臺灣博碩士論文加值系統

中文摘要
隨著積體電路產業矽晶圓尺寸的加大，製程線寬變窄的趨勢，清洗、蝕刻製程的發展，影響半導體產業的進步，製程潔淨程度直接影響元件的良率。因此，必須使用超高潔淨度化學品，以避免化學品中所含不純物污染到矽晶圓表面。而如何準確的分析、管制化學品中不純物的含量，成為維持高製程產率的關鍵因素。然而，複雜的樣品基質，將使低濃度金屬不純物的分析發生困難。為滿足製程需求，使用濃縮前處理技術，將樣品基質揮發去除，有效提高樣品中微量待測成份相對於基質成份之分析訊號的比值，將樣品中待測的微量元素濃縮至儀器穩定可偵測的濃度範圍，增加分析結果可靠性。
本研究選擇以揮發法(Volatilization)，將雙氧水樣品基質蒸發後，再以ICP-MS定量分析待測樣品中所含的微量金屬不純物。結果顯示，定量分析5 ppt標準樣品的添加樣品回收率為80~113%，可符合目前與未來國際半導體設備暨材料協會(Semiconductor Equipment and Materials International, SEMI ) 標準化學品的分析能力需求。

The metallic impurity level of process chemical for integrated circuits industry is getting lower, particularly as the industry moves to larger wafer size and smaller line-widths. To avoid contamination of the wafer surface by the cleaning solution itself, the purity of the reagents must be extremely high. The accurate determination and control of metallic impurities is key to maintaining high production yield. Traditionally, inductively coupled plasma mass spectrometry (ICP-MS) has been the technique of choice for ultra-trace element determinations in high-purity chemicals. However, direct determination by ICP-MS is unsatisfactory owing to insufficient detection power and interference from matrix of the chemicals.
In order to achieve the high sensitive ICP-MS determination, impurity were concentrated by a stabilization evaporator and measured under normal and cool plasma conditions. This study describes the determination of metallic impurities in hydrogen peroxide by ICP-MS after volatilization pretreatment. The result of quantitative spike recoveries at 5 ppt level are 80~113%, indicated excellent measurement accuracy, attain SEMI Grade 5 purity levels.

目錄
中文摘要……………………………………………………………I
英文摘要……………………………………………………………I
目錄…………………………………………………………………III
表目錄………………………………………………………………VI
圖目錄………………………………………………………………VII

第一章前言…………………………………………………… 1
1-1 研究背景…………………………………………………… 2
1-2 研究目標…………………………………………………… 2

第二章 文獻回顧…………………………………………………4
2-1 半導體製程中電子化學品微量金屬元素分析的重要性…4
2-2 現有金屬分析方法………………………………………….5
2-3 現有分析電子化學品微量元素的方法…………………….7
2-4 感應偶合電漿質譜儀…………………………………….…11
2-4-1 樣品導入裝置………………………………………....12
2-4-2 原子化及離子源……………………………………..13
2-4-3 離子聚焦質量分析裝置……………………………..17
2-4-4 ICP-MS的優、缺點…………………………………19

第三章 實驗步驟與樣品分析……………………………………21
3-1 實驗藥品與儀器設備………………………………………21
3-1-1 實驗藥品……………………………………………..21
3-1-2 儀器設備………………………………………………23
3-2 實驗室樣品前處理的環境…………………………………24
3-2-1 環境的污染及控制……………………………………24
3-2-2 試劑污染控制…………………………………………25
3-3 實驗室器皿…………………………………………….……27
3-4 實驗步驟………………………………………………….…28
3-4-1 標準品的製備……………………………………….…28
3-4-2 檢量線製備…………………………………………….28
3-4-3 樣品前處理步驟……………………………………….29
3-4-4 前處理最適化………………………………………….30
3-4-5 儀器最適化…………………………………………….31

第四章 結果與討論……………………………………………..33
4-1 污染控制條件的探討………………………………………..33
4-1-1 容器的污染及清洗……………………………………..33
4-1-2 人員操作污染控制……………………………………..34
4-2 ICP-MS操作條件與偵測極限的探討……………………..35
4-2-1 ICP-MS操作條件……………………………………….35
4-2-2 儀器偵測極限之探討……………………………………39
4-2-3 冷電漿參數………………………………………………39
4-3 前處理條件的探討…………………………………………..42
4-4 分析方法可行性(QA/QC)之探討…………………………..47
4-4-1 儀器檢量線……………………………………………..47
4-4-2 測試雙氧水中微量金屬的回收率……………………..51

第五章 結論…………………………………………………….54
參考文獻…………………………………………………………55

1. 丁志華、戴寶通：半導體廠超純水簡介，毫微米通訊，第七卷第四期，第31-39頁，民國八十六年。2. 江旭禎、楊惠珍：感應耦合電漿質譜儀，質譜分析技術專輯，第341-364頁，民國八十一年。3. 李匡邦、許東明、何東英：激發機理之探討，光譜化學分析，第166-188頁，民國八十六年。4. 陳順隆、張士仁、吳蓮芳、林雨平：分析化學在半導體的應用與原物料的品質保證，半導體人才培訓計畫講義，自強工業科學基金會，民國九十一年。5. 黃立心、林金全等：ICP-MS 專題，科儀新知第二十卷一期，民國八十七年。6. 黃傳捷：利用感應耦合電漿質譜儀進行生物樣品中微量元素及其物種分析研究，碩士論文，國立清華大學原子科學研究所，民國八十六年。7. 葛榮祖：利用微波消化前處理技術與電熱式汽化裝置連線技術配合感應耦合電漿質譜儀分析半導體用光阻劑中微量雜質元素之研究，碩士論文，國立清華大學原子科學研究所，民國九十年。8. 詹育智：利用超臨界流體萃取配合放射性示蹤技術進行矽晶圓表面超潔淨清洗效應之探討，碩士論文，國立清華大學原子科學研究所，民國八十七年。9. Barwick V. J., Stephen L.R. E., Ben F., (1999) Estimation of uncertainties in ICP-MS analysis: a practical methodology, Anal. Chim. Acta, 394, 281-29110. Becker J. S. and Dietze H. J., (1998) Inorganic trace analysis by mass spectrometry: review, Spectrochim. Acta Part B, 1475-150611. Becker J. S. and Dietze H. J., (2000) Inorganic mass spectrometrymethods for trace, ultratrace, isotope, and surface analysis, Int. J. Mass Spectrom, 197, 1-3512. Broekaert J.A.C., (2000) Stste-of-the-art and trends of development in analytical atomic spectrometry with inductively coupled plasmas as radiation and ion sources: review, Spectrochim. Acta Part B, 55, 739-75113. Collard J. M., Interox S., Kawabata K., Kishi Y. and Thomas R., (2002) Implementing enhanced ICP-MS technology to attain SEMI Grade 5 purity levels, Micro Magazine, (Critical Materials---Chemicals)14. Gupta J. G. S., and Bertrand N. B., (1995) Direct ICP-MS determination of trace and ultratrace element in geological materials after decomposition in a microwave oven, Part I Quantitation of Y, TH, U and the lanthanides, Talanta, 42, 1595-160715. Gupta J. G. S., and Bertrand N. B., (1995) Direct ICP-MS determination of trace and ultratrace element in geological materials after decomposition in a microwave oven, Part II Quantitation of Ba, Cs, Ga, Hf, In, Mo, Nb, Pb, Sn, Sr, Ta and Tl, Talanta, 42, 1947-195716. Hinn G. M. and Nelson B. K., (1997) Production and analysis of repetitive sub-boiling laboratory reagent for purity enhancement, Phys. Res. A, 397, 189-19317. Hutton R. C. and Grote B., (1996) Sample induction systems for ICP-OES and ICP-MS, Anal. Magazine, 24, 29-3118. McCurdy E. and Potter D.,(2001) Optimising ICP-MS for the determination of trace metals in high martix samples, Spectroscopy Europe, 13, 14-20.19. Niu H. and Houk R. S., (1996) Fundamental aspects of ion extraction in inductively coupled plasma mass spectrometry, Spectrochim. Acta Part B, 51, 779-81520. Rodushki I., Ruth T., Huhtasaari A, (1999) Comparison of two digestion methods for elemental determinations in plant material by IPC techniques, Anal. Chim. Acta, 378, 191-20021. Rouessac F. and Rouessac A., (2000) Chemical Analysis Modern Instrumentation Methods and Techniques, John Wiley& Sons, Ltd, New York, PP289-31522. Sing R., (1999) Direct sample insertion for inductive coupled plasma spectrometry, Spectrochim. Acta Part B, 54, 411-441.23. Takeda K., Ikushima S., Okuzaki J., Watanabe S., Fujimoto K. and Nakahara, (1998) Determination of ultra-trace impurities in semiconductor-grade water and chemical by inductively coupled plasma mass spectrometric following a concentration step by boiling with mannitol, Anal. Chim. Aata, 377, 47-5224. Takeda K., Ikushima S., Okuzaki J., Watanabe S., Fujimoto K. and Nakahara, (2001) Inductively coupled plasma mass spectrometric determination of ultra-trace elements in electronic-grade water and chemicals using dulcitol, Anal. Chim. Aata, 426, 105-10925. Tan S. H. and Horlick G., (1986) Background Spectral Features in Inductively Coupled Plasma Mass Spectrometry, Appl. Spectroscopy, 40, 445-46026. Tangen A., Lund W.,(1999) A multivarite study of the acid effect and the selection of internal standards for inductively coupled plasma mass spectrometry, Spectrochimica Acta Part B, 54, 1831-1838.27. Todoli J. L. and Mermet J. M., (1999) Acid interferences in atomic spectrometry: analyte signal effects and subsequent reduction, Spectrochimica Acta, Part B, 54, 895-929.28. Tsoupras G. (1996) ICP-MS application to semiconductor processing chemical materials analysis, Anal. Magazine, 24, 23-2829. Vaughan M. A. and Horlick G., (1986) Oxide, Hydroxide, and Doubly Charged Analyte Species in Inductively Coupled Plasma Mass Spectrometry, Appl. Spectroscopy, 40, 434-44430. Yuan H., Hu S., Tong J., Zhao L., Lin S. and Gao S.,(2000) Preparation of ultra-pure water and acids and investigation of background of an ICP-MS laboratory, Talanta, 53, 971-981