Synthesis and characterization of functional polymeric materials for use in organic photovoltaics




Moench, Sarah Joy

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Norbornene-type monomers with pendant oligothiophene donor and perylene diimide acceptor groups were synthesized and polymerized using ring-opening metathesis polymerization (ROMP) to yield donor and acceptor homopolymers. These semiconducting homopolymers were characterized by UV-Vis and fluorescence spectroscopy to determine absorbance maxima, emission and excitation profiles, optical bandgaps, molar absorbtivities, and quantum yields. The electrochemical behavior of the donor and acceptor materials was characterized by cyclic voltammetry to determine the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the organic semiconductors. Donor-acceptor diblock copolymers were synthesized using ROMP. Fluorescence spectroscopy demonstrated increased donor emission quenching with decreasing block length. Random donor-acceptor copolymers demonstrated almost complete quenching of the donor emission, likely due to increased donor-acceptor interfaces for charge transfer. Electron paramagnetic resonance spectroscopy (EPR) confirmed the formation of persistent donor radical cations and acceptor radical anions in the block copolymers. Small-angle X-ray scattering (SAXS) demonstrated bulk microphase separation with domain sizes between 24-28 nm. Furthermore, the formation of crystalline structure within the ordered microdomains was also observed. All of these studies indicate that the designed materials may be useful as the active layer in organic photovoltaic applications. As a route to functional hybrid materials, block copolymers containing a donor-segment and a Lewis-basic oligoethylene glycol segment, for preferential ZnO nanoparticle growth, were synthesized by ROMP. Photophysical and electrochemical characterization demonstrated that the donor electronic properties were maintained upon incorporation into the copolymer. SAXS was used to demonstrate lamellar morphology in bulk films of the symmetric block copolymers. ZnO nanoparticles were synthesized and incorporated into composite thin films with the block copolymers. These composite films demonstrated high photoluminescence quenching, which increased upon thermal annealing, as a result of favorable charge transfer from the photo-excited donor to the ZnO nanoparticles. These studies demonstrate that improved morphology control and self-assembly can increase charge transfer in hybrid materials through increased interfacial area. As an alternative route to directed ZnO nanoparticle growth, a copolymer containing pendant dipicolylamine moieties was synthesized and characterized by photophysical and electrochemical methods.



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