合成新穎導電高分子及利用高壓原位製程製備 奈米粒子混成系統：自組裝、光電性質研究

Abstract

本文中利用格林納聚合法成功合成出導性電高分子聚己烷噻吩以及新穎的全共軛共聚高分子。此兩種高分子再經由膠體滲透層析儀鑑定其分子量。 接著利用此兩種高分子作為樣板，與氧化鋅奈米粒子製作出原位奈米混成系統。我們使用二水合醋酸鋅作為氧化鋅之前驅物，而聚己烷噻吩鏈段作為其寄託處，將鋅離子螯合住。之後，利用一個全新的方式—高壓反應，將鋅離子轉化成氧化鋅奈米粒子。 高壓原位奈米混成系統樣品經由下面步驟製作。首先製備鋅離子與高分子之甲苯溶液，再將其塗佈至基材上，並等待甲苯及其他溶液揮發至乾燥。之後將乾燥後的樣品放入含有1.5毫升甲醇及1.5毫升水的高壓反應罐中，再放入150oC環境中反應兩個小時。 我們藉由X光電子能譜儀證實聚己烷噻吩鏈段有與鋅離子螯合。而此混成系統的形態由廣角度X光散射及穿透式電子顯微鏡來觀察分析。廣角度X光散射可以顯示出聚己烷噻吩鏈段在甲苯中有良好的排整性以及我們成功利用高壓反應將鋅離子轉換成氧化鋅；而穿透式電子顯微鏡也再一次證實聚己烷噻吩鏈段有與鋅離子螯合。紫外光-可見光光譜儀與光激發螢光頻譜則說明不同的氧化鋅奈米粒子的比例對於整個原位混成系統的影響。最後利用飛行時間二次離子質譜儀測試樣品的均一性以及是否分層。綜合上述，由於此高壓原位奈米混成系統具有特殊的光電性質，我們相信未來在應用上會有很大的潛力。

In this study, conventional conducting polymer poly(3-hexylthiophene)(P3HT) and brand new all-conjugated block copolymer poly(2,5-bis(2’-ethylhexyloxy) benzene)-b-poly(3-hexylthiophene)(PEHPP-b-P3HT) were synthesized via Grignard metathesis method (GRIM). Following, Gel permeation chromatographer (GPC) was used to characterize the synthesized polymers. Furthermore, we fabricated ZnO/conducting polymer in-situ nanohybrid system by using P3HT and PEHPP-b-P3HT as templates. We use zinc acetate dihydrate(Zn(Ac)2．2H2O) as the precursor of zinc oxide(ZnO) and P3HT segments as the anchorage to chelate zinc ions. After that, we utilize a novel method, high-pressure reaction, to convert chelated Zn2+ into ZnO. The high-pressure treatment in-situ nanohybrid samples were prepared by following steps. We prepared Zn2+/polymer toluene solution samples first and casted onto the substrates. Toluene and other solvents were evaporated slowly for several hours. When the samples were dried, they were put on the top of the solvent reservoir of the high-pressure reactor with some solvent composed of 1.5mL methanol and 1.5 mL water. Then, screwed the caps of high-pressure reactor tightly onto the reactor. And take the whole reactor in ambient atmosphere at 150oC for 2 hour. From XPS spectra, we ascertained that zinc ions were chelated by P3HT segments. And the morphology of ZnO/polymers hybrid samples were analyzed by GIWAXS and TEM. Through GIWAX, it indicated that P3HT dissolved in toluene possessed good orientation and Zn2+ was converted into ZnO successfully via high-pressure reaction. TEM images showed that P3HT segments successfully chelated zinc ions. UV-Vis and PL spectra illustrated the effects of different ZnO ratios in the nanohybrid system. Moreover, we use TOF-SIMS to test if the nanohybrid samples were homogeneous or not. In summary, because of the special optoelectronic properties of the high-press in-situ nanohybrid sytems, we confirmed that they will possess many applications in the future.