臺灣博碩士論文加值系統

本論文利用分子軌域理論計算方法預測矽甲烷/鍺甲烷反應系統合成鍺化矽薄膜程序的主要氣相反應途徑，並配合過渡態理論與量子穿隧理論修正，來求得反應速率常數。結果發現鍺甲烷脫去一個氫分子生成GeH2自由基的反應為系統中起始反應的主要途徑，反應活化能Ea為55 kcal/mol，且在反應溫度873 K下鍺甲烷的分解反應速率為0.8 s-1較矽甲烷快約100倍左右。即使如此，因為SiH2具有較高的插入反應速率並生成一系列SinGeH2(n+1)+2中間產物，其可能為實驗中薄膜的鍺矽含量比隨著反應滯留時間增加而降低的主要原因。

The major gas-phase reaction pathways in the SiH4/GeH4—Si1-xGex— CVD reaction system has been investigated by molecular orbital theory calculations, together with a kinetic evaluation by transition state theory. The results indicate that primary pathway in the beginning is the decomposition of GeH4 to form GeH2 and H2 with an activation energy of 55 kcal/mol and a decomposition rate of 0.8 s-1 at 873 K, 100 times that of SiH4. Nevertheless, SiH2, an intermediate from SiH4, plays an important role in the subsequent reactions because of its much higher insertion reaction rates to form a series of intermediate SinGeH2(n+1)+2, which may be responsible for the experimental decrease of Ge/Si molar ratio in the films with increasing reaction resident time.

中文摘要 --------------------------------------------------------------------------I
中文摘要 -------------------------------------------------------------------------II
致謝 ------------------------------------------------------------------------------III目錄 ----------------------------------------------------------------------------- IV圖索引 --------------------------------------------------------------------------VII
表索引 ---------------------------------------------------------------------------IX
第一章 緒論 --------------------------------------------------------------------1
第二章 理論計算方法 -------------------------------------------------------17
2.1 量子力學基本概念 ------------------------------------------------17
2.2 Born-Oppenheimer approximation --------------------------------20
2.3 分子軌域理論 ------------------------------------------------------22
2.4 變數定理 ------------------------------------------------------------23
2.5 Hartree-Fock方程式 -----------------------------------------------26
2.6密度泛函理論 -------------------------------------------------------30
2.7 原子基底函數 ------------------------------------------------------36
2.8 過渡態 ---------------------------------------------------------------42
2.8-1 反應速率常數--------------------------------------------------42
2.8-2 量子穿隧效應對反應速率常數的影響--------------------46
2.9 計算方法 ------------------------------------------------------------47
第三章 結果與討論 ----------------------------------------------------------49
3.1 SiH4單獨反應可能的氣相反應途徑-----------------------50
3.2 GeH4單獨反應可能的氣相反應途徑----------------------55
3.3 SiH4/GeH4混合系統下可能的氣相反應途徑------------60
3.4 動力學探討：反應速率常數---------------------------------75
3.4-1 量子穿隧效應對反應速率常數的影響--------------76
3.4-2 SiH4/GeH4混合系統中SiH4及GeH4的脫氫反應速率常數探討--------------------------------------------------------79
3.4-3 SiH4/GeH4混合系統下SiH2、GeH2與其他反應物的反應速率常數探討--------------------------------------------81
3.4-4 由理論計算結果推測SiH4/GeH4混合系統中主要的氣相反應途徑---------------------------------------84
第四章 結論 --------------------------------------------------------------------88
第五章 參考文獻 --------------------------------------------------------------90
附錄一 --------------------------------------------------------------------------95
作者簡介 -----------------------------------------------------------------------132

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