The molecular structure of a conjugated polymer critically impacts its physical and optoelectronic properties, thus determining its ultimate performance in organic electronic devices. In this work, new polymers and derivatives are designed, synthesized, characterized, and tested in photovoltaic devices. Through device engineering and nanoscale characterization, general structure-function relationships are established to aid the design of the next-generation of high performance polymer semiconductors for organic electronic applications.

Using a prototypical conjugated polymer, the influence of backbone regioregularity is examined and found to highly impact polymer crystallinity, solid state morphology and device stability. The investigation of alternative aromatic units in the backbone also led to new understandings in polymer processability and the development of promising materials for organic photovoltaics.

Besides the backbone structure, the side chain choice of the polymer can significantly affect material properties and device performance as well. In fact, the side chain substitution can influence both the optoelectronic properties and the physical properties of the polymer. A sterically bulky side chain can be used to tune the donor/acceptor separation distance, which in turn determines the charge separation efficiency. The addition of a polar side group increases the dielectric constant of a polymer and improves overall charge separation. Choosing the appropriate solubilizing group can also induce solid state packing of the polymer and considerably enhance device efficiency. Finally, the influence of post-fabrication processing techniques on the crystallinity and charge transport properties of a polymer is highlighted.