Growth mechanism study of boron nitride atomic layer deposition by experiment and density functional theory
Growth mechanism study of boron nitride atomic layer deposition by experiment and density functional theory
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DOI：
10.1016/j.commatsci.2022.111919
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发表时间：
2023-01
影响因子：
3.3
通讯作者：
Naoya Uene;T. Mabuchi;M. Zaitsu;Yong-Gi Jin;Shigeo Yasuhara;T. Tokumasu
中科院分区：
文献类型：
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作者：
Naoya Uene;T. Mabuchi;M. Zaitsu;Yong-Gi Jin;Shigeo Yasuhara;T. Tokumasu
我们通过密度泛函理论 (DFT) 模拟研究了决定原子层沉积 (ALD) 温度窗口极限的基本机制。使用 BCl3 或三二甲氨基硼烷 (TDMAB) 和 NH3on Si(1 0 0) 基板进行氮化硼 (BN) ALD 实验，以检查 ALD 温度窗口是否存在。随着生长温度的升高，BCl3 和 NH3 系统中 700 至 900 °C 之间的每次循环生长 (GPC) 的增加相对较小，而 TDMAB 和 NH3 系统中 GPC 呈指数增加。基于实验结果，我们进行了 DFT 模拟，以研究决定 BCl3 和 NH3 系统中较低 ALD 温度窗口的反应机制。对两个初始反应和两个循环反应进行了数值分析：(a) OH 封端 Si(1 0 0) 表面上的 BCl3 反应，(b) Cl 封端 Si(1 0 0) 表面上的 NH3 反应，(c) H 封端 BN 表面上的 BCl3 反应，以及 (d) Cl 封端 BN 表面上的 NH3 反应。我们发现反应 (c) 的活化能为 30.0 kcal/mol，决定了 ALD 温度窗口的下限。我们的实验得到反应(c)的活化温度为789℃，正好位于ALD温度窗口内。
We investigated the fundamental mechanisms determining the limit of the atomic layer deposition (ALD) temperature window by density functional theory (DFT) simulations. Boron nitride (BN) ALD experiments were performed using BCl3or tris-dimethylaminoborane (TDMAB) and NH3on Si(1 0 0) substrates to check whether the ALD temperature window exists or not. With increasing the growth temperature, an increase in growth per cycle (GPC) between 700 and 900 °C was relatively small in the BCl3and NH3system, while the GPC exponentially increased in the TDMAB and NH3system. Based on the experimental results, we performed DFT simulations to investigate the reaction mechanisms determining the lower ALD temperature window in the BCl3and NH3systems. The two initial reactions and two cyclic reactions were numerically analyzed: (a) BCl3reactions on OH-terminated Si(1 0 0) surface, (b) NH3reactions on Cl-terminated Si(1 0 0) surface, (c) BCl3reactions on H-terminated BN surface, and (d) NH3reactions on Cl-terminated BN surface. We found activation energies for reaction (c) is 30.0 kcal/mol, determining the lower limit of the ALD temperature window. The activation temperature of reaction (c) is obtained 789 °C which is just in the ALD temperature window by our experiments.