準直尖針狀矽晶及矽化物奈米線陣列之製備及其性質研究

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姓名

楊善淳(Shan-chun Yang) 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

準直尖針狀矽晶及矽化物奈米線陣列之製備及其性質研究

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摘要(中)

本研究成功利用聚苯乙烯球奈米球微影術(Nanosphere Lithography，NSL)結合金屬催化化學蝕刻法在(100)以及(111)矽晶圓上成功製備大面積準直排列規則有序矽晶奈米線陣列，此矽晶奈米線陣列的直徑以及長度可藉由氧氣電漿處理以及濕式蝕刻的時間來妥善調控，並在製備完成矽晶奈米線後，以金屬催化無電鍍蝕刻法，藉由銀離子的還原來修飾矽晶奈米線的形貌，將平頭矽晶奈米線轉變成尖針狀的形貌，藉由實驗的觀察發現尖針狀的樣貌由來是由於疏水性矽晶奈米線頂部的上方以及側壁蝕刻所造成，而後藉由傾斜角度的方法鍍製一層90nm的鎳金屬於矽晶奈米線側壁，進行不同時間以及溫度的熱退火處理，發現在經500oC 2小時以及700oC 2小時的熱處理後可獲得鎳金屬原子擴散一半的矽晶奈米線以及完全反應的矽化物奈米線，此矽化物的區域在半根反應時呈現(111)鋸齒狀刻面，經過穿透式電子顯微鏡以及選區電子繞射圖譜解析後得知鎳矽化物相為二矽化鎳相(NiSi2)。此反應在(111)晶圓上製備出來的矽晶奈米線會由於奈米線軸向為[111]的關係，而在側壁形成垂直於矽晶奈米線的三角形刻面。而此研究還針對矽化物奈米線進行場發射性質量測，可假設形貌不變的條件下，平頭矽晶奈米線以及尖頭矽晶奈米線之場增強因子不會改變，可在矽化反應之後獲得提早啟動的電場以及被降低的有效功函數(Effective Work Function)，啟動電場由5.56Vum-1提早至約1.2Vum-1而有效功函數由5.0eV下降至2.0eV左右。
本研究另在傾角鍍膜中發現可利用側壁鍍膜的陰影做為有效的遮罩來製備新穎的平躺奈米線結構，傾角鍍膜鍍製適當厚度的二氧化矽膜後，在凹槽當中鍍製一層金屬薄膜，而後結合掀離方法，便可獲得平躺的金屬奈米線，是一簡易方便且成本低廉的微影技術。

摘要(英)

In this study, we demonstrated that large-area arrays of vertically aligned Si nanowires were successfully fabricated on (001)Si and (111)Si substrates by using the PS nanosphere lithography combined with the Au-assisted selective chemical etching process. The diameter and length of these silicon nanowires are adjustable through O2 plasma treatment and wet etching time. The morphology of the silicon nanowires can be converted from flat top to sharp top by metal catalyzed electroless deposition etching method through the reduction of silver. In this research, we noticed that thin kind of etching process is due to the hydrophobic etching on the top and the side wall of the silicon nanowires. Through tilting angle deposition of 90nm Ni and 500oc, 700oC 2hr N2 annealing, we can obtain half silicidation and fully silicidation in the silicon nanowires. Through TEM observation and the SAED analysis, we noticed that the triangle facets are (111) planes of the Nickel disilicide phase (NiSi2). These facet will be perpendicular to the side wall of the [111] silicon nanowires due to the difference of the orientation. We also demonstrated the research of the field emission property of the silicide wire. According to the changeless morphology, the beta enhancement factor is supposed to be unchanged. So we can tell that, through silicidation, the turn on field was reduced from 5.56Vum-1 to 1.2Vum-1 ,and the effective work function was reduced from 5.0eV to about 2.0eV.
Another interesting issue in this research is about utilizing the shadow generated from the tilting angle process as the mask to fabricate the horizontally aligned metal wires. Through the deposition of proper thickness of SiO2 and lift off technique, we can obtain 20nm height of Ni wire horizontally aligned on the silicon wafer.

關鍵字(中)

★ 矽晶奈米線
★ 鎳矽化物
★ 場發射性質

關鍵字(英)

論文目次

中文摘要..............................................................I
英文摘要.............................................................II
致謝..................................................................III
目錄...................................................................IV

第一章前言及文獻回顧.........................................1
1-1前言...................................................................1
1-2矽單晶奈米線製備方法...................................................3
1-2-1氣-液-固法成長矽晶奈米線...........................................3
1-2-2固-液-固法成長矽晶奈米線...........................................5
1-2-3氧催化成長法.......................................................5
1-2-4反應性離子蝕刻法成長矽晶奈米線.....................................6
1-2-5金屬催化無電鍍蝕刻法成長矽晶奈米線.................................7
1-2-6金屬催化化學蝕刻法成長矽晶奈米線...................................8
1-3奈米球微影技術........................................................10
1-3-1奈米球的自組裝行為................................................10
1-3-2奈米球微影術的發展................................................11
1-4奈米球微影術結合金屬催化化學蝕刻法製備矽單晶奈米線....................12
1-5不同軸向之矽單晶奈米線製備............................................13
1-6矽晶基材蝕刻反應......................................................14
1-6-1有機以及鹼性溶液蝕刻矽晶基材......................................14
1-6-2金屬催化無電鍍銀蝕刻矽晶奈米線....................................15
1-7金屬矽化物............................................................16
1-7-1金屬矽化物之製程與應用............................................16
1-7-2薄膜鎳金屬矽化物. ................................................18
1-7-3鎳金屬矽化物奈米線................................................18
1-8水滴接觸角之相關理論..................................................19
1-9場發射電極元件........................................................21
1-9-1場發射相關理論....................................................21
1-9-2 矽晶基材的場發射效應研究.........................................22
1-10水平排列金屬奈米線陣列製備...........................................24
1-11研究動機及目標.......................................................25

第二章實驗步驟及儀器設備..................................26
2-1實驗步驟..............................................................26
2-1-1矽晶基材使用前處理................................................26
2-1-2奈米球陣列模板製備................................................26
2-1-3氧氣電漿調控奈米球陣列模板之尺寸..................................27
2-1-4金屬薄膜蒸鍍......................................................27
2-1-5化學濕式蝕刻製備不同軸向之矽單晶奈米線陣列........................27
2-1-6金屬催化無電鍍蝕刻法修飾矽單晶奈米線..............................28
2-1-7熱氧化法修飾矽單晶奈米線之線寬....................................28
2-1-8準直鎳矽化物單晶奈米線陣列製備....................................29
2-1-9水平排列金屬奈米線製備............................................29
2-2試片分析..............................................................30
2-2-1掃描式電子顯微鏡..................................................30
2-2-2穿透式電子顯微鏡..................................................31
2-2-3真空場發射性質量測系統............................................31
2-2-5影像式水滴接觸角量測儀............................................32

第三章結果與討論.............................................33
3-1聚苯乙烯奈米球模板製備................................................33
3-1-1單層聚苯乙烯奈米球模板製備.......................................33
3-1-2 經氧氣電漿蝕刻調控尺寸的奈米球模板..............................33
3-2製備不同晶面矽單晶奈米線陣列..........................................34
3-3以金屬催化無電鍍方式製備尖針狀矽單晶奈米線............................36
3-4矽化物奈米線製備......................................................38
3-4-1[100]成長方向平頂以及尖針狀矽化物奈米線製備......................38
3-4-2[111]成長方向矽化物奈米線製備....................................43
3-4-3小尺度的矽化物奈米線相轉變行為探討...............................44
3-5矽晶奈米線以及矽化物奈米線之場發射性質量測與探討。....................45
3-6接觸角量測分析........................................................46
3-6-1尖針化之矽晶奈米線的水滴接觸角變化................................46
3-6-2金屬矽化物奈米線之水滴接觸角變化..................................47
3-7二氧化矽膜遮罩製備大面積水平排列奈米線陣列。..........................48

第四章結論與未來展望......................................50
參考文獻............................................................52
圖目錄...............................................................62

參考文獻

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指導教授

鄭紹良

審核日期

2014-8-28

推文