臺灣博碩士論文加值系統

中文摘要
有效的化學機械研磨後清洗製程(Post-CMP Cleaning)是化學機械研磨(Chemical Mechanical Polishing，CMP)能否成功運用在半導體製程的重要因素。在有效移除微粒的清洗製程中，多孔性聚乙烯醇縮醛泡綿（PVA Foam）憑藉著平穩的表面接觸、強力吸水性、高度柔軟性及最好的回復性，比起傳統磨合式毛刷，PVA泡綿在使用上占有絕佳的優勢。PVA泡綿的清洗效能與PVA泡綿表面的孔洞呎吋(Pore Size)、粗糙度(Asperities)和黏附力(Adhesion) 有很大的關聯。在本文中，不同聚合度(DP=500 或 1700)的PVA泡綿經由相同的實驗流程製作成測試樣品，經由場發射掃描式電子顯微鏡（SEM）、熱重分析（TGA）、拉伸長度分析、硬度、透水性的實驗來比較其效能。實驗結果顯示，比起高聚合度PVA泡綿，低聚合度聚乙烯醇原料可製作出孔徑較大，三維交聯結構較為細緻柔軟且較低保水率的PVA泡綿。因此低聚合度的PVA泡綿在硬碟基材清洗實驗上，呈現的微粒塵殘留量及基材的刮傷片數都低於高聚合度PVA泡綿，清洗後的基材淨潔過片數比率高於高聚合度PVA泡綿2%。本研究結果證明了PVA泡綿的物性改變提升原有化學機械研磨後清洗製程效率的可能性，進而針對不同產品的化學機械研磨後清洗製程而製作相對應的客製化PVA泡綿，提升清洗製程的生產效益。
關鍵字：聚乙烯醇縮醛泡綿，化學機械研磨，化學機械研磨後清洗

Abstract
The performance of chemical mechanical polishing (CMP) process strongly depends on the effectiveness of the post-CMP cleaning. In particle removal using brush cleaning, polyvinyl alcohol (PVA) foam provides a fundamental advantage over standard friction-fitted brushes by providing consistent grapping, excellent water absorption, soft and best resilience. The cleaning performance of PVA foam strongly relates to the pore sizes, asperities and adhesion forces on the surface. In this thesis, two kinds of PVA foam were synthesized from water soluble PVA with different degrees of polymerization (500 or 1700) through identical modified procedure, and then were analyzed by using scanning electron microscopy (SEM), thermo-gravimetric analysis (TGA), and conductivity to compare the effectiveness between these two kinds of PVA foam. Experimental result shows that the lower degree of polymerization (500) PVA foam contains bigger pore size and more condensed structure. Therefore, as compared with higher degree of polymerization PVA foam, the PVA foam with lower degree of polymerization presents higher effectiveness after cleaning, including lower amount of particles/defects and 2% higher rate of successful wafers. The result proves that the attribute of PVA foam enhances feasibility of post-CMP cleaning process and provides customized PVA foams for different products to optimizing cleaning effectiveness of post-CMP.
Keywords: PVA foam, chemical mechanical polishing, post-CMP process

目 錄
中文摘要 ii
英文摘要 iii
誌 謝 iv
目 錄 v
圖目錄 vii
表目錄 x

第一章 緒論 1
1.1 前言 1
1.2 文獻探討 1
1.3 研究動機與目的 4
1.4 論文架構 4
第二章 現有技術簡介 5
2.1 聚乙烯醇的簡介 5
2.2 聚乙烯醇的化學性質 9
2.3 聚乙烯醇縮甲醛聚合物 12
2.4 PVA泡綿應用 21
第三章 實驗方法 25
3.1 實驗規劃 25
3.2 多孔性PVA泡綿的製備 32
3.3 反應率分析 35
3.4 PVA泡綿之物性測試 38
第四章 結果與討論 45
4.1 反應率分析 46
4.2 PVA 泡綿的物性分析 48
4.3 清洗機清洗測試結果 59
第五章 結論與未來研究方向 61
5.1 結論 61
5.2 未來研究方向 62
參考文獻 63


圖目錄
圖2 1 澱粉顆粒組織的結構示意圖 15
圖2 2 一般常見的澱粉顆粒懸浮液，在不同溫度與操作條件下，整體溶液黏度的變化情形 16
圖2 3 表示PVA泡綿以非接觸式的清潔模式：將膠體粒子由基材表面移除的示意圖 22
圖2 4 表示PVA泡綿的清潔模式：附著在基材表面上的膠體粒子，受到各種作用於其表面的作用力平衡示意圖 22
圖3 1 多孔性聚乙烯醇縮甲醛泡棉的製備流程圖 26
圖3 2 PVA 泡綿成型模具圖 27
圖3 3 以3.0 wt%的小麥澱粉作為造孔劑，來製備多孔性PVA泡綿 27
圖3 4 以3.0 wt%的小麥澱粉作為造孔劑，來製備多孔性PVA泡綿 28
圖3 5 PVA 泡綿物性測試流程圖 29
圖3 6 JEOL (Japan)場發射掃描式電子顯微鏡，型號：JSM - 7000F 38
圖3 7 INSTRON (USA) 拉力試驗機，型號：4467 39
圖3 8 DuPont (USA) 熱重分析儀，型號：TA Q50 41
圖3 9 ANS(Taiwan)邵氏硬度計，型號：302SL 42
圖3 10 透水速率實驗實作圖 43
圖3 11 PVA泡綿於硬碟基板清洗機清洗測試示意圖 44
圖4 1 利用UV-Visible Spectrophotometer在波長為412nm時，測量甲醛溶液的標準檢量線圖 47
圖4 2 聚乙烯醇與甲醛反應成為PVA泡綿的轉化率關係圖 47
圖4 3 以3.0wt%的小麥澱粉作為造孔劑，來製備多孔性的PVA泡綿，利用SEM觀察多孔性PVA 泡綿的表面結構 49
圖4 4 以3.0wt%的小麥澱粉作為造孔劑，來製備多孔性的PVA泡綿，利用SEM觀察多孔性PVA泡綿的表面結構 49
圖4 5 以3.0wt%的小麥澱粉作為造孔劑，來製備多孔性的PVA泡綿，利用拉伸試驗機測量PVA泡綿的機械強度與拉伸長度 51
圖4 6 以3.0wt%的小麥澱粉作為造孔劑，來製備多孔性的PVA泡綿，利用拉伸試驗機測量PVA泡綿的機械強度與拉伸長度 52
圖4 7 以3.0wt%的小麥澱粉作為造孔劑，來製備多孔性的PVA泡綿，利用TGA測量PVA泡綿的含水率 53
圖4 8 以3.0wt%的小麥澱粉作為造孔劑，來製備多孔性的PVA泡綿，利用TGA測量PVA泡綿的含水率 54
圖4 9 以3.0wt%的小麥澱粉作為造孔劑，來製備多孔性的PVA泡綿，利用TGA測量PVA泡綿的脫水速率 55
圖4 10 以3.0wt%的小麥澱粉作為造孔劑，來製備多孔性的PVA 泡綿，利用TGA測量PVA泡綿的脫水速率 55
圖4 11 利用硬度計測量多孔性PVA泡綿的硬度比較圖 56
圖4 12 利用滴管測量多孔性PVA泡綿的透水性比較圖 58
圖4 13 PVA泡綿於硬碟基材清洗機清洗後淨潔過片數比率比較圖 60
圖4 14 PVA泡綿於硬碟基材清洗機清洗測試粉塵殘留數比較圖 60


表目錄
表2 1 直鏈澱粉和支鏈澱粉的物理化學性質 14
表2 2 天然澱粉的糊化特性 18
表3 1 實驗儀器清單 29
表3 2 實驗藥品清單 31

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