研究生: |
馬正杰 Ching-kit Ma |
---|---|
論文名稱: |
矽烷/鍺烷在矽(100)-2x1 表面吸附反應機制之理論計算的研究 Theoretical Study of Surface Reaction of SiH4,Si2H6,GeH4 and Ge2H6 on Si(100)-2x1 surface : Mechanism and Kinetics |
指導教授: |
江志強
Jyh-Chiang Jiang |
口試委員: |
蔡大翔
none 王伯昌 none 林聖賢 none 洪儒生 none |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2005 |
畢業學年度: | 93 |
語文別: | 中文 |
論文頁數: | 146 |
中文關鍵詞: | 分子軌域理論 、過渡態理論 、鍺甲烷 、鍺化矽 、矽甲烷 |
外文關鍵詞: | molecular orbital theory, Ge2H6, tunn |
相關次數: | 點閱:204 下載:0 |
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摘要
本文使用 ab initio 分子軌域計算,配合過渡態理論求得的反應速率常數,以尋找矽烷、鍺烷反應系統合成鍺化矽薄膜程序的主要反應發生途徑。有關量子化學計算,皆採用 B3LYP/6-31G[d] 方法再配合較大的基底函數( B3LYP/aug-cc-pVTZ ),對反應相關物種作單點能量計算,能量的部份皆考慮零點振動位能校正。此外,亦嘗試用 ONIOM 方法計算較大的團簇模型。本研究分別討論矽甲烷/鍺甲烷氣體分子及高矽鍺烷類分子吸附在矽(2x1)-100 表面上的反應,而矽(2x1)-100 表面將採用簡單的分子團簇模型( Si9H12 )。結果顯示矽乙烷在表面吸附反應,會使分子矽矽之間的鍵結斷掉,形成二個 SiH3 的型態,由於此反應機制能障很低(反應能障低於1 kcal/mol),且分子吸附熱也比矽甲烷大,更適合在低溫下反應。至於反應速率常數計算,皆考慮量子穿隧效應的修正。計算結果顯示,相對於溫度及過渡態虛頻對量子穿隧效應的影響,一階及二階反應的能障差對量子穿隧效應的影響顯然是更不重要。在所有反應中,除了氣體脫氫的反應,鍺甲烷比矽甲烷快100倍之外,其他氣相和表面的反應,都是以矽烷類分子所主導反應,此計算結果與實驗推測結果相符。
Modeling of chemical vapor deposition (CVD) processes requires knowledge of the gas-flow dynamics and chemical reaction occurring in the reactor. In order to go beyond simple growth rate predictions based on the lumped kinetics from incomplete experimental kinetic data , quantum chemistry techniques are used to investigate kinetics of chemical reaction involved in the adsorption of SiH4, GeH4 Si2H6, Ge2H6 on the Si (100) surface. Ab initio calculations have been used to determine the structures, energetics and vibration frequency of initial, final and transition states. All the geometries were optimized at B3LYP/6-31G(d) level and the energies were determined at B3LYP/aug-cc-pVTZ level. In addition, transition state theory with the correction of tunneling effect is used to do the kinetic evaluation. The results demonstrate the disilane molecule which adsorbs on the surface, because of a relatively high sticking coefficient, and a low activation energy for breaking the Si-Si bond to produce two SiH3, maybe the favorably pathway, which is in good agreement with the experimental prediction.
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