Date of Award

Summer 8-2017

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry and Biochemistry

School

Mathematics and Natural Sciences

Committee Chair

Song Guo

Committee Chair Department

Chemistry and Biochemistry

Committee Member 2

Paige Buchanan

Committee Member 3

Wujian Miao

Committee Member 3 Department

Chemistry and Biochemistry

Committee Member 4

Sarah E. Morgan

Committee Member 4 Department

Polymers and High Performance Materials

Committee Member 5

Julie Pigza

Committee Member 5 Department

Chemistry and Biochemistry

Abstract

Chemically doped and non-doped P3HT nanoaggregates are studied to establish a comprehensive understanding of the interplay between their morphology and various optoelectronic properties. One-dimensional nanoaggregates of P3HT are chosen as the model systems here due to their high surface/volume ratio and suitability for microscopic investigations.

Atomic force microscopy (AFM) and kelvin probe force microscopy (KPFM) are used to correlate property/morphology characteristics of non-doped P3HT nanowhiskers. Topographical measurements indicate that individually folded P3HT motifs stack via interfacial interactions to form nanowhiskers in solution. Further aging leads to multi-layered nanowhiskers with greater stability and less instances of π-π sliding of interfacial edge-on oriented motifs. KPFM measurements show higher surface potentials on portions of nanowhiskers containing local defects and stacking faults due to overlapping, and nanowhiskers that are at least triple-layered.

Simultaneous UV-Vis and AFM characterizations compare the aggregation rates and morphologies of doped and non-doped P3HT nanowhiskers. Allowing fully solubilized P3HT to age without doping may produce high aspect ratio nanowhiskers containing disordered segments protruding out from the edges of the nanowhiskers. These protruding segments could also serve as “tie-molecules” between adjacent nanowhiskers. Doping fully solubilized P3HT will lead to substantially higher rates of P3HT aggregation. Doped nanowhiskers also display different morphologies. They pack tighter, are smoother, and are thicker and higher versus non-doped nanowhiskers, indicating a different aggregation mechanism.

Stopped flow-kinetics was employed to investigate the reactivity of two distinctively different morphological forms of P3HT towards dopants. Fully solubilized P3HT undergoes a slow doping mechanism whereas pre-aggregated P3HT undergoes a fast doping mechanism. Pseudo-single reactant rate fittings indicate that both mechanisms appear to be 1st order in P3HT, whereby pre-aggregated P3HT mixtures will produce more doped products per P3HT monomer unit than fully solubilized P3HT. This study highlights the impact of conjugated polymer’s morphology on their doping efficiency.

Density functional theory was used to investigate the charge transfer (CT) states between oligothiophene and F4-TCNQ. CT of several unreported complexes that feature two oligomers stacked in a sandwich or layered configuration is investigated. Our preliminary results suggest that these new complexes can generate substantially more charge per F4-TCNQ than previously reported.

ORCID ID

0000-0002-8191-962X

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