臺灣博碩士論文加值系統

長鏈烷基硫醇自組裝單分子層(Alkanethiol self-assembled monolayers, AT-SAMs)對於特定化學蝕刻液具特定抵抗性；同時，其與物理源(X-ray、離子束、電子束)具有誘導發生反應的作用而形成負/正型阻劑(resist)。因此，本研究企圖使用低能量(E＜1 keV)電子束微影術(Low energy electron beam lithography, LE-EBL)作為微影技術，並於微影後使用濕式蝕刻方式進行顯影來進行圖案的製作。首先，在矽晶圓上使用電子束蒸鍍5 nm Ti層，隨後在其上蒸鍍50 nm Au膜得到以Au(111)面為主的表面，同時將蒸鍍好的Au膜及對排列於Au膜面上之正十八硫醇(Octadecanethiol, ODT)試片進行濕式蝕刻分別得到兩種試片Au之蝕刻終止點，以確認ODT排列於Au膜上後對Au蝕刻液的抗蝕效果。接著，以靜態水滴接觸角分析50eV低能量電子束照射不同劑量並曝露於大氣後ODT/Au試片表面親疏水性的改變，以決定微影照射劑量；再將ODT/Au試片經所選擇的劑量照射並曝露於大氣後進行表面元素分析，最後以Au蝕刻液進行顯影。結果發現：以50 eV 低能量電子在照射劑量7.04 mC/cm2微影並曝露於大氣後，受到來自於ODT/Au碳鏈間的交聯、部分的S-Au鍵結破壞以及照射後立即曝露大氣所吸附於表面的碳氧化物種的共同影響下，ODT SAMa於Au膜基材上將形成更緊密複雜的結構而作為負型阻劑，經後續濕式蝕刻15分鐘後將顯影出來Au的負型圖案；當提升照射劑量至64.06及128.13 mC/cm2後，由於ODT/Au上碳鏈及S-Au鍵結的大量破壞，將使ODT/Au結構不能穩固且緊密地排列於Au膜基材上，顯影時Au蝕刻液將容易穿過ODT SAMs抵達S/Au界面而移除Au，而形成正型圖案。由此，ODT/Au可在控制不同LE-EBL照射劑量並曝露大氣後將可分別作為負型阻劑及正型阻劑，於Au蝕刻液中顯影出Au的負型圖案與正型圖案。

Alkanethiol self-assembled monolayers (AT-SAMs) have good resistance for specific wet-etching solutions and behave as negative/positive resists after irradiated by physical sources such as X-ray, ion beams, and electron beam. The aim of this study is to fabricate gold pattern via the low energy (E＜1 keV) electron beam lithography (LE-EBL) followed by exposing to air, then developing with gold-etching solutions for octadecanethiol (ODT) on the substrate. The substrate is prepared by first electron-beam evaporating a thickness of 5 nm titanium on the silicon wafer, and followed evaporating 50 nm thickness of gold on the titanium layer. Subsequently, immersing of the gold substrate and ODT/Au samples into the gold-etching solution in order to find out the end time point of gold layer of which, leading to understanding of the resistivity of ODT/Au in the etching solution. Also, the process doses of LE-EBL are determined from the dose-static contact angle relation, followed by HRXPS analysis. Finally, the gold patterns are obtained by gold-etching solution development. Concluded from the analyses of negative-positive resist transformation, the experimental procedure of ODT/Au was first irradiated by 50eV LE-EBL with three specific doses, after that proceeded to exposed to air. With the dose of 7.04 mC/cm2, ODT/Au will become a more strengthened structure and then form a negative resist in the correlation with cross-linking from alkyl matrix, partial breakdown of S-Au bonding and surface adsorption by air-borne species. Thus, it can obtain a gold pattern via gold-etching process. Besides, as a result of massive breakdown of alkyl matrix and S-Au bonding from ODT/Au under irradiation with doses of 64.06 and 128.13 mC/cm2, ODT SAMs would form a loose-packed structure on the gold substrate. The ODT/Au becomes less resistive for gold-etching and a positive gold pattern would form after gold-etching. By controlling LE-EBL doses and being exposed to air at the following step, ODT/Au could behave either as negative or positive resists. Finally, it will perform the negative and positive gold patterns after gold-etching process.

摘要 1
Abstract 2
誌謝 4
目錄 6
圖目錄 9
表目錄 12
第一章 緒論 13
1-1 前言 13
1-2 文獻回顧 14
1-2.1 自組裝單分子層 14
1-2.2 以烷基硫醇自組裝單分子層作為負型蝕刻阻劑之物理源微影術 16
1-2.3 經低能量電子束微影之烷基硫醇自組裝單分子層的原理 17
1-2.4 烷基硫醇自組裝單分子層在濕式蝕刻液中的行為 18
1-3 研究動機與目的 18
第二章 理論基礎 20
2-1 蒸鍍技術及原理 20
2-1.1薄膜沈積原理 20
2-1.2電子束蒸鍍原理及技術 22
2-2 自組裝單分子層原理及技術 23
2-2.1 自組裝單分子層的原理 23
2-2.2 硫醇類自組裝單分子層 24
2-3 物理源微影術對烷基硫醇自組裝單分子層的作用 27
2-3.1 物理源對SAMs的作用 27
2-3.2 電子束微影術對烷基硫醇自組裝單分子層的作用 31
2-4 濕式化學蝕刻 36
2-4.1濕式化學蝕刻原理 36
2-4.2 AT-SAMs/Au的濕式蝕刻原理 37
第三章 實驗材料與方法 40
3-1 Au薄膜製備與分析 41
3-2 自組裝單分子層成膜技術 43
3-3 Au蝕刻液對Au膜基材及ODT/Au自組裝薄膜的蝕刻終止點及分析 44
3-4 低能量電子束微影術及分析 44
3-5 材料表面形貌及元素分析 46
第四章 結果與討論 48
4-1 蒸鍍膜厚對ODT/Au自組裝薄膜成膜品質之評估 48
4-1.1對Au膜晶面及其平坦度的影響 48
4-1.2 膜厚50 nm的Au面之表面形貌與膜厚均勻性分析 50
4-1.3 ODT/Au自組裝薄膜膜厚及其表面形貌分析 51
4-2 蒸鍍Au膜及ODT/Au自組裝單分子層的蝕刻終點分析 53
4-3低能量電子束微影ODT/Au自組裝薄膜及經Au蝕刻液顯影的影響 54
4-3.1 不同照射劑量下的靜態水滴接觸角評估 54
4-3.2以低能量電子束微影ODT/Au後經濕式蝕刻顯影後之圖案 55
4-3.3以低能量電子束微影ODT/Au作為負型蝕刻阻劑經濕式蝕刻顯影後之圖案分析 58
4-3.4以低能量電子束微影ODT/Au作為正型蝕刻阻劑經濕式蝕刻顯影後之圖案分析 60
4-3.5 低能量電子束照射不同劑量對ODT/Au自組裝薄膜造成各元素的變化 65
4-3.6 ODT/Au在50 eV低能量電子束照射不同劑量後經曝露大氣產生之正/負型阻劑的可能機制 68
第五章 結論 71
第六章 參考文獻 72
附錄一 低掠角X光繞射分析 79
附錄二 橢圓偏光術原理及技術 80
附錄三 靜態水滴接觸角 83
附錄四 高解析X光光電子能譜分析術 85
附錄五 掃描式探針顯微鏡簡介 90

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