Kayanuma Megumi, Choe Yoong-Kee, Hagiwara Takayuki, Kameda Naoto, Shimoi Yukihiro
Research Center for Computational Design of Advanced Functional Materials, National Institute of Advanced Industrial Science and Technology, Central 2, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan.
Meiden Nanoprocess Innovations, Inc., 1569-9 Kotehashi-Mura, Hanamigawa-Ku, Chiba, Chiba 262-0013, Japan.
ACS Omega. 2021 Sep 28;6(40):26282-26292. doi: 10.1021/acsomega.1c03326. eCollection 2021 Oct 12.
The mechanism for the reaction of trimethylaluminum (TMA, Al(CH)) with ozone (O) was investigated in detail using density functional theory calculations to understand the atomic layer deposition processes that form aluminum oxide surfaces. We examined the reactions of TMA and some possible intermediates with O and revealed plausible paths to form methoxy (-OCH), formate (-OCHO), bicarbonate (-COH), and hydroxyl (-OH) species. These species have been observed in previous experimental studies. It was shown that TMA easily reacts with O to generate the Al(CH)(OCH)(O) intermediate. The subsequent reaction between the OCH and O groups finally generated an intermediate having a formate group. When all of the CH groups are converted into OCH or OCHO, O will react with these groups. In the latter reaction, bicarbonate was shown to be formed.
使用密度泛函理论计算详细研究了三甲基铝（TMA，Al(CH₃)₃）与臭氧（O₃）反应的机理，以了解形成氧化铝表面的原子层沉积过程。我们研究了TMA和一些可能的中间体与O₃的反应，并揭示了形成甲氧基（-OCH₃）、甲酸酯（-OCHO）、碳酸氢根（-CO₂H）和羟基（-OH）物种的合理途径。这些物种在先前的实验研究中已被观察到。结果表明，TMA很容易与O₃反应生成Al(CH₃)₂(OCH₃)(O)中间体。随后，OCH₃和O基团之间的反应最终生成了一个具有甲酸酯基团的中间体。当所有的CH₃基团都转化为OCH₃或OCHO时，O₃会与这些基团反应。在后一种反应中，显示会形成碳酸氢根。
