- 學位論文
立體規則性共軛高分子之合成與物性研究
Studies on the synthesis and physical properties of regioregular conjugated polymer
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摘要
摘 要 本研究以Still cross-coupling的聚合方法製備不同烷基側鏈長度的立體規則性聚（3-烷基噻吩乙烯）（RR-P3ATVs），探討共軛分子鏈的立體規則度及其超分子聚集與物性，比較不同烷基側鏈長度對共軛高分子之UV-Vis光譜、螢光（PL）光譜及熱分析，藉由製備立體規則性聚（3-烷基噻吩乙烯）之Schottky barrier 二極體來探討元件的電子特性與固態薄膜表面形態的關係。 依照1H NMR的結果得知，側鏈碳數為4、8、12的立體規則性聚（3-烷基噻吩乙烯）其立體規則度分別為83.2﹪、82.4﹪及94.5﹪。由溶合變色實驗得知，立體規則性聚（3-烷基噻吩乙烯）的UV-Vis吸收，隨著不良溶劑增加而產生紅位移，且較高立體規則度的立體規則性聚（3-烷基噻吩乙烯）有較小的溶合變色範圍，由UV-Vis的起始吸收推算，立體規則性聚（3-烷基噻吩乙烯）的能帶間隙約為1.64 ev。由於導入乙烯基於共軛鏈中，形成較高的共平面程度及較長的共軛長度，其值與立體規則性聚（3-烷基噻吩）（RR-P3ATs）比較，立體規則性聚（3-烷基噻吩乙烯）的紅位移約為100 nm。由於高立體規則度，立體規則性聚（3-烷基噻吩乙烯）的PL光譜僅於約630 nm有非常微弱的放射。 另一方面，立體規則性聚（3-烷基噻吩乙烯）的Schottky barrier 二極體出現很大的漏電流。經由AFM分析其表面型態的結果，發現立體規則性聚（3-烷基噻吩乙烯）有剛硬共軛鏈的各向異性聚集。由於這種表面形態的超分子聚集，對平面結構的薄膜電晶體可能有提高電荷載子遷移率的效果，此現象可由未來的研究證實。
並列摘要
Abstract In this study, the regioregular poly(3-alkylthienylenevinylene)s (RR-P3ATVs) with different alkyl side-chain length were prepared by Still cross-coupling polymerization to elucidate the effect of regioregularity and side-chain length of regioregular conjugated polymers on the supramolecular aggregation and physical properties via UV-vis spectra, photoluminescence (PL) spectra and thermal analysis. Schottky barrier diodes were also fabricated to study the electric characteristics of devices and relationship to the solid-film morphology of RR-P3ATVs. According to the 1H NMR results, the regioregularity for RR-P3ATVs with alkyl side-chains of butyl, octyl, and dodecyl were 83%, 82%, and 95%, respectively. Upon solvatchromism experiment, the UV-vis absorption red-shift for RR-P3ATVs occur on the addition of poor solvent, where the more regioregular RR-P3ATVs possess the less solvatochromic range. The bandgap (Eg) of RR-P3ATVs were about 1.64 eV estimated from the threshold electronic absorption of UV-vis spectra. As compared to the lmax absorption of regioregular poly(3-alkylthiophene)s (RR-P3ATs), the red-shift about 100 nm for RR-P3ATVs resulted from the more coplanarity and the longer conjugation length due to the additional vinylene linkage introduced to the conjugated chains. Due to the high regioregularity, the PL spectra of RR-P3ATVs only exhibit very weak emission around 630 nm. On the other hand, the large leakage-current appearing on the Schottky-barrier diodes of RR-P3ATVs were attributed to the anisotropic aggregation of rigid conjugated chains which were revealed by the AFM scanning image. For this supramolecular-stacked morphology, the in-plane architecture of thin-film transistor may benefit from the higher charge carrier mobility, which would be confirmed on the future research.
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