摘要

本研究以異位合成(ex-situ)的方式，首先將氧化鈰奈米顆粒與具備不同電特性之共軛高分子進行混成，經由分析結構變化與量測所得複合材料之光學特性，探討氧化鈰奈米顆粒-高分子複合物的介面電荷轉移作用。選擇氧化鈰的優點在於可經由Ce的價數變化，了解電荷轉移的方式以及轉移程度。所使用的高分子有兩類，第一為2,7-連接的9,9'-螺二芴和萘雙酰亞胺，是經由鈀催化的Suzuki-Miyaura交叉偶聯反應製備，為具備電子接受特性的共軛共聚物，在本研究中作為受體。另一種為常見之P3HT，具有供電子特性，在本研究中作為施體。接著，進一步比較P3HT與具備不同表面特性之氧化鈰奈米顆粒作用的結果。表面缺陷量高之氧化鈰奈米顆粒由共沉澱法合成，表面缺陷量低的則是經二羧酸進行表面改質。
根據穿透式電子顯微鏡觀察結果指出，所選用的兩種共軛高分子均能將氧化鈰奈米顆粒均勻的分散，複合物中的氧化鈰奈米顆粒含量可達40 wt%。進一步提高氧化鈰奈米顆粒的含量則會形成團聚。X光吸收光譜與拉曼光譜結果證實電荷轉移作用的發生，且電荷轉移程度與介面面積成正比。此外，電荷轉移的方向與高分子的類型有關。接著以穩態光譜分析光誘導的電荷轉移和復合過程，發現複合物有顯著的螢光猝滅，顯示複合材料具有更高的光活性。其中以施體類型的高分子-氧化鈰奈米顆粒複合物效果較佳。在由受體類型的高分子-氧化鈰奈米顆粒複合材料中，還觀察到光譜的紅移現象。最後，在所有高分子-氧化鈰奈米顆粒複合材料中均觀察到室溫鐵磁性，其起源可歸因於氧化鈰奈米顆粒表面的缺陷以及共軛高分子的層狀結構。

Abstract

In this study, ex-situ synthesis was used to mix cerium oxide nanoparticles with conjugated polymers with different electrical properties in the first part. Through analyzing the structural changes and measuring the optical characteristics of the composites, charge transfer at interface can be studied. The advantage of choosing cerium oxide is that the way and degree of charge transfer can be revealed easily through the valence change of Ce. Two types of polymers were chose. The first was a conjugated copolymer 2,7-linked 9,9′- spirobifluorene and naphthalene bisimide which was prepared by palladium catalyzed Suzuki-Miyaura cross coupling reaction. This polymer was used as electron acceptor polymer. The other is P3HT, which has electron-donating properties and was used as a donor in this study. In the second part, P3HT was mixed with cerium oxide nanoparticles with different surface characteristics. Cerium oxide nano particles with high surface defects were synthesized by co-precipitation method, while those with low surface defects were modified by dicarboxylic acid.
According to the transmission electron microscopy observation, the two conjugated polymers used can uniformly disperse the cerium oxide nanoparticles, and the content of the cerium oxide nanoparticles in the composite can reach 40 wt%. Further increasing the content of cerium oxide nanoparticles will lead to agglomeration. X-ray absorption and Raman spectroscopy results confirm that charge transfer occurs and that the degree of charge transfer is directly proportional to the interface area. In addition, the direction of charge transfer depends on the type of polymer. Then, the steady-state spectrum was used to analyze the light-induced charge transfer and recombination processes. It was found that the composite had significant fluorescence quenching, indicating that the composite had higher photoactivity than individual component. Among them, donor-type polymer-cerium oxide nanoparticle composites have better effects. In the acceptor-type polymer-cerium oxide nanoparticle composite, red shift was observed in photoluminescence spectrum. At last, room temperature ferromagnetism was observed in all polymer-cerium oxide nanoparticle composites, and its origin was attributed to defects on the surface of the cerium oxide nanoparticle and the layered structure of the conjugated polymer.

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