that physical size of poly[2-methoxy-5-(2´-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) chains can vary by a factor of two in different solvents such as chlorobenzene or tetrahydrofuran. Photoluminescence and wavelength-dependent excitation indicate that MEH-PPV forms aggregate species with an absorption and luminescence spectra that are distinctly red-shifted from the intrachain exciton. The degree of aggregation is both concentration and solvent dependent. The overall photoluminescence quantum yield is found to depend on both how restricted the polymer conformation is due to choice of solvent and polymer concentration due to aggregation. The excited state aggregates have a longer lifetime than their intrachain exciton counterparts, as evidenced by a near-infrared transient absorption in femtosecond pump-probe and anisotropy measurements. Memory of the chain conformation and extent of aggregation of MEH-PPV in solution is carried into cast films. Thus, many conflicting results presented on the degree of interchain interactions can be explained by noting that the film samples in different studies were cast from precursor solutions with different solvents and concentrations.