奈米尺度材料是近年來材料研發與分析的主要發展方向，其中過渡金屬更因其d層軌域電子的關係，可以表現出多種特別的性質或與氧原子表現出多種的氧化態而受到密切的注意，因此電子顯微鏡相關的儀器及技術的發展及應用也成為主流，隨著各種氧化物奈米線的製備成功，因其尺度微小，對量測環境的變化非常敏感，所以在量測其物理性質時非常容易受到儀器的影響而產生誤差，而造成往往量測到的訊號大部分皆由量測誤差貢獻，反而將奈米線本身的訊息掩蓋，而無法得到正確的資訊，因此發展精確量測並即時觀察單根氧化物奈米線的性質的量測技術有其必要。另一方面，在過渡金屬薄膜中，隨著奈米顆粒的加入，其物理性質如光學、光電、硬度等隨之產生改變，隨著所加入材料的分佈情形不同，對於其性質也產生巨大的改變，如果不能觀察到其正確的微結構分佈，也就沒有辦法推論影響其物理性質改變的原因，而由於奈米晶體於母材中分佈相對混亂，且通常其結構嵌合在母材中，因此很難利用常規的電子顯微鏡技術去觀察分析出奈米晶體於母材中的分佈情形，因此發展一先進電子顯微鏡技術去觀察奈米晶體於過渡金屬薄膜中的分佈也是當前研究奈米尺度材料不可或缺的發展方向。
本論文主要分為兩個部分:第一部分是利用穿透式電子顯微鏡以及附掛其上的穿隧式電子顯微鏡系統觀察量測氧化釕奈米線的結構、成份、成長方向以及其電學性質等特性，STM-TEM系統可以同時量測單根奈米線的電性又可即時觀測接觸情況。第二部份則是利用環狀物鏡光圈的概念所發展出的多重中心暗場成像技術，分析氮氧化鋯薄膜中氮化鋯以及氧化鋯兩相奈米結晶的分佈情形，並根據影像結果對氮氧化鋯薄膜中隨著氧原子含量的變化其硬度隨之變化的情形做出合理的解釋。隨著此項影像技術應用於多晶薄膜材料系統，對於多晶薄膜中，各項物理性質的變化，可以得到直接的分析並進行合理的解釋。

Single-crystalline RuO2 nanowires were grown by using a thermal evaporation method. A control of the sizes _width and length_ and the length-to-width ratio of the nanowires were achieved by tuning the growth time. A transmission electron microscope–scanning tunneling microscope technique invoking one-nanocontact electrical characterization was adopted to determine the room-temperature resistivity ~100 μΩ-cm of the nanowires. An e-beam lithography technique facilitating two-nanocontact measurements was performed to establish the metallic characteristic of individual nanowires. The authors found that a nanocontact may introduce high contact resistance, nonlinear current-voltage characteristics, and even semiconducting behavior in the temperature dependent resistance.
And a nanocrystalline ZrNxOy thin film was deposited using hollow cathode discharge ion-plating (HCDIP). ZrO2 and ZrN phases were detected by X-ray diffraction in the as-deposited film, suggesting phase separation during the growth process. This research performed a transmission electron microscopy (TEM) study on the mechanism of phase-separation and distribution in ZrNxOy thin films and related the phase fraction with the film properties. Since the crystallographic orientations of the ZrO2 and ZrN phases are random, the microstructure of the separated phases is studied with multiple central dark-field (MCDF) technique. The compositional distribution between the separated phases is analyzed with nano-beam energy dispersive X-ray spectroscopy (EDX). The results showed that zirconium oxynitride (ZrNxOy) thin film has a columnar structure with an alternate arrangement of columns of ZrN and ZrO2, indicating that oxygen atoms are inter-columnarly segregated with a lateral diffusion distance lower than 20 nm.

摘要……………………………………………………………………I
Abstract………………………………………………………………II
目錄……………………………………………………………………III
表目錄…………………………………………………………………VI
圖目錄…………………………………………………………………VII

第一章 前言………………………………………………………1
第二章 文獻回顧…………………………………………………5
2-1氧化釕………………………………………………………………6
2-1-1晶體結構…………………………………………………………7
2-1-2氧化釕之金屬導電性……………………………………………7
2-1-3氧化釕晶體的製備方式…………………………………………8
2-1-4氧化釕應用………………………………………………………10
2-1-5 氧化釕奈米線成長……………………………………………12
2-1-6微奈米級金電極四點量測奈米線電性…………………………13
2-1-7 TEM-STM系統兩點量測奈米線電性……………………………14
2-2 氮氧化鋯材料………………………………………………………16
2-2-1氧化鋯基本特性…………………………………………………17
2-2-2 氮化鋯基本特性………………………………………………18
2-2-3氮氧化鋯薄膜基本特性…………………………………………19
2-2-4 氮氧化鋯薄膜製備……………………………………………19
2-2-5 穿透式電子顯微鏡於觀察氮化鈦薄膜的應用…………………20
第三章 實驗及分析方法……………………………………………29
3-1 氧化釕奈米線…………………………………………29
3-2 掃瞄穿隧式顯微鏡應用於穿透式電子顯微鏡……………………30
3-3 氮氧化鋯薄膜分析實驗方法………………………………………31
3-4 穿透式電子顯微鏡分析氮氧化鋯薄膜方法………………………31
第四章 單根氧化釕奈米線實驗結果與討論………………………35
4-1掃瞄式電子顯微影像觀察…………………………………………35
4-2 TEM高分辨率顯微影像觀察………………………………………36
4-3 X光繞射分析………………………………………………………36
4-4 氧化釕奈米線成長特性分析………………………………………37
4-5 STM-TEM兩點量測系統電性分析…………………………………38
4-6 電子束微影探針量測系統…………………………………………38
4-7兩點量測系統之誤差來源--接觸電阻……………………………39
第五章 氮氧化鋯薄膜中雙相分佈分析結果與討論………………55
5-1 氮氧化鋯薄膜基本性質分析………………………………………55
5-2 穿透式電子顯微鏡分析……………………………………………57
5-2-1 厚度量測…………………………………………………………59
5-2-2 多重中心暗場成像………………………………………………59
5-2-3 能量色散X光繞射光譜分析……………………………………61
第六章 結論……………………………………………………………66
第七章 未來研究方向…………………………………………………68
參考文獻…………………………………………………………………70

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