Title: Understanding and Controlling Conjugated Polymer Conformation and Photophysics
Description: Conjugated polymers have been extensively studied over the past decades for their potential use in modern optoelectronic devices such as organic solar cells and light-emitting diodes. However, due to their multichromophoric nature, the relationship between conformation and photophysical properties of conjugated polymers is still largely obscure, especially on the molecular and mesoscopic length scales, where deeper understanding is needed to improve device efficiency. In this dissertation, using poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and wide-field single-molecule fluorescence microscopy, we investigate the relationship between conformation and photophysics both on the single-molecule and aggregate levels, towards developing control over these properties. In Chapter 2, we explore how complex photophysical behaviors of conjugated polymer single molecules can complicate the interpretation of experimental results of a commonly used technique, fluorescence polarization modulation depth (M) measurements, which indirectly reports on molecular conformation.

Through fluorescence imaging and simulations, we show that the sublinear relationship between excitation intensity and conjugated polymer photoluminescence decreases measured M values, especially in molecules with highly ordered conformations. These findings show that analysis of M measurements should be done with caution. In Chapter 3, first we examine the effect of solvent vapor annealing on MEH-PPV single-molecule conformation. We show that molecular conformation initially set by the dissolving solvent is preserved after solvent vapor annealing, even though molecular mobility is observed during the process. Then, solvent vapor annealing is applied to high-concentration MEH-PPV samples to produce aggregates consisting of a few to hundreds of single molecules. We show that single-molecule conformation acts as a template for the aggregates. In addition, although the aggregates prepared in this work are largely isotropic, photoluminescence spectra indicate that exciton diffusion in these aggregates is enhanced over short length scales.

In general, this work suggests techniques and approaches to enhance understanding of various photophysical phenomena in conjugated polymers and other multichromophoric systems over an array of length scales.