原子層沉積(Atomic Layer Deposition，ALD)是新一代的半導體產業的技術，比起一般常見的薄膜沉積有更高的沉積品質，已被廣泛所採用。六氯矽乙烷(Hexachlorodisilane, HCDS, Si2Cl6)有較低的沉積溫度，解離的矽原子也較容易填入更微小的溝槽，已取代其他矽烷氣體，成為ALD製程中矽沉積的主要前驅氣體。
但六氯矽乙烷極易與環境中的水氣反應，水解過程產生鹽酸蒸氣，且由事故與相關文獻中得知水解後的沉積物具有撞擊敏感性。在ALD製程中，多餘的六氯矽乙烷氣體有很高的機率在製程中結合，於尾氣端凝結，若再接觸到水氣而水解，將形成具有撞擊敏感性的沉積物，對於製程管線的維修、清理上有很大的風險，如處理不當則會造成非常嚴重的災害。
本研究使用六氯矽乙烷與小型石英管來模擬ALD製程，利用小規模的製程實驗來探討實際ALD製程的尾氣端是否會生成具有危害或撞擊敏感性的沉積物，並探討該沉積物之危害特性與找出可能的抑制方法。
研究結果發現，在模擬實際的ALD製程中，尾氣端在常溫段會有淡黃色之膠狀沉積物產生，且沉積量隨時間增加。此膠狀物不具有撞擊敏感性，但在水解之後極具有撞擊敏感性，後續也進行了不同的抑制測試，結果發現250℃以上的加熱可以抑制水解後沉積物之撞擊敏感性，而醇類配製的鹼性溶液對於水解前與水解後的沉積物皆有很好的溶解與分解效果。

Atomic Layer Deposition(ALD) is a new generation semiconductor manufacturing technology. ALD offers better deposition quality over traditional chemical vapor deposition methods and has been widely used. Hexachlorodisilane (HCDS, Si2Cl6) has a lower deposition temperature, the dissociated silicon can fill into a smaller trench, and thus has been replacing other silane gases as the ALD major silicon precursor gas.
However, HCDS reacts easily with moisture in the air, generating hydrogen chloride, and formed shock sensitive deposits according to past incidents and literatures. In the ALD processes, excess HCDS has high probability to recombine and condense in the exhaust. Shock sensitive deposit may form when contact moisture. These deposits pose significant hazards for maintaining and cleaning the exhaust line.
In this study, HCDS and a small-scale quartz tube were used to simulate the ALD process. The simulated experiments aimed to find out if hazardous or shock sensitive deposit may formed in the exhaust line and also to find out the hazardous properties and hazard suppression method for the deposit.
The results found that light yellow gel may formed in the exhaust line under ambient temperature. Amount of gel increased with increasing deposition time. This gel is found to be non-shock sensitive but became shock sensitive after hydrolysis. Different methods for suppression the hazards were done. It is found that heating to 250℃ and above will eliminate the shock sensitivity of the hydrolyzed gel. Alcoholic solutions of alkaline may dissolve and decompose the hydrolyzed and unhydrolyzed gel.

摘要 i
Abstract ii
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
第一章 緒論 1
1.1 研究動機 1
1.2 研究目的 2
第二章 文獻回顧 3
2.1 ALD原理與相關文獻 3
2.2 六氯矽乙烷事故案例與撞擊敏感性之探討 9
第三章 材料與方法 19
3.1 研究方法 19
3.1.1 實驗規劃 19
3.1.2 實驗架設 20
3.1.3 分析方法 29
3.2 研究架構 35
3.3 研究器材與設備 36
3.4 實驗流程 38
3.4.1 沉積物之生成 39
3.4.2 沉積物之分析 41
第四章 結果與討論 42
4.1 沉積物之生成與初步結果 42
4.1.1 第1筆測試 44
4.1.2 第2筆測試 47
4.1.3 第3筆測試 50
4.1.4 第4筆測試 53
4.1.5 第5筆測試 56
4.1.6 第6筆測試 58
4.2 沉積物之分析 61
4.2.1 重量比例分析 62
4.2.2 官能基分析 64
4.2.3 撞擊敏感性測試 68
4.2.4 水解穿透性測試 71
4.3 沉積物抑制測試 73
4.3.1 加熱測試 74
4.3.2 溶解測試 78
第五章 結論 86
參考文獻 88

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