利用自組裝高分子共聚物來製備規則奈米結構，近年來受到相當大的關注，本論文利用二嵌段聚苯乙烯和聚甲基丙烯酸甲酯(PS-b-PMMA)高分子共聚物經由自組裝來形成規則排列的奈米結構。透過MPTS的自組裝單分子層使得高分子材料和矽基材之間的界面能量中性化，當不對稱(asymmetric)比例的二嵌段高分子經過真空退火後，會微相分離成最密六方的柱狀(PMMA)和網狀(PS)的結構，再經過選擇性蝕刻移除掉PMMA後，就可形成孔洞大小約18奈米，孔洞間距約36奈米的高分子模板。本研究針對表面改質的情況、旋佈高分子轉速的影響以及退火時間長短的控制均有做深刻的討論。
而對體型微加工而言，我們提出了不需要高度真空及高貴的儀器的方法-金屬輔助化學蝕刻。利用金催化的特性以及光阻當遮蔽阻擋蝕刻，並透過HF和H2O2的混合蝕刻液，成功在矽基材上特定的區域進行非等向性蝕刻。此外我們結合了自組裝高分子共聚物模板以及金屬輔助化學蝕刻的結果，利用金粒子在模板孔洞內沉積的效果，在矽基材上蝕刻出和高分子模板相同規則且整齊的奈米孔洞。另一方面，透過模板lift off後產生的鉻粒子陣列當作遮蔽層，我們同樣使用金屬輔助化學蝕刻來蝕刻矽基材，藉此製備出規則排列的矽奈米線結構，更進一步結合黃光微影製程，成功使得矽奈米線結構具有選定的空間分佈。

This thesis presents a novel integration scheme that can fabricate complex micro-nano hybrid silicon structures. The structures are formed by metal-assisted chemical etching, while microlithography and self-assembled diblock copolymer nano- templates are employed to define their geometries. The nano-templates are made of P(S-b-MMA) copolymer that can self-assemble into arrays of 18-nm-diameter PMMA cylinders hexagonally packed in a PS matrix with a lattice constant of 36 nm. To facilitate the self-assembly process, a thin layer of 3-(p-methoxy-phenyl)propyl- trichloro-silane is coated between P(S-b-MMA) and silicon substrate. Once PMMA is selectively removed, the resulting nanoporous PS film is employed to control the deposition of metal nanodots. In the prototype demonstration either chromium or gold is deposited, while chromium and gold is used as the blocking and catalytic material in the etching process, respectively. Meanwhile, photolithography is employed to realize the micro-patterning of metallic thin films. Throughout the process, reactive ion etching is used repeatedly to clean the substrate surface. Finally, the gold-assisted chemical etching is carried out in a solution consisting of deionized water, H2O2, and HF to produce the desired micro-nano hybrid silicon structures. It is demonstrated that the presented integration scheme is a highly repeatable method to form well-aligned, crystalline silicon nanowires with tunable diameters below 100 nm and microstructures as well. As such, the presented integration scheme can fabricate complex micro-nano hybrid structures, which are desired for a variety of cooling and biological applications.

第一章 緒論 1
1-1 背景 1
1-2 自組裝高分子團聯式共聚物 2
1-2-1 何謂自組裝? 2
1-2-2 團聯式共聚物 3
1-2-3 自組裝高分子團聯式共聚物 3
1-3 自組裝單分子層 4
1-4 金屬輔助化學蝕刻 4
1-5 反應式離子蝕刻 6
1-6 研究動機與目標 7
第二章 文獻回顧與探討 9
2-1 自組裝高分子共聚物模板製作之研究 9
2-1-1 自組裝高分子團聯式共聚物 9
2-1-2 利用PS-r-PMMA當作中性層 13
2-1-3 利用金(Au)當作中性層 15
2-1-4 利用MPTS的自組裝單分子層當作中性層 16
2-1-5 添加油酸對於PS-b-PMMA自組裝的影響 17
2-2 金屬輔助化學蝕刻的應用 18
2-2-1 利用光阻當遮蔽蝕刻矽基材以產生微結構 18
2-2-2 利用陽極氧化鋁模板(AAO)作為模板製備矽奈米線 20
2-2-3 利用高分子球做為模板製備矽奈米線 22
2-2-4 利用自組裝高分子共聚物做為模板製備矽奈米線 24
2-3 自組裝高分子共聚物模板的其他應用 25
2-3-1 應用於Lift Off製程 25
2-3-2 應用於翻模PDMS結構 27
2-3-3 應用於提升MOS效能 28
2-4 利用SF6/O2電漿非等項性蝕刻矽基材 29
第三章 製程原理與方法 31
3-1 製程原理 31
3-1-1 利用高分子團聯式共聚物自組裝之原理 31
3-1-2 PS-b-PMMA高分子共聚物介紹 33
3-1-3 自組裝單分子層(SAMs)的作用 36
3-1-4 金屬輔助化學蝕刻之原理 36
3-1-5 給定莫耳濃度計算所需溶液的體積比例 39
3-1-6 RIE蝕刻機制 39
3-1-7 電子槍蒸鍍系統 40
3-1-8 場發射掃描式電子顯微鏡 41
3-2 實驗藥品 41
3-3 實驗儀器 42
3-4 自組裝高分子共聚物模板的製作 43
3-4-1 製備MPTS的自組裝單分子層 43
3-4-2 利用自組裝PS-b-PMMA高分子共聚物製備奈米模板 43
3-5 利用黃光微影製程搭配金屬輔助化學蝕刻製備微結構 45
3-5-1 黃光微影製程 45
3-5-2 金屬輔助化學蝕刻製備微結構 45
3-6 利用PS-b-PMMA高分子模板搭配金屬輔助化學蝕刻製備奈米孔洞結構 47
3-7 利用PS-b-PMMA高分子模板lift off後的Cr粒子陣列製備奈米線結構 48
3-8 整合黃光微影與奈米線製程製備可控制區域呈現奈米線結構 49
第四章 實驗結果與討論 50
4-1 自組裝高分子共聚物模板的製作 50
4-1-1 表面改質 50
4-1-2 轉速對自組裝的影響 53
4-1-3 退火時間對自組裝的影響 55
4-1-4 模板於AFM下的展示與其在matlab上的應用 57
4-2 利用RIE打氧電漿修飾模板孔洞大小 58
4-3 Lift Off製程 61
4-4 利用黃光微影製程搭配金屬輔助化學蝕刻製備微結構 66
4-4-1 金膜表面 66
4-4-2 金屬輔助化學蝕刻製備微結構 67
4-5 利用PS-b-PMMA高分子模板搭配金屬輔助化學蝕刻製備奈米孔洞結構 70
4-6 利用PS-b-PMMA高分子模板lift off後的Cr粒子陣列製備奈米線結構 72
4-6-1 利用RIE步驟加大Cr粒子與矽基材的高低落差 72
4-6-2 利用Cr粒子陣列搭配金屬輔助化學蝕刻製備奈米線結構 74
4-7 整合黃光微影與奈米線製程製備可控制區域呈現奈米線結構 75
4-7-1 利用黃光微影定義區域 77
4-7-2 將有光阻的區域轉成Cr粒子陣列 78
4-7-3 利用奈米等級的Cr粒子與微米等級的Cr區域製備奈微複合結構 79
第五章 結論 80
參考文獻 81

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