Quantum chemistry study on gas reaction path in InN MOCVD growth

doi:10.11949/0438-1157.20221276

Abstract

Abstract:

By performing density functional theory (DFT) calculations of quantum chemistry, the gas-phase reaction paths in the InN MOCVD process are systematically investigated. By calculating the changes of Gibbs energy (ΔG) and the energy barrier (ΔG^*/RT) of all proposed steps at different temperatures, the main gas reaction paths in InN growth from TMIn/NH₃ are determined. According to computational results, when N₂ is used as the carrier gas, the TMIn pyrolysis path competes with the adduct path could for the main reaction. The TMIn pyrolysis dominates the gas reaction path at high temperatures(T>873.0 K), whereas at low temperature (T<602.4 K), the adduct reaction to form TMIn:NH₃ is favored, and the decomposition of TMIn:NH₃ is predominant at medium temperature (602.4 K <T <873.0 K).When H₂ is used as the carrier gas, the H and NH₂ radicals can be generated through gas pyrolysis as well as surface reactions. Because H radicals can accelerate the TMIn pyrolysis and NH₂ radicals canreact with TMIn and DMIn to generate DMInNH₂, both radicals can disrupt InN MOCVD process. The formed amides can further react with H radicals and generate InNH₂ near the high temperature substrate, and hence swaps the surface reaction precursors from MMIn and In to InNH₂. Additionally, this study also illustrate how changing reaction temperature could affect InN MOCVD gas-phase pathways, and reveals novel reaction pathways with the interferences from H and NH₂ radicals.

Key words: density functional theory, InN, gas-phase reactions, MOCVD, radical

摘要：

利用量子化学的密度泛函理论，对MOCVD生长InN的气相反应路径进行较全面的计算分析，通过计算不同温度下各反应的Gibbs能差和反应能垒，分别从热力学和动力学角度确定从TMIn/NH₃生长InN的主要气相反应路径。研究发现：当载气为N₂时，InN生长的气相反应路径主要为热解路径与加合路径的竞争。在高温（T>873.0 K）时以TMIn的热解为主，在低温（T<602.4 K）时以TMIn与NH₃的加合反应为主，在中温（602.4 K<T<873.0 K）时以加合物TMIn:NH₃的分解反应为主。当载气为H₂时，由于气相热解和表面反应将产生H和NH₂自由基，H自由基将加速TMIn的热解，NH₂自由基将与TMIn、DMIn等反应生成氨基物DMInNH₂。H自由基还会与氨基物反应，在高温衬底附近生成InNH₂，从而使表面反应前体由传统的MMIn和In变为InNH₂。研究结果给出了InN MOCVD气相反应路径与温度的定量关系，以及H和NH₂自由基的参与引起的新的气相反应路径。

关键词: 密度泛函, InN, 气相反应, MOCVD, 自由基

CLC Number:

O 649.4

Xiaokun HE, Yuan XUE, Ran ZUO. Quantum chemistry study on gas reaction path in InN MOCVD growth[J]. CIESC Journal, 2022, 73(12): 5638-5647.

何晓崐, 薛园, 左然. MOCVD生长InN气相反应路径的量子化学研究[J]. 化工学报, 2022, 73(12): 5638-5647.

Figures/Tables 11

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反应	本文计算值/(kcal/mol)	文献值/(kcal/mol)	方法	文献
G4（0 K）	-20.17	-17.4	B3LYP/Lanl2dz	[26]
		-19.6	MP2/Lanl2dz	[26]
		-20.0	CCSD(T) Lanl2dz//B3LYP/Lanl2dz	[26]
		-19.8	CCSD(T) Lanl2dz//MP2/Lanl2dz	[26]
G4（298.15 K）	-20.62	-16.27	B3LYP/In:3-21G(d,p)&AKR4	[27]
		-16.08	B3LYP /LanL2DZ*	[28]
		-18.22	B3LYP /LanL2DZ*	[11]
G6（298.15 K）	-16.44	-14.27	B3LYP/In:3-21G(d,p)&AKR4	[27]
		-18.88	B3LYP /LanL2DZ*	[28]
		-19.09	B3LYP /LanL2DZ*	[11]

反应	本文计算值/(kcal/mol)	文献值/(kcal/mol)	方法	文献
G4（0 K）	-20.17	-17.4	B3LYP/Lanl2dz	[26]
		-19.6	MP2/Lanl2dz	[26]
		-20.0	CCSD(T) Lanl2dz//B3LYP/Lanl2dz	[26]
		-19.8	CCSD(T) Lanl2dz//MP2/Lanl2dz	[26]
G4（298.15 K）	-20.62	-16.27	B3LYP/In:3-21G(d,p)&AKR4	[27]
		-16.08	B3LYP /LanL2DZ*	[28]
		-18.22	B3LYP /LanL2DZ*	[11]
G6（298.15 K）	-16.44	-14.27	B3LYP/In:3-21G(d,p)&AKR4	[27]
		-18.88	B3LYP /LanL2DZ*	[28]
		-19.09	B3LYP /LanL2DZ*	[11]

Reaction	ΔG /(kcal/mol)
Reaction	298.15 K	473.15 K	673.15 K	873.15 K	1073.15 K
G1	59.03	52.53	45.02	37.54	30.12
G2	18.95	13.31	6.76	0.21	-6.31
G3	47.28	42.42	36.76	31.08	25.41

Reaction	ΔG /(kcal/mol)
Reaction	298.15 K	473.15 K	673.15 K	873.15 K	1073.15 K
G1	59.03	52.53	45.02	37.54	30.12
G2	18.95	13.31	6.76	0.21	-6.31
G3	47.28	42.42	36.76	31.08	25.41

Reaction	ΔG/(kcal/mol)
Reaction	298.15 K	473.15 K	673.15 K	873.15 K	1073.15 K
G13	-17.27	-17.00	-16.88	-16.87	-16.93
G14	-17.02	-17.35	-17.92	-18.60	-19.34
G15	-22.17	-22.39	-22.75	-23.16	-23.59
G16	-76.30	-69.54	-61.91	-54.42	-47.05
G17	-35.97	-30.66	-24.69	-18.81	-13.03
G18	-69.45	-64.82	-59.52	-54.25	-49.00