氣體電漿表面改質及濕式化學蝕刻法結合微奈米球微影術製備位置、尺寸可調控矽晶二維奈米結構陣列之研究

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姓名

林耀星(Yao-hsing Lin) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

氣體電漿表面改質及濕式化學蝕刻法結合微奈米球微影術製備位置、尺寸可調控矽晶二維奈米結構陣列之研究
(Fabrication of Site- and Size-controllable Periodic Arrays 2D Well-ordered Si Nanostructures by Plasma Modified Nanosphere Lithography and Chemical Wet Etching Processes)

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摘要(中)

本研究成功地利用奈米球微影術結合氣體電漿表面改質及非等向性鹼性溶液蝕刻技術在不同晶面指向之矽單晶基材上製備出密度、尺寸及形狀均可控制之規則有序排列矽基奈米結構陣列，並以SEM、AFM、TEM、SAED、EDS、XPS、UV-Vis及C.A.有系統地進行表面形貌、晶體結構、成分組成分析鑑定及光學和表面性質之量測。
在規則有序矽晶奈米孔洞陣列之製備方面，本研究利用氧氣電漿以反應性離子蝕刻方式調變出PS球奈米模板之球徑大小，並同時以經氧氣電漿處理後於矽晶基材上所生成非晶氧化矽層作為蝕刻遮罩，調變氫氧化鉀蝕刻時間後，成功地於各式矽單晶基材上製備出形狀、尺寸及位置皆可調變之矽晶奈米孔洞陣列。
另一方面本研究也結合奈米球微影術、氣體電漿表面改質或金屬矽化反應和選擇性化學蝕刻製程成功在(001)、(110)、(111)矽晶基材上製備出大面積，尺寸及高度皆可調變之規則有序矽晶奈米錐陣列。
經一系列不同尺寸矽晶奈米孔洞及奈米錐陣列試片之水滴接觸角量測發現，表面具有奈米結構陣列之矽晶試片其接觸角呈現不同程度之疏水特性，此現象可用Cassie Model來解釋。此外，以紫外光-可見光光譜分析可發現矽晶表面有奈米結構陣列時矽晶基材具有光捕捉效應，可大幅降低光之反射率。

摘要(英)

The present study has demonstrated the successful fabrication of density-, size- and shape-controllable Si nanostructure arrays on Si substrates of different orientation by using plasma modified nanosphere lithography and anisotropic wet etching process. The morphologies, crystal structures, compositions, optical and surface properties of the Si nanostructure arrays produced have been systematically investigated by SEM, AFM, TEM, SAED, EDS, XPS, UV-Vis and contact angle analyses.
For the fabrication of periodic Si nanohole arrays, we take advantage of O2 plasma RIE treatment, which allows us simultaneously to adjust the diameter of PS nanospheres template and to form a passivation a-SiOx layer on Si serving as the etching mask. The shapes, sizes and positions of Si nanoholes that formed on Si substrates could be tuned by adjusting the diameters of the colloidal nanospheres and the KOH etching time. On the other hand, by combining the plasma modified nanosphere lithography, selective chemical etching process or metal silicide formation, large-area, size- and height-tunable Si nanocone arrays were also successfully fabricated on (001), (110) and (111)Si substrates in this study. From the water contact angle measurements, the surface of HF-treated Si nanohole and nanocone arrays exhibited hydrophobic characteristics. The hydrophobic behavior of Si nanostructures could be explained by the Cassie model. Furthermore, UV-Vis spectroscopic measurements revealed that the nanostructured Si surfaces exhibit strong antireflection properties.The enhanced antireflection properties can be attributed to the light trapping effect resulting from the nanostructure-arrayed Si surfaces.

關鍵字(中)

★ 溼式蝕刻
★ 矽晶孔洞
★ 矽晶錐
★ 電漿處理
★ 奈米球微影術

關鍵字(英)

★ plasma treatment
★ nanosphere lithography
★ wet etching
★ silicon holes
★ silicon cones

論文目次

中文摘要 i
英文摘要 ii
致謝 iii
目錄 iv
圖目錄 vii
表目錄 xiv
第一章簡介 1
1-1 前言 1
1-2 矽晶微奈米結構陣列模板製備 3
1-2-1 微影技術 3
1-2-2 蝕刻製程 6
1-3 矽晶微奈米孔洞陣列模板在太陽能電池應用及其製程 8
1-4 矽晶微奈米錐陣列模板在場發射性質應用及其製程 10
1-5 微奈米球微影術 10
1-5-1 微奈米球微影術的發展 11
1-5-2 微奈米球自組裝技術 11
1-5-3 微奈米球微影術製備奈米結構 12
1-6 微奈米球微影術製備矽晶微奈米孔洞有序陣列 13
1-7 微奈米球微影術製備矽晶微奈米錐有序陣列 14
1-8 半導體製程中電漿表面改質行為及應用 15
1-9 研究動機 17
第二章實驗步驟及儀器設備 19
2-1 實驗步驟 19
2-1-1 矽晶基材使用前處理 19
2-1-2 自組裝製備微奈米球陣列 20
2-1-3 以反應性離子蝕刻調變微奈米球模板之直徑 21
2-1-4 不同晶向之矽晶基材上製備規則有序矽微奈米孔洞陣列 21
2-1-5 在預置規則圖案之Si(001)基材上製備規則有序矽微奈米孔洞陣列 21
2-1-6 在Si(001)基材上製備規則有序微奈米錐陣列 22
2-1-7 在Si(110)、Si(111)基材上製備規則有序微奈米錐陣列 22
2-2 試片分析 23
2-2-1 掃描式電子顯微鏡(SEM) 23
2-2-2 原子力顯微鏡(AFM) 23
2-2-3 穿透式電子顯微鏡(TEM) 24
2-2-4 高解析穿透式電子顯微鏡(HR-TEM)與X光能量散佈光譜儀(EDS) 24
2-2-5 X-Ray光電子能譜儀(XPS) 24
2-2-6 影像式接觸角量測儀 25
2-2-7 紫外光-可見光光譜儀 25
第三章結果與討論 26
3-1 單層微奈米球模板之製備 26
3-2 利用氧氣電漿蝕刻法調控微奈米球球徑之製程 27
3-3 矽晶基板經氧氣電漿處理後之遮罩結構及成份分析鑑定 28
3-4 微奈米球微影術結合氧氣電漿製備不同矽晶圓方向微奈米孔洞有序陣列及其蝕刻動力學探討 31
3-4-1 矽晶微奈米孔洞陣列外觀形貌觀察 31
3-4-2 接觸角量測分析表面潤濕性質 33
3-4-3 紫外光-可見光光譜儀量測分析 34
3-5預製圖案之(001)矽晶基材上製備微奈米孔洞陣列 35
3-5-1 利用氧氣電漿進行預置圖案之(001)矽晶基材與微奈米球模板製備 35
3-5-2 矽晶微奈米孔洞陣列於預置圖案(001)矽晶基材之外觀形貌觀察 35
3-6 微奈米球微影術結合氧氣電漿製備不同矽晶圓方向微奈米錐有序陣列及其蝕刻動力學探討 36
3-6-1 矽晶微奈米錐陣列外觀形貌觀察 37
3-6-2 接觸角量測分析表面潤濕性質 39
3-6-3 紫外光-可見光光譜儀量測分析 40
第四章結論與未來展望 41
4-1 結論 41
4-2 未來展望 42
4-2-1 (110)及(111)矽晶基材上製備大面積矽晶微奈米環陣列 42
4-2-2 製備大面積有序排列之金屬矽化物微奈米錐陣列 43
參考文獻 44

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指導教授

鄭紹良(Shao-liang Cheng)

審核日期

2012-8-27

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