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Photophysical Impacts of Aggregation on Organic Semiconducting Polymers

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Organic semiconductors have shown great promise for optoelectronic applications, particularly solar photovoltaics. Critical to their success is the ability to understand and manipulate the relationship between molecular structure and bulk properties. Substantial progress on understanding structural influences on electronic properties has been made for the conjugated polymers and small molecules that comprise the active layers of these devices, but it is still challenging relating these structural characteristics to optoelectronic functions in complex and significantly disordered assemblies like aggregates and film domains. Towards this end, this thesis examines the photophysical impacts of solution aggregation on organic semiconducting polymers with a focus on the influential PTB7. By isolating and determining the contributions of both its revolutionary “push-pull” electronic backbone and its robust solution aggregation, this thesis hopes to demonstrate the interplays between backbone, packing, and electronic structure in PTB7 to inform future materials and devices influenced by its design.

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