p型掺杂剂Cp2Mg在MOCVD气相中的反应机理研究

doi:10.11949/0438-1157.20191354

摘要/Abstract

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

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

中图分类号:

TN 304.2

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.

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.

图/表 8

图1 Cp2Mg在MOCVD气相过程中的化学反应路径示意图，主要分为加合路径(红色箭头所示)和氢解路径(蓝色箭头所示)，其中虚线表示理论上不可能实现的反应

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

图2 加合路径中主要物质的优化结构

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

表1 主要物质的优化键长和键角

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]

图3 不同温度下(T =293.15 ~1473.15 K)加合反应(G1和G2)的Gibbs自由能差(ΔG)

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

表2 不同温度下的相对Gibbs自由能

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

图4 氢解路径中主要物质和过渡态的优化结构

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

图5 不同温度下(T =293.15 ~1473.15 K)氢解路径(G3~G8)的Gibbs自由能差(ΔG)

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

图6 不同温度下(T =293.15~1473.15 K)氢解路径(G9~G14)的Gibbs自由能差(ΔG)

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

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p型掺杂剂Cp₂Mg在MOCVD气相中的反应机理研究

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

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