氧化鋅/聚己烷噻吩高分子與氧化鋅/雙嵌段共聚高分子奈米原位混成系統：自組裝、特性及光電應用之探討

Abstract

研究藉由聚己烷噻吩導電高分子以及新穎的共軛─共軛雙嵌段共聚高分子當結構模板，製作了一系列混成氧化鋅(ZnO)奈米粒子的有機/無機混成系統。本研究中揭露一種簡易的原位合成方法，探討zinc oxide/poly(3-hexylthiophene) (ZnO/P3HT)奈米混成系統和zinc oxide/ poly(2,5-dihexyloxy-p-phenylene)-b-poly(3-hexylthiophene) (ZnO/PPP-b-P3HT) 奈米混成系統的自組裝行為。因此在本實驗中使用醋酸鋅(Zn(CH3COO)2．2H2O)做為前驅物，而高分子P3HT的噻吩官能基能與鋅離子(Zn2+)進行螯合反應，接著藉由薄膜在大氣環境下加熱至200oC三十分鐘以上或者在混合溶液中添加有機鹼tetramethylammonium hydroxide (TMA-OH)，使鋅離子轉換為氧化鋅(ZnO)。 氧化鋅奈米粒子/高分子 混成薄膜可由兩種方法製備：第一種方法，首先製備鋅離子/高分子混合溶液後，接著將此溶液利用滴落塗佈方式在基材上使之成膜並在室溫乾燥，最後將基材放置於加熱台上，在空氣中以200oC加熱30分鐘。第二種方法，將TMA-OH加入準備好的鋅離子/高分子混合溶液，接著再將反應完的溶液以滴落塗佈法在基材上使之成膜並在室溫下乾燥。 從FTIR光譜的結果證實，P3HT上的C-S鍵與鋅離子的螯合效果產生化學位移，而UV-visible的吸收光譜也闡述了鋅離子在混合系統中的比例關係，至於氧化鋅奈米粒子/高分子混成系統的結晶度和形態則是分別透過GIWAXS光譜儀和TEM來了解其特性。利用GIWAXS光譜儀確認，成功的合成出氧化鋅奈米粒子，並且高分子在甲苯溶劑下有良好的方向性。經由TEM的型態可看出，因為高分子的噻吩官能基能與鋅離子(Zn2+)有螯合反應，所以利用加熱轉換的氧化鋅奈米粒子排列在高分子奈米線上，再經由退火實驗，能使高分子結晶更好，氧化鋅奈米粒子的結晶變成連續相，此現象有助於高分子與無機物的連續通道，可運用於太陽能元件上。

In this study, we fabricated organic/inorganic hybrid that contains zinc oxide (ZnO) nanoparticles synthesized in the presence of a conducting homopolymer and a novel conducting-conducting di-block copolymer as a structure template for the hybrid system. A simple in-situ synthesis of the self-assembly behavior zinc oxide/poly(3-hexylthiophene) (ZnO/P3HT) nanohybrid systems and zinc oxide/poly(2,5-dihexyloxy-p-phenylene)-b-poly(3-hexylthiophene) (ZnO/PPP-b-P3HT) nanohybrid systems were investigated. We use the zinc acetate dehydrate (Zn(CH3COO)2．2H2O) as a precursor for ZnO nanoparticles and P3HT as the functional host to chelate zinc ion. The chelated Zn2+ was converted into ZnO by heating in the air at 200oC or by adding tetramethylammonium hydroxide (TMA-OH) as the organic base. The film samples of ZnO/polymer hybrid were prepared by the following two methods. First, we prepared a Zn2+/polymers solution, and then drop casted the Zn2+/polymers solution directly onto substrates. The coated substrates were then heated at 200oC for 30 minutes for characterization. Second, we prepared the Zn2+/polymers solution, and then added TMA-OH into solution for the ZnO synthesis. Immediately, after that we drop casted the solution onto a substrate. From the study of FTIR spectra of the Zn2+/polymers solution, we confirmed that P3HT is chelated with zinc ion. The UV-Visible spectra measurement also illustrated the effect of ZnO nanoparticles ratio for in the hybrid system. The crystallinity and morphology of ZnO nanoparticles/polymer hybrid films were characterized by GIWAXS and transmission electron microscope (TEM). From GIWAXS spectra, the polymer which dissolved in toluene has good orientation and Zn2+ was converted into ZnO by heating in the air successfully. The TEM images show that P3HT was the chelating zinc ion when the film was heated in the air at 200oC, and it can enhance the co-organization crystalline of the P3HT/ZnO nanoparticles hybrid when put the heated film into annealer under inert atmosphere at 200oC for 1 day.