臺灣博碩士論文加值系統

使用紅外線光譜儀與紫外光-可見光光譜儀來描述添加不同重量之poly (styrene-co-maleic anhydride)修飾ZEP520電子束阻劑。發現經修飾阻劑的電子親和性物質並未改變，只有在主鏈上之聚合物結構稍有變化。使用n&k測厚儀、光學薄膜測厚儀、紅外線光譜儀與熱分析儀評估旋塗在晶圓上阻劑薄膜厚度特性，依次量測孔隙度、厚度、震動光譜和熱穩定性。我們分析結果顯示添加修飾劑之阻劑，其熱穩定性較佳，並發現阻劑有兩個主要熱解步驟，第一步微電子親和性物質分解，第二步是聚合物之aromatic ring分解。研究修飾之電子束阻劑在抗電漿蝕刻上，所使用的fluorine-containing電漿在ULSI應用上是對光罩與矽元件的蝕刻。研究結果得知修飾的電子束阻劑受fluorine-containing電漿蝕刻後，其靈敏度、對映比、解析度與溶解度比，與原來的電子束阻劑相較並沒有任何負面的影響。我們應用大氣壓力離子化質譜分析儀作為熱脫附系統的偵測工具，可用來分析像是水、有機物等之微量不純物，在大氣環境下這些不純物質約有pico-gram的含量吸附在晶圓表面上。
另外在不純物分析上，首先使用密閉式微波消化與開放式微波消化分解微影材料，再趕酸至盡乾，然後加水稀釋，再以UV-VIS光譜評估消化效率，感應耦合電漿質譜儀偵測其微量元素。另一方面不同的消化配方也可以使用總剩餘固體重量來評估消化率。研究兩種的消化方法其分析的偵測極限皆可低於ng/g的水準。對其數據精確的評估，結果得知兩種不同的消化方法是相呼應。所有元素添加回收率皆在70-130 %之間。在SIA roadmap所預測的微量污染物控制極限為前提下，在未來的十年，以我們所樹立的微影材料品質控制方法將是可預見的。

The modification of the electron-beam resist (ZEP520) after spiking with various amounts of poly(styrene-co-maleic anhydride) is characterized by the spectra of Fourier Transfer infrared red (FTIR) and ultraviolet visible (UV-VIS). The chemical structure of electron affinity compound is found to be unchanged after modification, while slight change in the polymer chain is observed. The resist layer coated onto the wafer is characterized by various methods including n&k analyzer, Nanospec, FTIR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) to fully evaluate the film properties in term of porosity, thickness, vibrational spectrum, and thermal stability. Our analysis results show that thermal stability of the resist is increase with spiking polymer, and the resist are mainly decomposed in two stages. The electron affinity compound is decomposed during the first stage, while the aromatic ring of polymer decomposes during the second stage. The invention is a modified electron-beam resist which is resistant to etch in fluorine-containing plasma, and therefore particularly useful for masking and etching the silicon device in ULSI applications. The additive copolymer is of a type and in an amount effective to substantially prevent etching of the modified electron-beam resist in a fluorine-containing plasma without adversely affecting the sensitivity, contrast, resolution and solubility ratio during fluorine-containing plasma exposure to an underlying layer to be patterned and etched. By applying Atmospheric Pressure Ionization Mass system (APIMS) for the detection tool for Thermal desorption system (TDS), we have made it possible to analyze the trace impurity such as H2O and organic compound etc., which is adsorbed on wafer surface down to the level of Pico-gram in the environment of atmospheric pressure.
In this work, the lithographic materials are first decomposed by the close-vessel and open-focused microwave oven, and the digest is evaporated to incipient dryness. After adding water, the sample solutions are used either for evaluating the completeness of the digestion process by UV-VIS spectrometer, or for the determination of eleven elements using inductively coupled plasma mass spectrometry (ICP-MS). In addition, the digestion efficiency is also evaluated by the weight of total dry residual after various digestion recipes. By the complementary digestion method, the method detection limits for analyzes can be achieved at lower than ng/g level. For evaluation of data accuracy, the results obtained by the two independent digestion methods are in good agreement. Moreover, the spiking recovery tests for all the elements are of 70 to 130%. According to the micro-contamination control limit predicted by the SIA roadmap, the established method can meet the requirements for the quality control of lithographic materials in the future ten years.

目錄 i
圖目錄v
表目錄ix
第一章 緒論1
1.1 微影製程發展現況1
1.2 阻劑的修飾3
1.3 微影材料不純物質之分析5
1.4 研究動機與本文大綱7
第二章 原理10
2.1 微影製程10
2.1.1 上底材（priming）11
2.1.2 上阻劑13
2.1.3 軟烤16
2.1.4 曝光18
2.1.5曝光後烘烤22
2.1.6顯影23
2.1.7硬烤24
2.2阻劑的基本性質25
2.2.1 I-line光阻劑25
2.2.2 KrF光阻劑28
2.2.3 ArF光阻劑30
2.2.4 e-beam阻劑31
2.3微影相關光學參數33
2.3.1折射率（n）與吸收係數（k）33
2.3.2 穿透度（T）、穿透率（T %）與吸收度（A）34
2.2.3透鏡之數值孔徑與f值35
2.3.4相擾度（degree of coherence , sigma , s）36
2.3.5阻劑搖擺比（swing ratio）38
2.3.6靈敏度與對映比39
2.3.7迪耳（Dill）參數41
2.4微影材料不純物分析方法42
2.4.1微波加熱理論43
2.4.2微波消化法44
第三章 實驗46
3.1化學藥品46
3.2儀器48
3.3實驗步驟53
3.3.1微影驗證的樣品製備與程序53
3.3.2微波消化與樣品分析60
第四章 結果與討論63
4.1微影製程驗證63
4.1.1轉速對阻劑薄膜厚度之影響63
4.1.2紫外光-可見光吸收光譜儀的特性評估65
4.1.3紅外光光譜儀的評估68
4.1.4熱分析71
4.1.5折射率（n）與吸收度（k）之量測80
4.1.6抗蝕刻89
4.1.7曝光後的影響90
4.1.8阻劑去除94
4.1.8.1一般製程94
4.1.8.2蝕刻製程109
4.1.8.3離子佈植113
4.2微影材料純度分析116
4.2.1密閉式微波消化法之效率評估116
4.2.2開放式微波消化法之效率評估123
4.2.3微影材料的分析127
第五章 結論132
參考文獻135

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