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The Development of Semiconducting Materials for Organic Photovoltaics


The chemical structure of conjugated semiconducting materials strongly influences the performance of organic photovoltaic (OPV) devices. Thus a good understanding of the structure-function relationships that govern the optoelectronic and physical properties of OPV materials is necessary. In this dissertation, organic polymers and small molecules are evaluated in terms of OPV device output parameters, and molecular design rules are elucidated.

The development of molecules with alternating electron-rich and electron-deficient backbone units provides materials with suitable optoelectronic properties for OPVs and favorable modularity for organic semiconductor design. The choice of specific aromatic units and side chains for conjugated materials are shown to modulate the energy levels and architecture of OPV devices, affecting each of the four mechanistic steps of OPV operation.

In Chapter 2, the relationship between molecular packing parameters and the bulkiness of aliphatic solubilizing group extending away from a polymer backbone is elucidated, and high-performance OPV devices are achieved. In Chapter 3, the inclusion of a post-processing functionality on a polymer side chain is found to have a positive effect on the bulk morphology and overall performance of OPV devices. In Chapter 4, the influence of electron-withdrawing and quinoidal monomers on the optoelectronic properties of conjugated polymers is established, and energy level modulation is shown to affect the electron accepting and donating capabilities of OPV materials in a blended device. In Chapter 5, small molecules are designed with complementary light absorption properties in order to investigate a rarely observed charge generation mechanism.

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