奈米球微影術製備規則有序排列之低電阻鈷矽化物及矽單晶奈米點陣列之研究

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楊鎮宇(Chen-Yu Yang) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

奈米球微影術製備規則有序排列之低電阻鈷矽化物及矽單晶奈米點陣列之研究
(Fabrication of Well-ordered Arrays of Low-Resistivity CoSi2 nanodots and Single Crystalline Si Nanodots by Nanosphere Lithography.)

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摘要(中)

本研究中分別利用自然滴製法與LB-like法在矽晶及矽鍺基材上製備出大面積排列規則的PS球陣列結構充當模板(Template)，並以此模板製備出不同尺度奈米點陣列，同時針對其界面反應、晶體結構、成長機制、表面性質進行鑑定分析。
在與矽鍺基材反應之實驗方面，我們首度結合自然滴製法與蒸鍍適當厚度比例之Co/a-Si雙薄膜結構，成功地在矽鍺基材上製備出大面積規則排列且尺寸均一之低電阻CoSi2奈米點陣列，有效地降低反應過程中鍺偏析現象發生及提高其熱穩定性。由AFM、TEM與SAED分析結果發現，在400 ℃熱退火處理後Co/a-Si點陣試片會先形成多晶高電阻CoSi相，但經500 ℃-950 ℃之熱退火處理後，點陣會轉化生成多晶低電阻CoSi2相。且由橫截面TEM觀察發現在SiGe晶片上所生成之CoSi2奈米點陣介面十分平整，顯示奈米尺度Co/a-Si有助於CoSi2相生成。而當退火熱處理溫度升高至1000 ℃時，則會發現奈米線結構的產生，由TEM、SAED及EDS分析，可得知此奈米線結構主要是由矽、氧成分所組成之SiO2奈米線，其大小約為15-35 nm且為非晶質結構，並推測其生長為固-液-固(Solid-Liquid-Solid, SLS) 之成長機制。
本研究也首度結合奈米球模板與選擇性化學濕式蝕刻技術，成功在矽晶基材上製備出大小與高度可控制之規則有序矽單晶奈米點陣列結構，並深入探討其性質。經水滴接觸角實驗發現，表面生成矽單晶奈米點陣列之試片其接觸角呈現大幅度增加，可達112°-124°，此種因表面奈米結構造成接觸角提升的現象可用Cassie Model解釋。而在利用紫外光-可見光光譜儀分析中可發現，表面具有奈米點陣列結構的矽晶試片於可見光波長範圍內（400-800 nm）其反射率相較於未經蝕刻反應之矽晶片(33 %)會大幅下降至16 %-22 %，其主要是由於矽單晶奈米點陣提供了入射光額外的散射機制，增加入射光在內部的行徑距離使入射光被吸收的程度提高所致。

摘要(英)

The present study has demonstrated that well-ordered arrays of polystyrene(PS) nanosphere were successfully fabricated on (001)Si and (001)Si0.7Ge0.3 substrates by using the drop-coating and LB-like technique. The self-assembled PS nanosphere arrays were used as the deposition templates.
Large-area, well-ordered arrays of low-resistivity CoSi2 nanodots were successfully fabricated on (001)Si0.7Ge0.3 substrate by combining the nanosphere lithography and Co/amorphous-Si bilayer structure. Based on the AFM, TEM and SAED analyse, polycrystalline CoSi nanodots were found to form in sample annealed at 400 ℃.As the annealing temperatures were increased to 500-950 ℃, low-resistivity CoSi2 nanodots were successfully grown on (001)Si0.7Ge0.3 substrate. From cross-sectional TEM observation, the interface between CoSi2 nanodot and (001)Si0.7Ge0.3 substrate was found to be rather smooth. For the Co/a-Si nanodot samples further annealed at 1000 ℃, many SiOx nanowires of 15-35 nm in diameter were observed to grow from the CoSi2 nanodot regions. The growth process of amorphous SiOx nanowires could be explained by the solid–liquid–solid (SLS) mechanism.
By combining the nanosphere template and selective chemical etching, large-area size- and height-tunable Si nanodot arrays were successfully fabricated on (001)Si substrates. From the water contact angle measurements, the surface of HF-treated Si nanodot arrays exhibited strong hydrophobic characteristics. The hydrophobic behavior of Si nanodots could be explained by the Cassie model. The UV-Vis analysis results revealed that the reflectance of Si substrate with Si nanodot arrays was found to decrease from 33 % to 16-22 % in visible light range (400-800 nm). The low visible reflectance of Si nanodots samples is due to the fact that surface of Si nanodots sample is rough, resulting in trapping and scattering of light.

關鍵字(中)

★ 奈米點陣列
★ 矽者基材
★ 鈷矽化物
★ 奈米球微影
★ 選擇性化學蝕刻

關鍵字(英)

★ nanodot
★ SiGe substrate
★ cobalt silicide
★ nanosphere lithography
★ elective chemical etching

論文目次

第一章簡介............................................1
1-1 前言...............................................1
1-2奈米球微影術........................................2
1-2-1奈米球微影術的發展................................2
1-2-2各種奈米球自組裝技術..............................4
1-2-2-1 自然滴製法.....................................4
1-2-2-2 旋轉塗佈法.....................................5
1-2-2-3 LB-Like 技術...................................5
1-2-3利用奈米球微影術製備各式奈米結構..................6
1-2-3-1金屬薄膜沉積技術................................7
1-2-3-2電化學沉積技術 ..................................8
1-2-3-3反應蝕刻技術....................................8
1-3蝕刻技術............................................9
1-3-1濕式蝕刻..........................................9
1-3-1-1矽晶基材濕式蝕刻..........................10
1-3-1-2選擇性矽晶基材濕式蝕刻....................10
1-3-2乾式蝕刻.........................................11
1-4 金屬矽化物........................................12
1-4-1 金屬矽化物在半導體工業上的應用及其製程..........12
1-4-2 鈷金屬矽化物................................14
1-5 矽鍺元件..........................................15
1-5-1 矽鍺元件中之金屬接觸............................15
1-6 矽鍺基材上之金屬矽化物...........................16
1-7 研究動機..........................................17
第二章實驗步驟.......................................19
2-1 奈米球模板之製備..................................19
2-1-1 基材使用前處理..................................19
2-1-2 奈米球膠體溶液配製..............................19
2-1-3 自組裝奈米球陣列................................20
2-2大面積低電阻相鈷金屬矽化物奈米點陣列之製備.........20
2-2-1金屬薄膜蒸鍍.....................................21
2-2-2奈米球舉離.......................................21
2-2-3退火熱處理.......................................21
2-3大面積有序矽單晶奈米點陣列結構之製程...............22
2-3-1 反應性離子蝕刻控制奈米球模板球徑大小............22
2-3-2金屬薄膜沉積與奈米球舉離.........................22
2-3-3退火熱處理.......................................23
2-3-4選擇性化學濕式蝕刻...............................23
2-4 分析儀器與鑑定....................................23
2-4-1 掃描式電子顯微鏡(SEM)...........................23
2-4-2 原子力顯微鏡(AFM)...............................23
2-4-3 穿透式電子顯微鏡(TEM)與X光能量散佈光譜儀........24
2-4-4接觸角(Contact Angle)量測儀......................24
2-4-5紫外光-可見光光譜儀(UV-Vis)......................25
第三章結果與討論.....................................26
3-1 奈米球模板之製備..................................26
3-2於矽鍺基材上沉積Co/a-Si雙薄膜結構製備大面積低電阻鈷矽化物奈米點陣............................................28
3-2-1 Co/a-Si雙薄膜結構及其矽化反應...................29
3-2-2 Co/a-Si雙薄膜結構及其矽化物之表面高低形貌分析...30
3-2-3 Co/a-Si雙薄膜結構與Si0.7Ge0.3基材之界面反應分析 .31
3-3矽晶基材上製備大面積矽單晶奈米點陣列...............36
3-3-1 矽單晶奈米點陣列外觀形貌觀察....................36
3-3-2 接觸角量測分析表面潤濕性質......................38
3-3-3 可見光-紫外光光譜儀量測分析.....................40
第四章結論與未來展望 .................................42
4-1 結論..............................................43
4-2 未來展望..........................................44
4-2-1矽鍺基材上製備不同金屬矽化物有序奈米點陣列.......44
4-2-2不同矽基材上製備大面積規則矽單晶奈米點陣列結構...44
4-2-3以KOH + KI蝕刻法製備新穎矽基奈米結構.............44
參考文獻..............................................45
表目錄................................................54
圖目錄................................................57

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指導教授

鄭紹良(Shao-Liang Cheng)

審核日期

2010-7-28

推文