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Control of color, molecular order and charge transport in conjugated polymers

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  1. Tez No: 401583
  2. Yazar: ÜNSAL KOLDEMİR
  3. Danışmanlar: PROF. JOHN R. REYNOLDS
  4. Tez Türü: Doktora
  5. Konular: Kimya, Chemistry
  6. Anahtar Kelimeler: Belirtilmemiş.
  7. Yıl: 2012
  8. Dil: İngilizce
  9. Üniversite: University of Florida
  10. Enstitü: Yurtdışı Enstitü
  11. Ana Bilim Dalı: Belirtilmemiş.
  12. Bilim Dalı: Belirtilmemiş.
  13. Sayfa Sayısı: 180

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Özet (Çeviri)

Conjugated polymers with a high degree of molecular order were developed and integrated into organic electronic applications, where the mechanical robustness, processibility, and high charge transport properties of these materials were taken advantage of to yield high performance devices. This dissertation examines strategies for improving device performance first through optimizing synthetic protocols for the scalable preparation of photovoltaic materials with aesthetically pleasing color; and also through synthetic manipulation, via heavy atom substitution and end capping, of commonly used polymers to yield improved charge transport in field effect transistor applications. A dioxythiophene donor-acceptor based polymer, PGreen, was synthesized through oxidative polymerization (later optimized through Stille polymerization) and implemented in photovoltaic devices. The synthesis was both reproducible and scalable. PGreen was chosen because of its aesthetically pleasing green color, achieved via a trough in its absorption profile in the green region of the spectrum. This work is the first to study the scalability of both the synthesis and processing of a polymer other than poly(3-hexylthiophenes) for large area solar cell applications. In 16 particular, the performance differences between spin coated, small area solar cells, and large scale slot die coated solar cells were investigated to highlight the importance of processing techniques on device performance. In the second portion of this thesis, a germanium atom was substituted in place of a silicon atom as the bridging atom in fused thiophene aromatic units in six polymers obtained by Stille polycondensation by 1% stoichiometric imbalance. Heavy atom substitution is discussed as a means of increasing the molecular organization of conjugated polymers, leading to higher charge transport properties. Ge atom substitution provided a way to tune both the HOMO and LUMO levels and thereby the absorption profiles of the polymers in the visible spectrum. Furthermore, longer C-Ge bond lengths enhanced Pi stacking with closer intermolecular interactions, as shown by X-ray analyses, resulting in higher charge carrier mobilities. As an alternative approach, the effects of end groups on the molecular order of the best performing dithienogermole-benzothiadiazole based copolymer were studied and compared with the performance of a non-end capped control polymer. End groups were confirmed by 1H-NMR, 2D NMR and MALDI-MS analyses. The presence of end groups resulted in an increased tendency to stack with closer intermolecular interactions. Independent of the processing conditions, a much higher hole mobility was obtained by end capping.

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