添加甲醇/乙醇於氫氟酸/氟化銨溶液對其製作p-型(100)矽微米孔洞之影響

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姓名

周裕齊(Yi-Chi Chou) 查詢紙本館藏

畢業系所

機械工程學系

論文名稱

添加甲醇/乙醇於氫氟酸/氟化銨溶液對其製作p-型(100)矽微米孔洞之影響
(The effect of Methanol/Ethanol added-HF/NH4F solution)

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摘要(中)

本研究以電化學方法在p-型（100）矽單晶上，蝕刻出微米級巨孔陣列結構。研究方式利用陽極極化法及定電位蝕刻，在氫氟酸及氟化銨溶液中，分別就不同添加劑改變溶液潤濕性、蝕刻時間、試片圖案孔洞尺寸，不同pH值等參數，探討其對蝕刻之影響。
研究結果顯示，p-型（100）矽單晶，隨著2M氫氟酸中添加乙醇之溶液中，其潤濕係數從0.15、0.42，0.59增加到0.82時，對p-Si(100)的蝕刻8小時，其孔洞寬度維持在7.8μm，但蝕孔深度由14.6μm增加到34.3μm，即蝕刻速率由1.825μm/h增加到4.29μm/h。若在2M氟化銨溶液中潤濕係數由0.15增加到0.60時，對p-Si(100)蝕刻8小時，其深度由9.2μm增加到21.6μm(蝕刻速率由1.15μm/h增加至2.7μm/h)。進一步延長氫氟酸溶液蝕刻時間至64小時可以有效增加蝕刻的深度至120μm。
預蝕刻時若圖案孔徑（L）從4、6、8到12μm進行蝕刻，不管是在氫氟酸或是氟化銨溶液中，都會有擴孔的現象，但是蝕刻孔洞的壁厚（P－L）均趨於定值，理論上與兩倍空間電荷層（2W）厚度相當近似。
使用潤濕係數 0.82之氫氟酸溶液，控制其蝕刻電流與蝕刻時間可以分別在P4試片和P12試片上得到深215μm、421μm的微米巨孔陣列。

摘要(英)

Formation of macro-pore arrays on p-type silicon in fluoride-containing solution by electrochemical etching has been investigated in this work. Effect of wetting coefficient, etching time, Size of the pre-etched holes and pH value are discussed in fluoride-containing solution by dc-potentiodynamic polarization and potentiostatic etching.
The depth of etching pores on p-type(100) silicon increases from 14.6μm to 34.3μm(etching rate from 1.825μm/h to 4.29μm/h) with increasing the wetting coefficient from 0.15 to 0.82 in 2M HF solutions containing various concentration of methanol and ethanol for 8h. The width of etching pores keeps at constant(roughly at 7.8μm). The depth of etching pores increase from 9.2μm to 21.6μm with increasing the wetting coefficient from 0.15 to 0.59 in 2M NH4F solutions containing various concentration of methanol and ethanol for 8h. The total etching depth increases to 120μm with increasing the etching time up to 64h in hydrofluoric acid solution.
Regardless the etching extended in 2M ammonium fluoride or 2M hydrofluoric acid, the opening of the etched pore expanded a little for the patterns with increasing the pre-etched pit from P4, P6, P8 to P12. The wall width for all the etching structures keeps at constant that is theoretically determined at the twice of the SCR region.
Galvanostatic etching of p-Si(100) with pattern P4 for 32h in 2MHF containing 8MEtOH results in macro-pore arrays at a depth of 215μm depths. Galvanostatic etching with pattern P12 in 2MHF containing 8MEtOH for 16h leads to macro-pore arrays at a depth of 421μm .

關鍵字(中)

★ 潤濕係數
★ 氫氟酸
★ 氟化銨
★ 電化學蝕刻
★ p-型Si(100)單晶

關鍵字(英)

★ p-type(100) silicon
★ electrochemical etching
★ Ammonium fluoride
★ Hydrofluoric Acid
★ Wetting coefficient

論文目次

中文摘要 Ⅰ
英文摘要 Ⅱ
誌謝 Ⅲ
目錄 Ⅳ
表目錄 IX
圖目錄 XII
第一章簡介 1
一、研究背景 1
1-1 矽晶圓蝕刻的發展與應用 1
1-2 電化學蝕刻與其他矽晶圓蝕刻技術 1
二、研究目的 3
第二章基礎原理及文獻回顧 4
一、半導體電化學理論 4
2-1 半導體材料電子能階 4
2-2 電解液的電子能階----絕對電極電位 4
2-3 半導體卅電解液界面 5
2-3-1 平衡狀態 5
2-3-2 平坦帶電位（flat-band voltage） 7
二、多孔矽形成機制 8
2-4 矽在電解液中的電流—電壓（I-V）特性 8
2-5矽的陽極溶解反應 9
2-6 多孔矽的形成模型 11
2-6-1 Beale 模型 11
2-6-2 Zhang 模型 14
2-7電化學蝕刻製作多孔矽結構 15
2-8 溶液界面張力與潤濕性 18
2-9界面活性劑理論 19
2-10混合溶液之界面張力 20
第三章研究方法 22
3-1實驗流程 22
3-2試片選擇 22
3-3試片前處理 23
3-4實驗設備 24
3-5蝕刻液選擇 25
3-6接觸角量測 25
3-7電化學方法 26
3-8蝕刻表面觀察 26
第四章結果 27
4-1氫氟酸中乙醇濃度 27
4-1-1接觸角（contact angle）量測 27
4-1-2開路電位（OCP）量測 27
4-1-3陽極動態極化行為 28
4-1-4定電位蝕刻 29
4-2氫氟酸中甲醇濃度 31
4-2-1接觸角（contact angle）量測 31
4-2-2定電位蝕刻 32
4-3 氫氟酸溶液中不同蝕刻時間的影響 32
4-4 不同蝕刻圖案對氫氟酸蝕刻形貌的影響 33
4-5不同試片阻值對氫氟酸蝕刻形貌的影響 34
4-6氟化銨濃度 35
4-6-1開路電位(OCP)量測 35
4-6-2 陽極動態極化曲線 36
4-6-3 定電位蝕刻 37
4-7 不同蝕刻圖案對氟化銨蝕刻形貌的影響 38
4-8不同試片阻值對氟化銨蝕刻形貌的影響 38
4-9 不同濃度乙醇添加對氟化銨蝕刻的影響 38
4-9-1接觸角（contact angle）量測 39
4-9-2 定電位蝕刻 40
4-10 不同濃度甲醇添加對氟化銨蝕刻的影響 41
4-10-1接觸角（contact angle）量測 41
4-10-1接觸角（contact angle）量測 42
4-11改變溫度對氟化銨蝕刻的影響 43
4-12 氟化銨溶液中不同蝕刻時間的影響 43
4-13 相同氟離子濃度下不同pH值對蝕刻之影響 44
4-14 微米巨孔陣列的製作 45
第五章討論 46
5-1氫氟酸添加乙醇改變潤濕性對蝕刻的影響 46
5-2氟化銨溶液添加乙醇改變潤濕性對蝕刻的影響 48
5-3氟化銨溶液添加甲醇改變潤濕性對蝕刻的影響 50
5-4氫氟酸添加甲醇改變潤濕性對蝕刻的影響 52
5-5溶液潤濕性對氫氟酸與氟化銨溶液蝕刻的影響 53
5-6溶液潤濕性與蝕刻時間 55
5-7改變溫度對氟化銨蝕刻的影響 56
5-8孔洞寬度與空間電荷層之關係 56
5-9氫氟酸與氟化銨的比較 58
第六章結論 60
第七章參考文獻 62

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指導教授

林景崎(Jing-Chie Lin)

審核日期

2006-7-18

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