本篇嘗試將第二類型導電高分子透過物理性改質製備成二極體第二類型導電高分子為高分子本身不導電，透過奈米導電材(奈米碳管或碳黑)的添加形成導電網路，物理改質是將無機酸(硫酸鐵溶液)加入親水性高分子(聚乙烯醇)再加入奈米碳管。本實驗利用球磨機震盪以及攪拌磁石隔水加熱Fe2(SO4)3/多壁奈米碳管/聚乙烯醇複合材料，在乾燥過程中施加不同大小的電壓，藉以分離硫酸鐵之正、負電荷在試片上下兩面，期望達到二極體P-N介面之效果。
研究發現在乾燥過程中施加高電壓可以較有效的分離電荷，且透過量測功函數的結果發現藉由施加電壓分離電荷之效果與半導體中N-doped、P-doped之影響相似。此外在電性量測上，在各種硫酸鐵濃度以及乾燥過程中施加不同電壓大小的試片中，以添加0.5M硫酸鐵、乾燥時施加電壓600V製成的試片，在-5V、+5V時，具有最大的電阻值比。觀察其I-V curve圖可以發現，此試片比其他添加不同硫酸鐵濃度之試片在負偏壓時，漏電流遠小於其他試片，因此具有最大的電阻值比。因此推測添加0.5M硫酸鐵且在乾燥過程中施加電壓600V製成的試片，其形成的載子空乏區能最有效減少漏電流的產生，因此具有較良好的二極體表現。
本研究結果顯示可以使用親水性高分子、奈米碳管及無機酸製作出無毒性且製作過程較容易，同時也對環境較友善之二極體。

This project intends to make diodes based on the second type of conductive polymers which are made by mixing dielectric polymers with conductive nanostructures, such as carbon nanotubes and carbon blacks. Processes involve two steps including (i) mixing of Fe2(SO4)3(aq), PVA(aq) and carbon nanotubes; (ii) physical modification (i.e. electric field treatment of mixture, 0-600 V, 1 cm spacing when solidification). The aim of (ii) is to separate ions (Fe3+ and SO43-) toward both sides of solution prior to film solidification, so composite films become Fe3+ enriched on one side of the film and SO43- for the other. Unequal distribution of cations and anions which resembles that of p- and n- interfaces allows electric potential to be established, thus producing rectifying effect upon forward-reverse bias applications.
We observed the solution solidifying in high electric field is more effective to separate ions, and work function measurements show that charge separation under high electric field is similar to N- and P-doped semiconductors. In addition, electrical measurement shows that the specimen made of 0.5M Fe2(SO4)3 under 600V when solidifying gains the highest value of resistance ratio at -5V、+5V. Observing its I-V curve, this specimen gains a much lower leakage current under negative bias than others with different concentrations of Fe2(SO4)3, so it yields the largest value of resistance ratio. Specimen made of 0.5M Fe2(SO4)3 under 600V when solidifying produces the best depleted region that can effectively reduce the leakage current and possess an excellent performance of diode.
This work demonstrates that it is possible to use hydrophilic polymers, carbon nanotubes, and inorganic acid to manufacture non-toxic, processing with ease and eco-friendly diodes.

第一章 前言與實驗動機 1
第二章 基礎理論與文獻回顧 2
2-1奈米碳管的基本介紹 2
2-2奈米碳管的基本電性 4
2-3奈米碳管的合成 6
2-3-1電弧放電法 6
2-3-2雷射蒸發法 7
2-3-3化學氣相沉積流動法 8
2.4高分子與聚乙烯醇 9
2.4.1高分子 9
2-4-2聚乙烯醇(PVA) 11
2.5奈米碳管-高分子複合材料 12
2.5.1奈米碳管-高分子複合材料簡介 12
2.5.2奈米碳管-高分子複合材料導電性 12
2.5.3濕度對奈米碳管-水溶性高分子複合材料的影響 14
2.6二極體的基本介紹 16
第三章 研究方法 20
3.1實驗器材 20
3.1.1.藥品與耗材 20
3.1.2.儀器與設備 21
3.2實驗步驟 22
3.3實驗流程 23
3.4量測與分析 25
3.4.1.掃描式電子顯微鏡(Scanning Electron Microscopy，SEM) 25
3.4.2.化學分析電子能譜儀(Electron Spectroscopy for Chemical Analysis，ESCA) 26
第四章 實驗結果與討論 31
4.1. SEM微結構分析 31
4.2. 化學分析電子能譜儀 36
4.2.1.表面元素比例分析 36
4.2.2.複合材料之功函數量測 39
4.3.複合材料的電性量測 47
4.3.1.施加電場大小對試片電性的影響 47
4.3.2.硫酸鐵濃度對試片電性的影響 48
4.3.3.熱壓對試片電性的影響 48
4.3.4.試片電性的結果討論 49
第五章 結論 61
參考文獻 62

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