GaN-MOVPE寄生反应的密度泛函理论研究

doi:10.11949/0438-1157.20190116

摘要/Abstract

摘要：

利用量子化学的密度泛函理论，探讨了TMG(Ga(CH₃)₃)/NH₃/H₂体系中的气体反应机理，特别关注了氨基物DMGNH₂的形成及其后的纳米粒子形核路径。通过计算不同温度下不同反应路径上Gibbs自由能的变化，从热力学和动力学两方面分析纳米粒子形核可能的产物。研究发现当T<622 K时，氨基物DMGNH₂可由加合物TMG:NH₃脱去CH₄生成，也可由TMG和NH₃双分子碰撞直接生成；当T>622 K时，氨基物DMGNH₂直接由TMG和NH₃双分子碰撞反应生成。当 662.5 K<T<939 K时，二聚物[DMGNH₂]₂相继脱去CH₄，变成[MMGNH]₂的反应容易发生。当389 K<T<734.7 K时，三聚物[DMGNH₂]₃相继脱去CH₄，变成[MMGNH]₃的反应容易发生。对于[MMGNH]₂和[MMGNH]₃相继脱去CH₄的反应，因为所有反应的ΔG>0，所以很难生成[GaN]₂和[GaN]₃。因此认为[MMGNH]₂和[MMGNH]₃是GaN-MOVPE低聚物纳米形核最可能的产物。

关键词: 密度泛函理论, 化学反应, GaN, MOVPE, 纳米形核, 计算化学

Abstract:

Using density functional theory(DFT) of quantum chemistry, the gas reaction mechanism in TMG/NH₃/H₂ system is explored, especially the formation of amide DMGNH₂ and its following nano-nucleation path. By calculating the changes of Gibbs free energy along different reaction path under different temperature, the most probable gas products of nucleation of nanoparticles are determined both thermodynamically and kinetically. It is found that DMGNH₂ can be formed by elimination of CH₄ from the adduct or by bimolecular collision when T < 622 K. DMGNH₂ can be directly formed by the bimolecular collision reaction of TMG and NH₃ when T > 622 K. When 662.5 K < T < 939 K, the reactions of dimer [DMGNH₂]₂ to [MMGNH]₂by successive elimination of CH₄ are easy to occur. When 389 K < T < 734.7 K, the reactions of trimer [DMGNH₃]₃ to [MMGNH]₃by successive elimination of CH₄ are easy to occur too. However, further elimination of CH₄ from [MMGNH]₂ and [MMGNH]₃ to form [GaN]₂and [GaN]₃ are both thermodynamically unfavorable, because the changes of Gibbs free energy of the reactions are greater than 0. Thus indicates that [MMGNH]₂ and [MMGNH]₃ are the two probable gas reaction products for the nucleation of oligomers in GaN-MOVPE growth.

Key words: density functional theory, chemical reaction, GaN, MOVPE, nano-nucleation, computational chemistry

中图分类号:

TN 304.2

张红, 唐留. GaN-MOVPE寄生反应的密度泛函理论研究[J]. 化工学报, 2019, 70(9): 3275-3282.

Hong ZHANG, Liu TANG. Density functional theory study on parasitic reactions of GaN-MOVPE[J]. CIESC Journal, 2019, 70(9): 3275-3282.

图/表 8

图1 GaN-MOVPE纳米粒子形核路径示意图

Fig.1 Schematic diagram of nano-nucleation paths of GaN-MOVPE growth

图2 GaN-MOVPE纳米形核过程中主要反应物和产物的分子结构

Fig.2 Optimized molecular structure of major reactants and products in nano-nucleation of GaN-MOVPE

图3 TMG加合路径在不同温度下的Gibbs自由能变化

Fig.3 Changes of Gibbs free energy for adduct-amide formation at different temperatures

图4 TMG和NH3的双分子反应在不同温度下的Gibbs自由能变化

Fig.4 Changes of Gibbs free energy for bimolecular collision reaction of TMG and NH3 at different temperatures

图5 [MMGNH]2的形成和分解反应路径在不同温度下的Gibbs自由能变化

Fig.5 Changes of Gibbs free energy for [MMGNH]2 formation and following CH4 elimination at different temperatures

表1 各反应式在不同温度下产物与反应物的Gibbs自由能差ΔG

Table 1 Changes of Gibbs free energy between products and reactants for each reaction at different temperatures

反应	ΔG/(kJ/mol)
反应	293.15 K	473.15 K	573.15 K	873.15 K	1273.15 K	1473.15 K
G5	314.09	290.96	278.57	242.80	197.40	175.39
G6	-497.10	-474.30	-461.83	-425.22	-377.65	-354.13
G7	-1053.95	-1000.31	-970.69	-884.62	-772.53	-717.47
G18	220.66	192.76	177.65	134.01	78.45	51.55
G19	205.18	177.82	163.09	120.50	66.48	40.33
G20	189.91	163.09	148.66	107.11	54.52	29.12

图6 [DMGNH2]2的形成和分解反应路径在不同温度下的Gibbs自由能变化

Fig.6 Changes of Gibbs free energy for direct [DMGNH2]2 formation and following CH4 elimination at different temperatures

图7 [DMGNH2]3的形成和分解反应路径在不同温度下的Gibbs自由能变化

Fig.7 Changes of Gibbs free energy for direct [DMGNH2]3 formation and following CH4 elimination at different temperatures

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