| 摘要: | 摘要 自1977年Shirakawa ; MacDiarmid ; Heeger將具有共軛結構的高分子聚乙炔摻雜(doping)後，導電度提高了109倍，這個發現被視為是一大突破，此之後共軛高分子的研究迅速的成長。在1983年被合成出來的聚?吩，經摻雜後有良好的導電性，但不溶於一般有機溶劑，於是在?吩的第3個位置接上烷基，合成出聚3-烷基?吩，可溶於一般有機溶劑，卻又衍生了去摻雜的問題。本實驗是設計合成出一系列不同側鏈基密度的聚3-烷基?吩衍生物，如:poly (3-octylthiophene)簡稱(POTH)、Poly(3,3"-dioctyl-2,2';5',2"– terthioph ene)(POTTOT)、Poly(3'-octyl -2,2'-bithiophene)(POTT)、Poly (3-octyl- 2,2';5',2"-terthiophene)(PTOTT)等。以探討其導電穩定性。實驗發現側鏈基密度越大的聚合物，摻雜後具有較好的結晶性，導電度也較好，其中又以主鏈堆疊最緊密的POTTOT導電度最好但導電穩定性不佳，去摻雜速度也最快。此外聚?吩的螢光效率，也受側鏈基的影響，研究結果發現，聚合物的側鏈基密度越低，結晶性越差螢光強度越強，但因POTTOT主鏈堆疊最緊密，螢光強度最弱。然而側鏈基密度的大小對其螢光的放光波長並沒有很大的影響，但若在POTTOT與POTT兩聚合物主鏈上的?吩用?啶取代，所得之Poly(2,6-Bis-(3-octylthiophene-2yl)-pyridine) (POTPyOT)與Poly(2-(3- octylthiophene -2-yl) -pyridine)(POTPy)，其放光波長除了有明顯的藍位移外而且螢光效率好很多。聚合物製成薄膜時完全沒有結晶性，可見在主鏈加入?啶環可使聚合物呈現非晶性，而且增加聚合物的放光強度。 Abstracte In 1977, Shirakawa, MacDiarmid, and Heeger had reported the doping of polyacetylene to increase its conductivity up to 109 times. The era of conducting polymer was starting. Polythiophene was synthesized in 1983 and showed good conductivity in the doped state, Nevertheless, it was not soluble in common organic solvent, therefore hard to process. Therefore, the alkyl group was added in the thiophene to increase its solubility, unfortunately, the conducting stability of polyalkylthiophene decreased due to the mobility of the alkyl side chain, it showed a room temperature dedoping phenomenon. In this thesis, we synthesized a series of poly3-alkylthiophene derivatives with different side chain density ( such as Poly(3-octylthiophene) (POTH)、Poly (3,3"-dioctyl-2,2';5',2"–terthiophene) (POTTOT)、Poly(3'-octyl-2,2'-bi thiophene) (POTT)、Poly(3-octyl-2,2';5',2"-ter thiophene) (PTOTT) ) try to find a polymer with good conducting stability and still keep good solubility. We found that polymer with high side chain has high crystallization and conductivity after doping. POTTOT has the highest conductivity due to the close packing of the polymer chains in film state, but at the same it also has the lowest conducting stability. Polythiophene also has luminescence property. We found that polymer with lower side-chain density has a higher quantum yield. We also prepared polythiophenes with pyridine ring (such as Poly(2,6-Bis-(3-octyl thiophene-2yl)-pyridine) (POTPyOT) and Poly(2-(3-octylthiophene-2-yl) -pyridine) (POTPy) ) . The luminescence studies showed that the pyridine ring in polymer backbone caused the blue-shift of the emission spectra and at the same time destroy the order arrangement of the polythiophene chains, therefore, enhanced the luminescence intensity significantly. |
