臺灣博碩士論文加值系統

矽乙烷(Disilane, Si2H6)，屬於自燃性氣體，作為特用電子氣體，在半導體先進製程扮演關鍵材料，是一種重要的矽源前驅物；目前矽乙烷文獻的燃燒下限為0.1~0.5 vol.%不等，為了更全面了解矽乙烷，故本研究分為三個階段，首先會在穩態排放下，觀察矽乙烷自燃的引燃行為及臨界出口流速，接著利用臨界出口流速，製備矽乙烷/氮氣與空氣的混合物，且測定燃燒下限及限氧濃度，最後階段，將壓縮空氣與穩定流動中的矽乙烷/氮氣混合，找出適當矽乙烷/氮氣稀釋比例。
第一項階段為矽乙烷穩態排放測試，藉由質量流量控器控制氣體流量，搭配電子四向閥的開關來切換平行的矽乙烷以及氮氣流，確保矽乙烷能以穩態的流量排放至排放出口端，臨界出口流速與矽乙烷濃度及排放出口端內徑有關，並藉助高速攝影機擷取，量測立即引燃距離，且經由邊界層理論，求得純矽乙烷於一般大氣下的最強反應混合濃度為61 vol.%。
第二項階段為矽乙烷燃燒下限與限氧濃度的測定，皆在20升爆炸鋼球進行測定，於燃燒下限之測試，將矽乙烷/氮氣以高過臨界出口流速灌至爆炸鋼球，本研究成功製備矽乙烷/氮氣與壓縮空氣或乾燥空氣之混合物範圍為0.1~2.14 vol.%，當矽乙烷/氮氣與壓縮空氣混合物濃度> 2.14 vol.%，則會發生本體自燃現象。以此測出矽乙烷之最小燃燒下限為0.50 ± 0.02 vol.%；在限氧濃度之測試中，發現純矽乙烷與0.1 vol.%的氧氣/氮氣之混合物仍會產生反應，代表著矽乙烷是極度容易與氧氣進行反應，以此推論矽乙烷之燃燒上限近乎100 vol.%。
最後一項階段為模擬矽乙烷釋放測試，會透過震波管道進行初步模擬，觀察矽乙烷/氮氣混合物與壓縮空氣反應的最大升溫、最大升壓，發現由矽乙烷/氮氣(1.1~5.6 vol.%)與壓縮空氣接觸僅只有發生溫和燃燒而無爆炸與過壓，且藉由更換溫度量測點位，得知最大升溫變化會發生在管道中心；接著於壓克力管道進行測試，利用壓克力管道透明特性，觀察矽乙烷/氮氣混合物與壓縮空氣燃燒的現象；結果證實只需將矽乙烷/氮氣濃度保持在5.6 vol.%以下，而不是文獻中的矽乙烷燃燒下限0.1~0.5 vol.%，此結果有助於科技廠真空泵的氮氣吹驅量，並以升溫變化作為一種安全指標。

Disilane(Si2H6), is a pyrophoric gas and used as a special electronic gas which plays a key role in advanced semiconductor manufacturing process as an important silicon source precursor. In order to have a more comprehensive understanding of disilane, this study is divided into three parts. Firstly, the pyrophoric behavior of disilane and the critical exit velocity of disilane are observed under steady-state release condition. Then, the critical exit velocity is used to prepare the mixture of disilane/nitrogen and air. The lower flammability limit and limiting oxygen concentration were determined. Finally, minimum dilution ratio of disilane/nitrogen in the exhaust duct which do not lead to excessive combustion and temperature rise when air leaked in was determined.
In the first part of study, the steady flow release test of Disilane into air was performed with mass flow controllers and an electrically four-way switching valve so that steady disilane flow was released without acceleration to the vent stub. The critical exit velocity was found to be a function of disilane concentration and vent stub inner diameters. High-speed camera was used to measure the ignition distance. The most reactive fraction of pure disilane in ambient atmosphere was calculated to be 61 vol.% by using boundary layer theory.
The second stage is the determination of the lower flammability limit (LFL) of disilane and limiting oxygen concentration (LOC). The determination is carried out in a 20-litre explosion sphere apparatus. At the LFL, the mixture of disilane/nitrogen with compressed air or dry air is successfully prepared in the range of 0.1~2.14 vol.%. When the concentration of disilane in air mixture is greater than 2.14 vol.%, bulk autoignition occurred, The LFL of disilane is determined to be 0.50 ± 0.02 vol.%. It was also found that pure disilane will react with oxygen/nitrogen mixture even with only 0.1 vol.% oxygen. Thus, the upper flammability limit of disilane is close to 100 vol.%.
The final part is to simulate the exhaust test of nitrogen diluted disilane. Preliminary simulation is carried out through the shock pipe to observe the maximum temperature rise and maximum overpressure of the reaction between the disilane/nitrogen mixture and the compressed air. It is found that only mild combustion occurs without explosion and overpressure when the disilane/nitrogen mixture (1.1~5.6 vol.%) contacts the compressed air. It is found that the maximum temperature change will occur in the center of the pipe; The combustion of the mixture of disilane/nitrogen and compressed air was visualized by using an acrylic pipe. The results show that it is safe to keep the disilane concentration below 5.6 vol.%, rather than the LFL of disilane in the literature 0.1~0.5 vol.%. The results are useful to the nitrogen purge of vacuum pumps and the temperature rise can be used as a safety index.

摘 要 i
ABSTRACT ii
誌 謝 iv
目 錄 v
表 目 錄 vii
圖 目 錄 viii
名 詞 解 釋 xi
1 壹、緒論 1
1.1 矽乙烷的危害特性 1
1.2 矽乙烷事故案例回顧與分析 3
1.3 研究主要目標 4
1.4 論文架構 5
2 貳、文獻回顧 6
2.1 矽乙烷穩態排放 6
2.2 矽乙烷燃燒下限與限氧濃度 10
2.3 固液相官能基分析 15
2.4 文獻總表 17
3 參、研究方法與材料 18
3.1 研究架構 18
3.2 研究方法 19
3.2.1 矽乙烷穩態排放測試 (一般大氣) 19
3.2.2 矽乙烷穩態排放測試 (控制水氣之燃燒腔室) 21
3.2.3 矽乙烷燃燒下限測定與限氧濃度測定 23
3.2.4 模擬矽乙烷釋放測試 28
3.3 研究材料與設備 31
3.3.1 氣體規格 31
3.3.2 配管、氣材料 31
3.3.3 偵檢設備 32
3.3.4 研究主要裝置 32
4 肆、結果與討論 33
4.1 矽乙烷穩態排放測試 (一般大氣、控制水氣之燃燒腔室) 33
4.1.1 矽乙烷穩態排放測試 (一般大氣) 33
4.1.2 矽乙烷穩態排放測試 (控制水氣之燃燒腔室) 45
4.2 矽乙烷之燃燒下限與限氧濃度 47
4.2.1 矽乙烷之燃燒下限 (於壓縮空氣、乾燥空氣) 47
4.2.2 矽乙烷之限氧濃度 62
4.3 模擬矽乙烷釋放測試 64
4.3.1 模擬矽乙烷釋放測試 (震波管道) 65
4.3.2 模擬矽乙烷釋放測試 (壓克力管道) 72
4.4 固液相官能基分析 76
5 伍、結論與建議 79
5.1 研究結論 79
5.2 未來研究建議 80
參考文獻 81
6 附錄一 穩態排放系統研究條件 83
7 附錄二 燃燒下限與限氧濃度測定研究條件 98
8 附錄三 模擬矽乙烷釋放測試研究條件 103

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