MOCVD生长InN气相反应路径的量子化学研究

doi:10.11949/0438-1157.20221276

摘要/Abstract

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

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

中图分类号:

O 649.4

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.

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.

图/表 11

图1 MOCVD生长InN的气相反应路径示意图— 热解路径; —加合路径; H自由基参与路径; NH2自由基参与路径; 聚合路径

Fig.1 Schematic of InN MOCVD gas-phase reaction pathway

图2 优化后的InN MOCVD过程中的主要气相物质的分子结构

Fig.2 Optimized molecular structures of major gas species in InN MOCVD process

图3 反应过程的Gibbs能变化和判据

Fig.3 Schematic diagrams of the Gibbs energy changes and the criteria of determining the reaction process

表1 优化后的TMIn：NH3、DMInNH2键长和键角对比

Table 1 Comparisons of optimized bond lengths and bond angles for TMIn：NH3 and DMInNH2

TMIn:NH₃

DMInNH₂

B3LYP/Lanl2dz

B3LYP/In:3-21G(d,p)&AKR4

C、H、N:6-311G(d,p)

M062X/6-31G(d)/LanL2DZ

B3LYP/Lanl2dz

B3LYP/In:3-21G(d,p)&AKR4

C、H、N:6-311G(d,p)

M062X /6-31G(d)/LanL2DZ

2.368

2.450

2.394

1.975

2.058

1.977

2.176

2.223

2.170

2.147

2.196

2.143

118.2

119.0

118.8

127.5

131.0

126.5

96.0

96.3

116.5

115.0

116.8

[26]

[27]

本文

[26]

[27]

本文

表2 反应G4、G6的ΔH的计算值与文献值的对比

Table 2 Comparisons of the ΔH of reactions G4， G6 calculated in this study and reported from literatures

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]

表3 TMIn热解反应的Gibbs能差ΔG

Table 3 The changes of Gibbs energy ΔG in TMIn pyrolysis

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

图4 加合路径的ΔG/RT变化（弧线代表反应G6）

Fig.4 The changes of ΔG/RT in the adduct reaction path (the arcs represent reaction G6)

图5 TMIn及其热解产物与H自由基反应的ΔG/RT变化

Fig.5 The changes of ΔG/RT in TMIn pyrolysis path with radical H

图6 DMInNH2与H自由基反应的ΔG/RT

Fig.6 The changes of ΔG/RT in DMInNH2 reactions with radical H

表4 TMIn及其热解产物与NH2自由基反应的Gibbs能差ΔG

Table 4 The changes of Gibbs energy ΔG in TMIn pyrolysis with NH2 radical

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

表5 DMInNH2二聚反应（G19）和三聚反应（G20）的Gibbs能差ΔG

Table 5 The changes of Gibbs energy ΔG in dimerization （G19） and trimerization （G20） of DMInNH2

Reaction	ΔG/(kcal/mol)
Reaction	298.15 K	473.15 K	673.15 K	873.15 K	1073.15 K
G19	-43.49	-34.62	-24.43	-14.26	-4.14
G20	-23.20	-14.60	-4.91	4.62	14.00

参考文献 32

1	郑有炓, 江风益, 张荣, 等. 第三代半导体材料与器件进展[M]. 南京: 南京大学出版社, 2015.
	Zheng Y L, Jiang F Y, Zhang R, et al. Research Progress of the Third Generation Semiconductor Materials and Devices[M]. Nanjing: Nanjing University Press, 2015.
2	陆大成, 段树坤. 金属有机化合物气相外延基础及应用[M]. 北京: 科学出版社, 2009.
	Lu D C, Duan S K. Basic and Applications of Metal-organic Compound Gas Phase Epitaxy[M]. Beijing: Science Press, 2009.
3	Dauelsberg M, Talalaev R. Progress in modeling of Ⅲ-nitride MOVPE[J]. Progress in Crystal Growth and Characterization of Materials, 2020, 66(3), 100486.
4	Sengupta D, Mazumder S, Kuykendall W, et al. Combined ab initio quantum chemistry and computational fluid dynamics calculations for prediction of gallium nitride growth[J]. Journal of Crystal Growth, 2005, 279(3/4): 369-382.
5	Wang G T, Creighton J R. Complex formation of trimethylaluminum and trimethylgallium with ammonia: evidence for a hydrogen-bonded adduct[J]. Journal of Physical Chemistry A, 2006, 110(3): 1094-1099.
6	Simka H, Willis B G, Lengyel I, et al. Computational chemistry predictions of reaction processes in organometallic vapor phase epitaxy[J]. Progress in Crystal Growth and Characterization of Materials, 1997, 35(2/4): 117-149.
7	张红, 左然. GaN-MOVPE生长的气相反应中自由基的作用[J]. 中国科学: 技术科学, 2019, 49(8): 939-946.
	Zhang H, Zuo R. Effect of radicals on gas phase reactions in GaN MOVPE process[J]. Scientia Sinica Technologica, 2019, 49(8): 939-946.
8	张禹, 王克昌, 张荣, 等. GaN MOCVD生长机制的量子化学计算[J]. 材料导报, 2007(9): 127-129.
	Zhang Y, Wang K C, Zhang R, et al. Quantum chemistry calculation of GaN growth mechanism by MOCVD[J]. Materials Reports, 2007(9): 127-129.
9	Creighton J R, Wang G T. Reversible adduct formation of trimethylgallium and trimethylindium with ammonia[J]. Journal of Physical Chemistry A, 2005, 109(1): 133-137.
10	Sekiguchi K, Shirakawa H, Chokawa H, et al. Thermodynamic considerations of the vapor phase reactions in Ⅲ-nitride metal organic vapor phase epitaxy[J]. Japanese Journal of Applied Physics, 2017, 56(4S): 04CJ04.
11	Nakamura K, Makino O, Tachibana A, et al. Quantum chemical study of parasitic reaction in Ⅲ-Ⅴ nitride semiconductor crystal growth[J]. Journal of Organometallic Chemistry, 2000, 611(1/2): 514-524.
12	Thon A, Kuech T F. High temperature adduct formation of trimethylgallium and ammonia[J]. Applied Physics Letters, 1996, 69(55): 55-57.
13	Cavallotti C, Moscatelli D, Masi M, et al. Accelerated decomposition of gas phase metal organic molecules determined by radical reactions[J]. Journal of Crystal Growth, 2004, 266(1/2/3): 363-370.
14	McDaniel A H, Allendorf M D. Autocatalytic behavior of trimethylindium during thermal decomposition[J]. Chemistry of Materials, 2000, 12(2): 450-460.
15	Creighton J R, Wang G T, Breiland W G, et al. Nature of the parasitic chemistry during AlGaInN OMVPE[J]. Journal of Crystal Growth, 2004, 261(2/3): 204-213.
16	Zhang H, Zuo R, Zhang G Y. Effects of reaction-kinetic parameters on modeling reaction pathways in GaN MOVPE growth[J]. Journal of Crystal Growth, 2017, 478(15): 193-204.
17	Moscatelli D, Caccioppoli P, Cavallotti C. Ab initio study of the gas phase nucleation mechanism of GaN[J]. Applied Physics Letters, 2005, 86(9): 091106.
18	Creighton J R, Wang G T, Coltrin M E. Fundamental chemistry and modeling of group-Ⅲ nitride MOVPE[J]. Journal of Crystal Growth, 2007, 298: 2-7.
19	Tan A K, Hamzah A, Ahmad M A, et al. Recent advances and challenges in the MOCVD growth of indium gallium nitride: a brief review[J]. Materials Science in Semiconductors Processing, 2022, 143: 106545.
20	Parikh R P, Adomaitis R A. An overview of gallium nitride growth chemistry and its effect on reactor design: application to a planetary radial-flow CVD system[J]. Journal of Crystal Growth, 2006, 286(2): 259-278.
21	Zhang H, Zuo R, Zhong T T, et al. Quantum chemistry study on gas reaction mechanism in AlN MOVPE growth[J]. Journal of Physical Chemistry A, 2020, 124(15): 2961-2971.
22	Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 09[CP]. 2013.
23	Lu T, Chen Q X. Shermo: a general code for calculating molecular thermochemistry properties[J]. Computational and Theoretical Chemistry, 2021, 1200: 113249.
24	Alecu I M, Zheng J, Zhao Y, et al. Computational thermochemistry: scale factor databases and scale factors for vibrational frequencies obtained from electronic model chemistries[J]. Journal of Chemical Theory and Computation, 2010, 6(9): 2872-2887.
25	Atkins P, Panla J D. Atkins' Physical Chemistry[M]. New York: Oxford University Press, 2002.
26	Tzeng Y R, Raghunath P, Chen S C, et al. Computational study of reaction pathways for the formation of indium nitride from trimethylindium with HN₃: comparison of the reaction with NH₃ and that on TiO₂ rutile (110) surface[J]. Journal of Physical Chemistry A, 2007, 111(29): 6781-6788.
27	Cardelino B H, Moore C E, Cardelino C A, et al. Theoretical study of indium compounds of interest for organometallic chemical vapor deposition[J]. Journal of Physical Chemistry A, 2001, 105(5): 849-868.
28	Ikenaga M, Nakamura K, Tachibana A, et al. Quantum chemical study of gas-phase reactions of trimethylaluminium and triethylaluminium with ammonia in Ⅲ-Ⅴ nitride semiconductor crystal growth[J]. Journal of Crystal Growth, 2002, 237/238/239: 936-941.
29	Ohkawa K, Ichinohe F, Watanabe T, et al. Metalorganic vapor-phase epitaxial growth simulation to realize high quality and high-In-content InGaN alloy[J]. Journal of Crystal Growth, 2019, 512: 69-73.
30	Zuo R, Yu H Q, Xu N, et al. Influence of gas mixing and heating on gas-phase reactions in GaN MOCVD growth[J]. ECS Journal of Solid State Science and Technology, 2012, 1: 46.
31	Moscatelli D, Cavallotti C. Theoretical investigation of the gas-phase kinetics active during the GaN MOVPE[J]. Journal of Physical Chemistry A, 2007, 111(21): 4620-4631.
32	Jacko M G, Price S J W. The Pyrolysis of trimethylindium[J]. Canadian Journal of Chemistry, 1964, 42(5): 1198-1205.

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