化學溶液蝕刻法製備大面積規則排列矽單晶奈米柱陣列之研究

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陳建佑(Jian-you Chen) 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

化學溶液蝕刻法製備大面積規則排列矽單晶奈米柱陣列之研究
(Fabrication of Large-area Periodic Arrays of Single-crystalline Silicon Nanorods by Chemical Wet Etching Processes)

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摘要(中)

本研究利用聚苯乙烯奈米球微影術（Polystyrene Nanosphere Lithography, PS NSL）結合金催化選擇性化學蝕刻法，成功地在(001)矽基材上製備出大面積垂直排列且可調變長度之矽晶奈米柱陣列，並對矽晶奈米柱之晶體結構及反應動力學作深入探討。實驗中也將探究水滴在表面生成奈米柱結構的試片上之潤濕行為及其光學性質之變化。
由掃描式電子顯微鏡（SEM）及穿透式電子顯微鏡（TEM）觀察可發現，金屬催化選擇性蝕刻所生成之奈米柱不但具有相當好的均一性，且與實驗所用之奈米球模板之直徑相當吻合，其奈米柱寬度約為126 nm。而從TEM影像及其相對應之電子繞射圖形分析鑑定可得知本研究所製備之矽晶奈米柱均為單晶結構，且軸向方向沿著[001]方向生成。此外，藉由一系列SEM橫截面影像觀察，可獲得不同反應溫度及時間下矽晶奈米柱之生成長度變化。藉由量測不同反應溫度下奈米柱之生成速率，可由阿瑞尼士（Arrhenius）關係圖中求得其生成反應活化能約為76.7（kJ/mole）。
經水滴接觸角實驗觀察與分析結果發現，表面生成矽晶奈米柱陣列之試片經HF清洗後呈現相當高的疏水性，其接觸角可達125°-150°，此種因表面奈米柱結構造成接觸角提升的現象可用Cassie Model解釋。利用紫外光-可見光光譜儀分析反應後試片可發現，表面具有奈米柱陣列結構的試片在可見光波長範圍內（400-800 nm）呈現相當低的反射率（﹤5％）。

摘要(英)

In the present study, we have demonstrated that large-area, length-tunable arrays of vertically aligned Si nanorod arrays were successfully produced on (001)Si substrates by using the PS nanosphere lithography combined with the Au-assisted selective chemical etching process. The crystal structures, formation kinetics, surface wetting behaviors, and optical properties of the Si nanorods produced have been investigated.
The SEM and TEM examinations revealed that the diameter of the Si nanorods produced was very uniform and observed to be approximately 126 nm, corresponding to that of RIE-reduced PS sphere mask used. Based on the analyses of the TEM image and the corresponding SAED pattern, it can be concluded that all the produced Si nanorods were single crystalline and the Si nanorods formed along the [001] direction. After a series of cross-sectional SEM examinations, the length variations of Si nanorods produced with etching time for various reaction temperatures were obtained. By measuring the formation rates of Si nanorods at different reaction temperatures, the activation energy for the linear formation of Si nanorods could be determined from an Arrhenius plot to be about 76.7 kJ/mole.
The results of the water contact angle measurements indicated that the surfaces of HF-treated Si nanorod arrays exhibited strong hydrophobicity with water contact angle of 125°-150°. The hydrophobic behavior of the HF-treated Si nanorods was discussed in the context of the Cassie model. The UV-Vis analysis results indicated that Si substrate with Si nanorod arrays exhibited low reflection properties (﹤5％) over the visible light range (400-800 nm).

關鍵字(中)

★ 矽晶奈米柱
★ 奈米球微影術
★ 金屬催化蝕刻
★ 單晶矽

關鍵字(英)

★ Metal-assisted Etching
★ Single-crystalline Silicon
★ Silicon Nanorod
★ Nanosphere Lithography

論文目次

目錄..........................................I
第一章前言及文獻回顧.........................1
1-1 前言......................................1
1-2 矽晶奈米線製備方法........................2
1-2-1 化學氣相沉積法..........................2
1-2-2 金屬輔助化學蝕刻法......................5
1-2-3 金屬催化結合濕式蝕刻法..................5
1-3 奈米球微影術..............................7
1-3-1 奈米球的自組裝行為......................7
1-3-2 奈米球微影術的發展......................7
1-4 接觸角之相關原理與測定....................8
1-4-1 理論架構................................8
1-4-2 動態接觸角..............................10
1-5 研究動機..................................11
第二章實驗步驟及儀器設備.....................12
2.1實驗步驟...................................12
2-1-1 基材使用前處理..........................12
2-1-2 奈米球模板製備..........................12
2-1-3 以反應性離子蝕刻調變奈米球模板之直徑....13
2-1-4 蒸鍍金屬薄膜............................13
2-1-5 常溫常壓下在矽晶圓上製備矽晶奈米柱陣列..14
2-2 試片分析..................................14
2-2-1 掃描式電子顯微鏡（SEM）.................14
2-2-2 影像式接觸角量測儀（Software-Controlled
Multi Dosing System-DSA10）...................14
2-2-3 穿透式電子顯微鏡（TEM）.................15
2-2-4紫外光-可見光光譜儀......................15
第三章結果與討論.............................16
3-1 奈米球模板製備............................16
3-2 利用反應性離子蝕刻調變球徑大小............17
3-3 以金屬催化蝕刻法結合奈米球微影術製備矽單晶
奈米柱陣列................................18
3-4 矽單晶奈米柱之結構及晶向鑑定..............20
3-5 矽單晶奈米柱之反應機制....................21
3-6 以金屬催化蝕刻方式製備矽晶奈米柱陣列之成長
動力學探討................................23
3-7 反應面積對蝕刻速率之影響..................27
3-8 接觸角量測分析............................29
3-9 可見光-紫外光光譜儀量測分析...............31
第四章結論與未來展望.........................33
4-1 結論......................................33
4-2 未來展望..................................34
4-2-1 在預置規則圖案中成長寬度及長度均可精準控
制之有序排列的矽單晶奈米柱陣列..........34
4-2-2 製備有序排列之金屬矽化物奈米柱陣列結構..35
參考文獻......................................36
圖目錄........................................41

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指導教授

鄭紹良(Shao-liang Cheng)

審核日期

2009-7-30

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