界面活性劑在銅晶片表面潤濕行為之研究

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姓名

王清標(Ching-Biau Wang) 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

界面活性劑在銅晶片表面潤濕行為之研究
(Surfactants on the surface of copper wafer for wetting behavior research)

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摘要(中)

本文是針對未來半導體的生產過程中，化學機械研磨後的表面清洗作一界面現象的研究。本實驗是利用銅表面清潔後，接觸角的量測的方法，儘量去得到很低的接觸角標準差。特別是在晶片表面平坦化之後，會有許多微粒子以及金屬離子產生。使用DSA-10的液滴量測儀器在短時間的量測時能得到良好的實驗結果。液滴角度量測的原理是利用液滴外觀影像與基材的基準線，利用楊氏方程式計算可以求得接觸角。
本文的研究內容，主要是觀察界面活性劑在銅晶片表面的潤濕現象，表面越溼潤時，表面接觸角會越小，代表著銅晶片表面能量越低。例如；去離子水在表面氧化亞銅的銅晶片，及接觸角是100度，是非常的疏水，在銅表面上能量也是相當的高。
為了避免表面產生不良的缺陷，如金屬離子殘留或水痕等缺陷。因此這個研究是以添加界面活性劑的水溶液對銅晶片的潤溼性做研究，實驗中發現當動態接觸角量測時間在第30秒時，接觸角變化幅度趨於平緩；濃度到達十倍臨界微胞濃度(CMC)時，其動態接觸角會接近最低角度。這可意味著含有界面活性劑的清潔液在第30秒及10倍臨界微胞濃度時表面能會比較穩定。在比較陽離子或陰離子型界面活性劑時，可從實驗數據觀察到同一類型的界面活性劑，如SDS及DTAB界面活性劑，在頭基相同情況下，比較其尾鏈對銅濕潤性影響。
我們可以發現尾基碳鏈越長越親水；帶有雙尾鏈的DDAB及AOT界面活性劑溶液接觸角更可達到30以下。SDS系列的陰離子界面活性劑，以去離子水浸泡後回復的接觸角更可以到達95度，很接近初始值100度，表示表面能又回到原來的狀態，添加酸鹼及鹽類到不同型態溶液中，也可讓接觸角降低，使得銅晶片表面具有濕潤性質。

摘要(英)

In this paper, we can know that the semiconductor production process, especially the Post CMP process is very important. The Post CMP cleaning can let to know how to research the phenomena of copper surface. We present our method for the measurement of contact angles on the surface of copper wafer cleaning process because the standard deviation obtained in our measurements achieved unexpectedly low error. DSA-10 equipment that construction of a goniometer connected with a specially prepared computer program allowed us to repeat measurements several times over a short time course, yielding excellent results. After defining points on the outline of the image of a drop and its baseline as well of the first approximation of the outline of the drop, an iterative process is initiated that is aimed at fitting the model of the drop and baseline. The measurements were made, the work of adhesion is determined according to Young’s equation.
In this study, the main to observe wetting behavior phenomena solders which surfactants on the copper wafer. No sooner had the surface wet than the contact angle became lower. It is represented that surface energy is lower. Example, DI-water wet on the copper wafer surface of cuprous oxide that contact angle is 100° and the surface is very hydrophobic. The surface energy is highly on the surface of copper wafer.
For avoid to the defects on the surface, such as the metal ions and the water mark were remained. In this study, we add the surfactants in the DI-water solvent to research wetting behavior on the copper wafer. In our experiment, we can found the dynamic contact angle that measurement time is 30th seconds and the angle variable is stable status. When the critical micelle concentration (CMC) reach tenth times that the angle variable is the lowest. That is show the cleaning solution that include the surfactants is status in 30th dynamic contact angle and 10th CMC. In compare to the cation and anion of surfactant, we can observe that have the same characteristic type surfactant, having the same head group and the different tail chain. In order to compare the tail chain affects the wet behavior on the surface of copper that we do experiment about the SDS and DTAB different tail chain effect.
We can find that when the carbon tail chain is longer, it wetting ability is more hydrophilic. With double tail chain surfactant, as like the DDAB and AOT that contact angle can lower than 30 degree. When use SDS types surfactant to immerse the DI-water that the contact angle can recover to 95 degree. That approach to the initial number 100 degree. It is show that surface energy recovers initial status. Add to the acid, alkali and salt solution to decrease the contact angle for wetting the surface of copper wafer.

關鍵字(中)

★ 化學機械研磨後清潔
★ 表面接觸角

關鍵字(英)

★ Contact angle
★ Post CMP

論文目次

摘要 ........................................................................Ι
Abstract ..................................................................III
誌謝 ........................................................................V
目錄 .......................................................................VI
圖目錄 ......................................................................X
表目錄 ...................................................................XIII
第一章緒論..................................................................1
1.1前言.......................................................................1
1.2 化學機械研磨介紹…........................................................2
1.2.1 化學機械研磨的發展背景…................................................2
1.2.2 化學機械研磨的設備及材料介紹............................................4
1.2.3 化學機械研磨的製程原理..................................................9
1.3 化學機械研磨後清洗介紹...................................................13
1.3.1 化學機械研磨後清洗的發展背景...........................................13
1.3.2 化學機械研磨後清洗的設備及材料介紹.....................................14
1.3.3 化學機械研磨後清洗的製程原理...........................................18
1.4 界面活性劑介紹...........................................................21
第二章半導體清潔製程與文獻回顧.............................................27
2.1微粒(particle)的發生源 ..................................................27
2.2 微粒(particle)的吸附類型.................................................29
2.3微粒(particle)產生的影響..................................................30
2.4微粒(particle)的去除與影響................................................32
2.4.1 有機物的去除...........................................................32
2.4.2 金屬物的影響...........................................................32
2.4.3 銅離子在矽基板的反應機制...............................................33
2.5清洗液的介紹..............................................................34
2.6文獻回顧..................................................................37
2.6.1專利查詢................................................................37
2.6.2表面潤濕性專利..........................................................38
第三章實驗介紹.............................................................72
3.1實驗儀器介紹..............................................................72
3.1.1 影像式接觸角量測儀.....................................................72
3.1.1.1 接觸角原理介紹.......................................................73
3.1.1.2 表面能原理介紹.......................................................74
3.1.2 旋轉塗佈機(Spin coater) ...............................................75
3.2實驗材料介紹..............................................................76
3.2.1 銅金屬簡介.............................................................76
3.2.2 銅晶片簡介.............................................................78
3.2.3 實驗用界面活性劑簡介...................................................79
3.2.4 實驗用添加劑簡介.......................................................83
3.3實驗流程介紹..............................................................84
3.3.1 實驗前銅晶片表面清潔...................................................84
3.3.2 實驗儀器參數設定.......................................................84
3.3.2.1影像式接觸角量測儀參數設定............................................84
3.3.2.2 旋轉塗佈機參數設定...................................................85
3.3.3 界面活性劑潤濕性實驗流程...............................................90
3.3.3.1 動態表面接觸角量測...................................................91
3.3.3.2 界面活性劑清潔液濃度與銅表面接觸角相關性.............................91
3.3.3.3 比較相同濃度下碳鏈長短對接觸角的影響.................................92
3.3.3.4 界面活性劑加入添加劑的影響...........................................92
第四章實驗結果與討論.......................................................93
4.1 動態表面接觸角量測研究...................................................93
4.2 界面活性劑清潔液濃度與銅表面接觸角相關性研究.............................95
4.2.1 銅與空氣表面能測定方法.................................................96
4.3 比較相同濃度下碳鏈長短對接觸角的影響....................................104
4.4 界面活性劑加入添加劑的影響..............................................106
4.4.1 去離子水中添加酸或鹼..................................................106
4.4.2 去離子水中添加鹽類....................................................107
4.4.3 界面活性劑添加酸、鹼、鹽溶液的潤濕行為................................109
第五章結論................................................................117
第六章參考文獻............................................................118

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指導教授

曹恒光(Heng-Kwong Tsao)

審核日期

2006-6-15

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