Study on reaction mechanism of p-type dopant Cp2Mg in MOCVD gas phase

doi:10.11949/0438-1157.20191354

Abstract

Abstract:

Using the density functional theory calculation of quantum chemistry, the reaction mechanism of p-type dopant Cp₂Mg in the metal organic chemical vapor deposition (MOCVD) gas phase process was proposed and studied. The possibility of each reaction proceeding at various temperatures was determined, respectively. It was found that Cp₂Mg mainly has two competing addition paths and hydrogenolysis paths. For adduct reaction path, complex Cp₂Mg∶NH₃ or Cp₂Mg∶(NH₃)₂ will be formed in the temperature range of 293—573 K. For the hydrogenolysis pathway, the H radical in the gas phase was a “double-edged sword”. On the one hand, H radical exerted a positive auxiliary effect on Cp₂Mg decomposition, significantly lowering the decomposition temperature of Cp₂Mg. On the other hand, due to passivation, Mg-H gas phase complexes will be formed, which affects the p-type doping effect.

Key words: MOCVD, DFT, p-type doping, reaction mechanism, computational chemistry

摘要：

采用量子化学的密度泛函理论计算，提出并研究了金属有机化学气相沉积(MOCVD)气相过程中p型掺杂剂Cp₂Mg的反应机理。特别判断了不同温度下各反应进行的可能性。发现Cp₂Mg主要有两条相互竞争的反应路径，加合路径和氢解路径。对于加合路径，在293~573 K的温度范围内，会形成络合物Cp₂Mg∶NH₃或Cp₂Mg∶(NH₃)₂。对于氢解路径，气相中的H自由基是一把“双刃剑”。一方面H自由基对Cp₂Mg的分解有积极的辅助作用，明显降低了Cp₂Mg的分解温度；另一方面由于钝化作用会形成Mg-H气相络合物，影响p型掺杂效果。

关键词: 金属有机化学气相沉积, 密度泛函理论, p型掺杂, 反应机理, 计算化学

CLC Number:

TN 304.2

Hong ZHANG, Liu TANG. Study on reaction mechanism of p-type dopant Cp₂Mg in MOCVD gas phase[J]. CIESC Journal, 2020, 71(7): 3000-3008.

张红, 唐留. p型掺杂剂Cp₂Mg在MOCVD气相中的反应机理研究[J]. 化工学报, 2020, 71(7): 3000-3008.

Figures/Tables 8

Fig.1 Schematic diagram of the chemical reaction pathway of Cp2Mg in the MOCVD gas-phase process, which is mainly composed of the adduct reaction path (shown by the red arrow) and the hydrogenolysis reaction path (shown by the blue arrow), where the dotted line indicates the theoretically impossible reactions

Fig.2 Optimized structures of the main species in adduct reaction path

Table 1 Optimized bond lengths and angles of the main species

Cp₂Mg
Cp-Mg-Cp	Mg-Cp/ ?	Mg-C/ ?	C—C/ ?	方法	文献
180.0°	2.068	2.366	1.424	B3LYP/6-31G(d)	本文
—	2.008	2.339	1.423	El-diff	[37]
—	1.977	2.304	1.390	X-ray	[40]
—	2.031	2.361	1.416	B3LYP/6-31	[41]
178.7°	2.030	—	—	B3LYP/6-31G(d)	[29]
Cp₂Mg∶NH₃
Cp(1)-Mg-Cp(2)	Mg-Cp(1)/Cp(2) / ?	Mg-N/ ?		方法	文献
155.3°	2.118/2.561	2.149		B3LYP/6-31G(d)	本文
157.3°	2.095/2.565	2.149		B3LYP/6-31G(d)	[29]
Cp₂Mg∶(NH₃)₂
Cp(1)-Mg-Cp(2)	Mg-Cp(1)/Cp(2) / ?	N(1)-Mg-N(2) / ?	Mg-N(1)/N(2) / ?	方法	文献
143.8°	2.821/2.102	93.0°	2.171/2.210	B3LYP/6-31G(d)	本文
144.1°	2.789/2.175	92.9°	2.170/2.210	B3LYP/6-31G(d)	[29]

Fig.3 Changes of Gibbs free energy (ΔG) of adduct reactions (G1 and G2) at different temperatures (T =293.15—1473.15 K)

Table 2 Calculated relative Gibbs free energy at different temperatures

温度/K	G /(kJ/mol)
温度/K	Cp₂Mg	Cp₂MgH	CpMgH	MgH
293.15	0	7.38	0	257.45
573.15	0	21.30	0	208.76
873.15	0	35.04	0	157.15
1273.15	0	51.88	0	89.66
1473.15	0	59.75	0	56.40

Fig.4 Optimized structures of the main species and transition states in hydrogenolysis reaction path

Fig.5 Changes of Gibbs free energy (ΔG) of hydrogenolysis reactions (G3—G8) at different temperatures (T =293.15—1473.15 K)

Fig.6 Changes of Gibbs free energy (ΔG) of hydrogenolysis reactions (G9—G14) at different temperatures (T =293.15—1473.15 K)

References 41

1	Safvi S A, Redwing J M, Tischler M A, et al. GaN growth by metallorganic vapor phase epitaxy[J]. Journal of the Electrochemical Society, 1997, 144(5): 1789-1796.
2	Creighton J R, Breiland W G, Coltrin M E, et al. Gas-phase nanoparticle formation during AlGaN metalorganic vapor phase epitaxy[J]. Applied Physics Letters, 2002, 81(14): 2626-2628.
3	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.
4	Lundin W V, Nikolaev A E, Rozhavskaya M M, et al. Fast AlGaN growth in a whole composition range in planetary reactor[J]. Journal of Crystal Growth, 2013, 370: 7-11.
5	Zhao D G, Liu Z S, Zhu J J, et al. Effect of Al incorporation on the AlGaN growth by metalorganic chemical vapor deposition[J]. Applied Surface Science, 2006, 253(5): 2452-2455.
6	Cherns D, Sahonta S L, Liu R, et al. The generation of misfit dislocations in facet-controlled growth of AlGaN∕GaN films[J]. Applied Physics Letters, 2004, 85(21): 4923-4925.
7	Detchprohm T, Sano S, Mochizuki S, et al. Growth mechanism and characterization of low-dislocation-density AlGaN single crystals grown on periodically grooved substrates[J]. Physica Status Solidi (A), 2001, 188(2): 799-802.
8	Keller S, Denbaars S P. Metalorganic chemical vapor deposition of group Ⅲ nitrides-a discussion of critical issues[J]. Journal of Crystal Growth, 2003, 248: 479-486.
9	Li D B, Jiang K, Sun X J, et al. AlGaN photonics: recent advances in materials and ultraviolet devices[J]. Advances in Optics and Photonics, 2018, 10(1): 43-110.
10	Nam K B, Nakarmi M L, Li J, et al. Mg acceptor level in AlN probed by deep ultraviolet photoluminescence[J]. Applied Physics Letters, 2003, 83(5): 878-880.
11	Nakamura S, Iwasa N, Senoh M, et al. Hole compensation mechanism of p-type GaN films[J]. Japanese Journal of Applied Physics, 1992, 31(A): 1258-1266.
12	Götz W, Johnson N M, Walker J, et al. Activation of acceptors in Mg-doped GaN grown by metalorganic chemical vapor deposition[J]. Applied Physics Letters, 1996, 68(5): 667-669.
13	Wen T C, Lee S C, Lee W I, et al. Activation of p-type GaN in a pure oxygen ambient[J]. Japanese Journal of Applied Physics, 2001, 40(B): L495-L497.
14	Götz W, Johnson N M, Walker J, et al. Hydrogen passivation of Mg acceptors in GaN grown by metalorganic chemical vapor deposition[J]. Applied Physics Letters, 1995, 67(18): 2666-2668.
15	Hull B A, Mohney S E, Venugopalan H S, et al. Influence of oxygen on the activation of p-type GaN[J]. Applied Physics Letters, 2000, 76(16): 2271-2273.
16	Clerjaud B, Cte D, Lebkiri A, et al. Infrared spectroscopy of Mg-H local vibrational mode in GaN with polarized light[J]. Physical Review B, 2000, 61(12): 8238-8241.
17	Götz W, Johnson N M, Bour D P, et al. Local vibrational modes of the Mg–H acceptor complex in GaN[J]. Applied Physics Letters, 1996, 69(24): 3725-3727.
18	Sheu J K, Chi G C. The doping process and dopant characteristics of GaN[J]. Journal of Physics: Condensed Matter, 2002, 14(22): R657-R702.
19	Matlock D M, Zvanut M E, Wang H, et al. The effects of oxygen, nitrogen, and hydrogen annealing on Mg acceptors in GaN as monitored by electron paramagnetic resonance spectroscopy[J]. Journal of Electronic Materials, 2005, 34(1): 34-39.
20	Zvanut M E, Matlock D M, Henry R L, et al. Thermal activation of Mg-doped GaN as monitored by electron paramagnetic resonance spectroscopy[J]. Journal of Applied Physics, 2004, 95(4): 1884-1887.
21	Amano H, Kito M, Hiramatsu K, et al. P-type conduction in Mg-doped GaN treated with low-energy electron beam irradiation (LEEBI)[J]. Japanese Journal of Applied Physics, 1989, 28(Part 2): L2112-L2114.
22	Nakamura S, Mukai T, Senoh M, et al. Thermal annealing effects on p-type Mg-doped GaN films[J]. Japanese Journal of Applied Physics, 1992, 31(2B): L139-L142.
23	Tokunaga H, Ubukata A, Yano Y, et al. Effects of growth pressure on AlGaN and Mg-doped GaN grown using multiwafer metal organic vapor phase epitaxy system[J]. Journal of Crystal Growth, 2004, 272(1/2/3/4): 348-352.
24	Zvanut M E, Sunay U R, Dashdorj J, et al. Mg-hydrogen interaction in AlGaN alloys[J]. Proceedings of SPIE the International Society for Optical Engineering, 2012, 8262: 82620L-1-6.
25	Neugebauer J, van de Walle C G. Hydrogen in GaN: novel aspects of a common impurity[J]. Physical Review Letters, 1995, 75(24): 4452-4455.
26	Yuan C. Investigation of n- and p-type doping of GaN during epitaxial growth in a mass production scale multiwafer-rotating-disk reactor[J]. Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, 1995, 13(5): 2075-2080.
27	Pearton S J, Lee J W, Yuan C. Minority-carrier-enhanced reactivation of hydrogen-passivated Mg in GaN[J]. Applied Physics Letters, 1996, 68(19): 2690-2692.
28	Haffouz S, Beaumont B, Leroux M, et al. P-doping of GaN by MOVPE[J]. MRS Internet Journal of Nitride Semiconductor Research, 1997, 2(33): 37-41.
29	Wang G T, Creighton J R. Complex formation between magnesocene (MgCp₂) and NH₃: implications for p-type doping of group Ⅲ nitrides and the Mg memory effect[J]. The Journal of Physical Chemistry A, 2004, 108(22): 4873-4877.
30	Moscatelli D, Cavallotti C. Theoretical investigation of the gas-phase kinetics active during the GaN MOVPE[J]. The Journal of Physical Chemistry A, 2007, 111(21): 4620-4631.
31	Yoshida M, Watanabe H, Uesugi F. Mass spectrometric study of Ga(CH₃)₃ and Ga(C₂H₅)₃ decomposition reaction in H₂ and N₂[J]. Journal of the Electrochemical Society, 1985, 132(3): 677-679.
32	Zhang X J, Yang J C. Study on the structures and properties of CeSi_n (n = 1 - 8) with density functional theory[J]. Journal of Advances in Physical Chemistry, 2014, 3(4): 12-18.
33	Lee C T, Yang W T, Parr R G. Development of the colic-salvetti correlation-energy into a functional of the electron density[J]. Physal Review B, 1988, 37(2): 785-789.
34	Becke A D. Density-functional thermochemistry (Ⅲ). The role of exact exchange[J]. The Journal of Chemical Physics, 1993, 98(7): 5648-5652.
35	Canneaux S, Bohr F, Henon E. KiSThelP: a program to predict thermodynamic properties and rate constants from quantum chemistry results[J]. Journal of Computational Chemistry, 2013, 35(1): 82-93.
36	Simka H S. Application of quantum chemistry calculations in modeling chemical vapor deposition processes[D]. Boston: MIT, 1998.
37	Haaland A, Lusztyk J, Brunvoll J, et al. On the molecular structure of dicyclopentadienylmagnesium[J]. Journal of Organometallic Chemistry, 1975, 85(3): 279-285.
38	Andersen R A, Boncella J M, Burns C J, et al. The molecular structures of bis(pentamethylcyclopentadienyl)-calcium and-ytterbium in the gas phase: two bent metallocenes[J]. Journal of Organometallic Chemistry, 1986, 312(3): C49-C52.
39	Blom R, Faegri K, Volden H V. Molecular structures of alkaline earth-metal metallocenes: electron diffraction and ab initio investigations[J]. Organometallics, 1990, 9(2): 372-379.
40	Bünder W, Weiss E. Verfeinerung der kristallstruktur von dicyclopentadienylkobalt, (η⁵-C₅H₅)₂Co[J]. Journal of Organometallic Chemistry, 1975, 92(1): 65-68.
41	Jr Faegri K, Almlöf J, Lüth H P. The geometry and bonding of magnesocene. An ab-initio MO-LCAO investigation[J]. Journal of Organometallic Chemistry, 1983, 249(2): 303-313.

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Study on reaction mechanism of p-type dopant Cp₂Mg in MOCVD gas phase

p型掺杂剂Cp₂Mg在MOCVD气相中的反应机理研究

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