臺灣博碩士論文加值系統

六氯矽乙烷(Hexachlorodisilane，HCDS)是新世代半導體化學氣相沉積製程的矽來源氣體，但其極易水解，且因水解產物具有撞擊敏感性，容易因撞擊而發生爆炸性反應，因此本研究透過能精確控制六氯矽乙烷水解過程的系統進行六氯矽乙烷及其水解產物危害與安全處理方法之研究。而且本研究使用落槌測試儀來鑑認撞擊敏感性，並使用協調全反射式傅立葉轉換紅外線光譜儀(Attenuated total reflection-Fourier transform infrared spectroscopy，ATR-FTIR)來分析水解產物之官能基。
經實驗結果發現六氯矽乙烷水解會生成矽醇(Si-OH)和氯化氫，在水解過程中水解產物會將六氯矽乙烷中的Si-Si鍵保留下來。而Si-Si鍵會因撞擊而斷鍵，並讓成對相鄰的矽醇發生分子內自氧化反應生成產生網狀結構矽的氧化物和氫氣。水解產物的最小撞擊能量(Limiting impact energy，LIE)水解產物中的氧/矽比成正比。除此之外，還發現濃鹽酸可以抑制造成水解產物撞擊敏感性不可或缺官能基之一的Si-Si鍵，進而消除撞擊敏感性；而氫氧化鉀/醇溶液可以完全將六氯矽乙烷蒸氣溶解並生成無危害性的二氧化矽，提供一個能安全處理六氯矽乙烷的方法。在本文最後會針對四種現實中六氯矽乙烷外洩之狀況，包含六氯矽乙烷水解產物、六氯矽乙烷液體溢出、六氯矽乙烷蒸氣洩漏以及六氯矽乙烷液體洩漏且伴隨火災，提供相關處理和消除撞擊敏感的實務建議，讓與六氯矽乙烷產業相關之從業人員能安全地處理六氯矽乙烷及其水解產物，進而減少火災爆炸事故的發生。

Hexachlorodisilane (HCDS) is a new generation silicon source gas for chemical vapor deposition processes. However, HCDS can hydrolyze rapidly with water. The hydrolyzed products are known to be shock-sensitive and it may be ignited easily by mechanical impact to generate explosive reaction. In the present work, hazards and disposal methods for HCDS and its hydrolyzed products was studied through systems which can control accurately the HCDS hydrolysis processes. Moreover, a fall hammer apparatus was used to determine shock sensitivity and an attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) was used to analyze chemical functional groups of hydrolyzed products in this work.
It was found that hydrolysis of HCDS forms silanols (Si-OH) and HCl. In the hydrolysis process, hydrolyzed products retained Si-Si bonds in HCDS. The Si-Si bond can be cleaved by shock leading to intramolecular oxidation by the paired silanols to form a networked silicon oxide and hydrogen. The limiting impact energy (LIE) of hydrolyzed products was also found proportional to the oxygen/silicon ratio in the hydrolyzed products. In addition, concentrated sulfuric acid was found to can suppress the Si-Si bonds, one of the essential roles of chemical functional groups in shock sensitivity of the HCDS hydrolyzed products to diminish the shock sensitivity. KOH/alcohol solution can completely dissolve the HCDS vapor to non-hazardous silica, so that, it provided a safe way to dispose HCDS. Finally, practical recommendations about disposing and diminishing the risk of shock sensitivity are given for four realistic situations of HCDS releases including HCDS hydrolyzed products, HCDS liquid spill, HCDS vapor vent and HCDS liquid spill with fire. The results in this work will benefit the workers in the industries related to HCDS to dispose HCDS and its hydrolyzed products safely and reduce fire and explosion incidents.

摘要 i
ABSTRACT iii
誌 謝 v
目 錄 vi
表目錄 viii
圖目錄 ix
專有名詞縮寫之中英文對照 xi
第一章 前言 1
1.1研究背景 1
1.2事故案例 3
第二章 文獻回顧 5
2.1六氯矽乙烷危害特性 5
2.2六氯矽乙烷及其水解產物處理方法 9
2.3研究目的 13
2.4研究架構 13
第三章 實驗方法與設備 15
3.1撞擊敏感性鑑認 15
3.2官能基與形態鑑認 18
3.3六氯矽乙烷水解過程 19
3.3.1液相水解控制系統 20
3.3.2氣相水解控制系統 22
3.4六氯矽乙烷處理方法 23
3.4.1測試材料 24
3.4.2抑制劑測試系統 25
3.4.3六氯矽乙烷蒸氣在抑制劑中溶解量測試系統 25
3.5六氯矽乙烷水解產物處理方法 26
第四章 六氯矽乙烷及其水解產物危害之探討 28
4.1六氯矽乙烷水解產物撞擊敏感性 28
4.1.1六氯矽乙烷液體於大氣環境中水解 33
4.1.2液相水解產物撞擊敏感性與空氣濕度的關係 35
4.1.3液相水解產物撞擊敏感性與水解時間的關係 38
4.1.4六氯矽乙烷氣相水解產物 41
4.2六氯矽乙烷水解產物特性 42
4.2.1水解產物結構 42
4.2.2水解產物型態 48
4.2.3水解產物燃燒熱 51
4.2.4惰性環境中之撞擊引燃測試 52
4.2.5水解產物熱安定性測試 55
4.2.6撞擊敏感性機制 58
第五章 六氯矽乙烷及其水解產物安全處理方法之探討 61
5.1六氯矽乙烷蒸氣之處理 61
5.1.1抑制劑確認 61
5.1.2氫氧化鉀溶解六氯矽乙烷之機制 73
5.1.3六氯矽乙烷蒸氣在氫氧化鉀/醇類溶液中最大溶解量 74
5.2六氯矽乙水解產物之處理 79
5.2.1過量水測試 79
5.2.2高溫苛性鹼水溶液測試 81
5.2.3硫酸水溶液測試 83
5.3處理六氯矽乙烷及其水解產物之實務建議 86
第六章 結論 88
參考文獻 90

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