溼式蝕刻製程製備矽單晶奈米結構陣列及其性質研究

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姓名

林毓源(Yu-Yuan 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

溼式蝕刻製程製備矽單晶奈米結構陣列及其性質研究
(Wet etching process and properties of single-crystalline silicon nanowires)

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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，PSNSL）結合金屬催化化學蝕刻法，成功地在（001）及（111）不同晶面之矽基材上，製備出大面積垂直排列且長度尺寸均一之矽晶奈米線陣列，其寬度約為120 nm。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，且軸向方向沿著基材晶面方向生成。為了進一步控制所生成矽晶奈米線的外觀，我們利用稀釋的氫氧化鉀溶液，進行溼式蝕刻製程。本實驗中，在20℃下以不同蝕刻時間進行蝕刻，可以對奈米線的寬度及長度進行控制並縮小其尺寸，其奈米線尖端的尺寸可由原本的120 nm 縮小至12 nm。由場發射性質量測所得到的數據可知，和原本的矽晶奈米線相比，經過氫氧化鉀蝕刻後的矽晶奈米線可顯著提升場發射的性質；本實驗中，所量測的最低啟動電場為1.21 V/μm，而場發射增強因子β可以增加至8127。
在氣體量測實驗中，利用平板矽試片、矽晶奈米線以及表面孔洞結構之矽晶奈米線等三種不同條件的試片做成感測器的偵測元件，並於室溫下通入水氣、酒精和丙酮等氣體進行偵測。從量測結果可清楚得知，氣體偵測的靈敏度會隨著通入氣體濃度的提升而增加；而不論是何種通入氣體，表面孔洞結構之矽晶奈米線其靈敏度相比其他兩種試片都是較高的，在11 ppm的低濃度時有著9.7 %的靈敏度，推測是因為其較高的表面積比例，可增加氣體量測性質的靈敏度。

摘要(英)

In the present study, we have demonstrated that large-area, length-tunable arrays of vertically aligned Si nanowire were successfully produced on (001)Si and (111)Si substrates by using the PS nanosphere lithography combined with the Au-assisted selective chemical etching process. The diameter of the Si nanowire produced was very uniform and observed to be approximately 120 nm. Based on the analyses of the TEM image and the corresponding SAED patterns, it can be concluded that the Si nanowires produced have single-crystalline nature and form along the [001] and/or [111] directions. In order to further modulate the morphologies of the Si nanowires, a post wet etching process with a dilute KOH solution was developed. In this work, the tapering process was performed at 20℃ for various etching time. The length and width of Si nanowires can be controlled and reduced by adjusting the KOH etching duration. After appropriate KOH etching, the diameter of the Si nanowire tips can be reduced from 120 nm to about 12 nm. Field emission measurements showed that the KOH-etched Si nanowires exhibited significantly improved field emission properties compared to the as-produced Si nanowires. In the study, a low turn-on field of 1.21 V/μm was obtained, and the corresponding field enhancement factor, β value, was greatly enhanced to as high as 8127.
For the gas sensing experiments, three kinds of samples, blank-Si wafer, Si nanowires, and porous Si nanowires, were prepared and used as the gas sensing in this study. Their gas sensing properties towards water vapor, ethanol, and acetone were investigated at room temperature. The measurement results clearly show that the response magnitudes of the three kinds of sensors improved significantly with increasing the gas concentrations. Whether exposed to water vapor, ethanol, or acetone, the sensitivity of the porous Si nanowires sensor is much higher than that of the blank-Si and Si nanowires sensors. In this work, the sensitivity of the porous Si nanowires sensor reaches as high as 9.7% for 11 ppm acetone. The enhanced sensing performances of the porous Si nanowires sensor can be attributed to its high surface-to-volume ratio.

關鍵字(中)

★ 溼式蝕刻
★ 矽單晶奈米結構

關鍵字(英)

★ wet etching
★ silicon nanowires

論文目次

目錄
中文摘要 i
英文摘要 ii
致謝 iii
目錄 iv
圖目錄 viii
表目錄 xiii
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 3
1-2-1 氣-液-固成長機制 3
1-2-2 氧催化成長機制 4
1-2-3 固-液-固成長機制 5
1-2-4 反應性離子蝕刻法 6
1-2-5 金屬催化無電鍍蝕刻法 7
1-2-6 金屬催化化學蝕刻法 8
1-3 奈米球微影技術 9
1-3-1 奈米球的自組裝行為 9
1-3-2 奈米球微影術的發展 10
1-4 金屬催化結合奈米球微影技術製備矽晶奈米線 11
1-5 不同平面之矽單晶奈米線製備 11
1-6 鹼性溶液蝕刻矽基材 12
1-6-1 矽蝕刻液種類 12
1-6-2 氫氧化鉀蝕刻矽基材 13
1-7 矽晶奈米線表面粗糙化 14
1-8 場發射電極元件 14
1-8-1 場發射理論 14
1-8-2 場發射元件發展 16
1-8-3 以矽為基材的場發射元件研究 18
1-9 化學感測器 19
1-9-1 化學感測器簡介 19
1-9-2 矽晶奈米線化學感測器之研究 20
1-10 研究動機及目標 20
第二章實驗步驟及儀器設備 22
2-1 實驗步驟 22
2-1-1 矽晶基材使用前處理 22
2-1-2 奈米球陣列模板製備 22
2-1-3 以電漿蝕刻調變奈米球模板之尺寸 23
2-1-4 蒸鍍金薄膜 23
2-1-5 化學溼式蝕刻製備不同平面之矽單晶奈米線陣列 23
2-1-6 氫氧化鉀蝕刻製備準直有序矽單晶奈米結構陣列 24
2-1-7 製備氣體感測元件 24
2-2 試片分析 24
2-2-1 掃描式電子顯微鏡 ( SEM ) 24
2-2-2 穿透式電子顯微鏡 ( TEM ) 25
2-2-3 真空場發射特性量測系統 25
2-2-4 紫外光-可見光光譜儀 26
2-2-5 影像式接觸角量測儀 26
2-2-6 氣體感測性質量測裝置 26
第三章結果與討論 28
3-1 奈米球模板製備 28
3-2 製備不同晶面矽單晶奈米線陣列 29
3-2-1 不同濃度對製備不同晶面矽單晶奈米線的影響 29
3-2-2 不同晶面矽單晶奈米線結構分析 30
3-3 氫氧化鉀蝕刻不同晶面之矽單晶奈米線 31
3-3-1 大面積有序排列之不同晶面矽單晶奈米結構 32
3-3-2 不同晶面之矽單晶奈米結構分析 34
3-4 不同平面矽單晶奈米結構之場發射性質量測 36
3-5 氣體感測性質分析 39
3-5-1 不同結構矽基材試片對不同氣體的偵測性質 39
3-5-2 表面粗糙之矽晶奈米線試片作為氣體偵測元件的性質測試 42
3-6 可見光-紫外光光譜儀量測分析 43
3-7 接觸角量測分析 44
第四章結論與未來展望 46
4-1 結論 46
4-2 未來展望 47
4-2-1 氧化氫氧化鉀蝕刻後的矽晶奈米線 47
4-2-2 矽晶奈米線為基礎的氣體感測性能提升及研究 48
參考文獻 49

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指導教授

鄭紹良(Shao-liang Cheng)

審核日期

2012-8-27

推文