臺灣博碩士論文加值系統

自我組裝單分子層(self-assembled monolayers, SAMs)受X-ray、電子束或離子束等物理源照射後可呈現負型或正型阻劑的特性；且利用電子束照射可促進SAMs分子的置換反應；除了前述的物理源之外，順流式微波電漿也是一種對SAMs改質的方法。因此，本研究利用順流式微波氮氣電漿對以化學吸附於金面上的octadecanethiol (ODT) SAMs進行改質，ODT/Au以金網遮罩後暴露於電漿進行圖案轉移，接著利用金蝕刻液進行蝕刻反應使轉移後的圖案顯影；隨後利用Mercapto-undecanoic acid (MUA)的酒精溶液進行置換反應測試電漿處理過的ODT/Au，觀察是否存在來自MUA的新S-Au鍵結及COOH尾端官能基來識別置換反應的發生。藉由同步輻射高解析X光光電子能譜術及掃描式光電子顯微術分析各個不同階段的表面鍵結變化，以探討兩個主題：形成負型或正型阻劑的可能機制，以及隨著電漿處理後進行的置換反應發生程度。
實驗結果顯示，藉著控制不同電漿處理時間，可使電漿改質後的ODT/Au呈現出負型或正型阻劑的特性，造成此現象的可能效應有：頭端分子、碳鏈層及尾端官能基的氧化及脫附而破壞SAMs在金面上的結構，還有碳鏈的交錯鏈結而強化分子的結構。經電漿處理過的ODT分子則會因MUA而發生脫附與置換。基於這些研究結果，利用電漿在SAMs上進行圖案轉移並結合分子的置換反應，未來可應用於製作微米/奈米等級元件如微流道、微型生物感晶片等。

Self-assembled monolayers (SAMs) can behave as negative or positive resist after irradiated by physical sources such as X-ray, electron beam or ion beam. As well, the electron beam irradiated SAMs can thereafter promote exchange reactions with other SAMs molecules. In addition to the mentioned physical sources, the downstream microwave plasma can provide an alternative method to modify SAMs. In this study, we applied the downstream microwave nitrogen plasma for the modification of the octadecanethiol (ODT) SAMs chemically adsorbed on Au. The ODT/Au was masked by Au mesh and patterned by the exposure of plasma. The patterned ODT/Au was then developed by Au etching process. Subsequently the plasma-exposed ODT/Au was particularly examined by the molecular exchange reaction with Mercapto-undecanoic acid (MUA) in ethanol. The exchange reaction on the plasma-exposed ODT/Au was distinguished by the presence of newly formed S-Au bonds and the COOH tail group from MUA. Synchrotron-based high resolution X-ray photoemission spectroscopy and scanning photoelectron microscopy were applied to characterize the surfaces prepared in different stages. Two topics were discussed: a possible mechanism that formed a negative or positive resist and an extent of subsequent exchange reaction on the plasma-exposed ODT/Au. Experimental results demonstrated that by controlling the plasma exposure time, the modified ODT/Au was competent to behave as negative or positive resist. The most probable process is related to the oxidization or molecular desorption (i.e. with the tail group, alkyl chains, and the head group) that tends to damage SAMs structure adsorbed on Au as well as cross-linking among alkyl chains (i.e. with a significant amount of lasting S-Au bonds) that tends to enhance the molecular configuration. The plasma-exposed ODT molecules on Au could also be desorbed and exchanged by MUA. Based on these findings, it is promising to apply the plasma-patterned SAMs combined with the molecular exchange reaction for making the variety of micro/nano devices such as micro-fluid channels and micro-scale bio-chip.

第一章 序論 1
1.1 前言 1
1.2 研究動機 2
1.3文獻回顧 2
1.3.1 自組裝單分子層 2
1.3.2 以自組裝單分子層作為蝕刻阻劑 4
1.3.3 藉由電子束照射促進自組裝單分子層的置換反應(exchange reaction) 5
1.3.4 電漿對自組裝單分子層之表面處理 6
1.4 研究目的 7
第二章 理論基礎 8
2.1 自組裝單分子層 8
2.1.1 自組裝單分子層基本介紹 8
2.1.2 自組裝單分子層的結構描述與排列方式 11
2.2 電漿簡介 14
2.2.1 電漿放電形式 14
2.2.2 電漿反應 15
2.2.3 電漿表面改質 16
2.2.4 電漿系統 18
2.3 高解析光電子能譜儀以及掃描式光電子顯微術分析 26
第三章 材料與方法 31
3.1 自組裝單分子層製備 31
3.2 實驗設計 31
3.2.1 順流式氮氣電漿應用於SAMs為超薄光阻的Au表面圖案轉移 32
3.2.2 ODT SAMs經順流式微波氮氣電漿處理後分子的置換反應 34
3.3 順流式微波電漿機台 34
第四章 順流式氮氣電漿應用於SAMs為超薄光阻層的Au表面圖案轉移 36
4.1 順流式氮氣電漿處理後ODT/Au的表面型態及鍵結變化情形 36
4.1.1 SEM表面型態觀察 36
4.1.2 XPS與SPEM分析表面鍵結變化 38
4.2 順流式氮氣電漿處理ODT/Au經濕式蝕刻顯影後之圖案 48
第五章 ODT SAMs經順流式微波氮氣電漿處理後分子的置換反應 51
5.1 未經電漿處理的SAMs分子置換反應 51
5.2 ODT SAMs經電漿處理後分子的置換反應 53
5.2.1 XPS分析表面化學鍵結變化 53
5.2.2 SPEM分析表面微區化學鍵結變化 56
結論 63
參考文獻 64

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