BCl3-NH3-H2-N2前驱体化学气相沉积法制备氮化硼涂层

doi:10.15541/jim20180021

摘要/Abstract

摘要：

以BCl₃-NH₃-H₂-N₂为前驱体系统, 在垂直放置的热壁反应器中利用化学气相沉积工艺制备氮化硼(BN)涂层, 分析了工艺参数对沉积速率的影响, 通过扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和X射线衍射技术(XRD)分析了碳化硅纤维表面BN涂层的形貌和微观结构, 提出了BN沉积过程中主要的气相和表面反应, 以及关键气相组分。研究结果显示：在600~850℃的范围内, 随着沉积温度的升高, BN沉积速率逐渐加快, 同一温度下, 沉积区域内BN沉积速率沿气流方向逐渐减缓, 表明气相组分在气流方向逐渐消耗; 随着系统压力的提高, BN沉积速率先加快后减缓, 表明沉积过程由表面反应控制转变为质量传输控制; 随滞留时间延长, 距气体入口1~3 cm处, BN的沉积速率逐渐增大, 而距气体入口4~5 cm处, 沉积速率先增大后逐渐变小。SEM照片显示碳化硅纤维表面BN涂层光滑致密, XPS结果表明主要成分为BN及氧化产物B₂O₃, XRD图谱表明热处理前BN为无定形态, 1200℃热处理后BN的结晶度提高, 并向六方形态转变。BN的沉积是由BCl₃和NH₃反应所生成的中间气相组分Cl₂BNH₂、ClB(NH₂)₂和B(NH₂)₃来实现的。

关键词: 化学气相沉积, 氮化硼, 沉积速率, 微观结构, 沉积过程

Abstract:

Boron nitride (BN) coatings were prepared using BCl₃-NH₃-H₂-N₂precursor system by chemical vapor deposition process in a vertically-placed hot wall reactor. The effect of processing parameters on the deposition rates was analyzed. The morphology and microstructure of the BN coating on the surface of the silicon carbide fiber were characterized by scanning electron microscope (SEM), X-ray photoelectron spectroscope (XPS) and X-ray diffraction (XRD) . The dominant gas-surface reactions and crucial gas-phase components during BN deposition process were established. The results show that the deposition rates of BN increase gradually with the elevating deposition temperature from 600℃ to 850℃. And at a defined temperature, the deposition rates of BN gradually decrease along the gases flow direction in the deposition area, indicating that the gas-phase components are gradually consumed along the gases flow direction. The deposition rates of BN increase firstly and then decrease with the increase of system pressures, which suggests that the deposition process change from surface reactions control to mass transfer control. The BN deposition rates increase at 1-3 cm away from gases inlet, but decrease after increase firstly at 4-5 cm away from gases inlet as the residence time getting longer. SEM results show that BN coating on the surface of silicon carbide fiber is relatively smooth and dense. The chemical compositions of coating determined by XPS are BN and B₂O₃. XRD results indicate that the deposited BN at 650℃is amorphous. After heat-treatment at 1200℃ for 2 h, it transformed into the hexagonal BN(h-BN). The deposition of BN is achieved by the intermediate gas-phase species composed of Cl₂BNH₂, ClB(NH₂)₂ and B(NH₂)₃ which were generated by the reaction of BCl₃ and NH₃.

Key words: chemical vapor deposition, boron nitride, deposition rate, microstructures, deposition process

中图分类号:

TQ174

王梦千, 贾林涛, 李爱军, 彭雨晴, 张方舟. BCl₃-NH₃-H₂-N₂前驱体化学气相沉积法制备氮化硼涂层[J]. 无机材料学报, 2018, 33(11): 1179-1185.

WANG Meng-Qian, JIA Lin-Tao, LI Ai-Jun, PENG Yu-Qing, ZHANG Fang-Zhou. Preparation of Boron Nitride Coating from BCl₃-NH₃-H₂-N₂ Precursor by Chemical Vapor Deposition[J]. Journal of Inorganic Materials, 2018, 33(11): 1179-1185.

图/表 12

图1 不同沉积温度下BN的沿程沉积速率

Fig. 1 Deposition rates of BN along gas flow direction deposited at various temperatures^(7 kPa, 0.5 s, nBCl3 : nNH3 : nH2 : nN2=1 : 3 : 1 : 6)

图2 600和650℃下沉积得到的BN涂层的傅里叶变换红外图谱

Fig. 2 Fourier transform infrared spectra of BN deposited at 600℃ and 650℃^(7 kPa, 0.5 s, nBCl3 : nNH3 : nH2 : nN2=1 : 3 : 1 : 6)

图3 不同压力下BN的沿程沉积速率

Fig. 3 Deposition rates of BN along gas flow direction deposited at various pressures^(650℃, 0.5 s, nBCl3 : nNH3 : nH2 : nN2=1 : 3 : 1 : 6)

图4 BN的沿程沉积速率随滞留时间的变化

Fig. 4 Deposition rates of BN along gas flow direction at various residence times^(650℃, 10 kPa, nBCl3 : nNH3 : nH2=1 : 3 : 1)

图5 在650℃、7 kPa、0.5 s、nBCl3 : nNH3 : nH2 : nN2=1 : 3 : 1 : 6条件下, SiC纤维表面沉积BN涂层不同放大倍数的SEM照片

Fig. 5 Different magnification SEM images of BN coatings deposited on SiC fibers surface at 650℃, 7 kPa and 0.5 s, while nBCl3 : nNH3 : nH2 : nN2=1 : 3 : 1 : 6

图6 在650℃、7 kPa、0.5 s、nBCl3 : nNH3 : nH2 : nN2=1 : 3 : 1 : 6条件下, 沉积BN涂层的XPS图谱

Fig. 6 XPS spectra of BN coatings deposited at 650℃, 7 kPa and 0.5 s, while nBCl3 : nNH3 : nH2 : nN2=1 : 3 : 1 : 6

图7 在650℃、7 kPa、0.5 s、nBCl3 : nNH3 : nH2 : nN2=1 : 3 : 1 : 6条件下, SiC纤维表面沉积BN涂层的XRD图谱

Fig. 7 XRD patterns of BN coatings deposited on SiC fibers surface at 650℃, 7 kPa and 0.5 s, while nBCl3 : nNH3 : nH2 : nN2=1 : 3 : 1 : 6^(a) Deposited at 650℃; (b) Deposited at 650℃ and then heat-treated at 1200℃

表1 相关气相组分的化学反应项

Table 1 Reaction terms of related gaseous species

Species	c_i	dc_i/dt
BCl₃	c₁	c₁×(-k₁-k_Ⅰ)
NH₃	c₂	c₂× (-k₁-k_Ⅰ)
Cl₂BNH₂	c₃	c₁×k₁-c₃× (k₂+k₄+k_Ⅱ)
ClBNH	c₄	c₃×k₄-c₄×k_Ⅲ
ClB(NH₂)₂	c₅	c₃×k₂-c₅× (k₃+k_Ⅳ)
B(NH₂)₃	c₆	c₅×k₃-c₆×k_Ⅴ
HCl	c₇	c₁×k₁+c₃× (k₂+k₄+k_Ⅱ)+c₄×k_Ⅲ+c₅×k_Ⅳ+c₆×k_Ⅴ

图8 BN化学气相沉积过程示意图

Fig. 8 Schematic of chemical vapor deposition process for BN

表2 气相反应的热力学数据

Table 2 Thermodynamic data for gaseous reactions

Reactions	Pre-exponential factor, A/(cm³•mol^-1•s^-1)	Apparent activation energy, E_a/(kJ•mol^-1)
1	4.21×10¹¹	34.95
2	3.88×10¹¹	77.44
3	1.66×10¹¹	83.30
4	3.89×10¹⁴	330.68

图9 在650℃ (a)和850℃ (b)温度下BN沉积过程的气相浓度变化

Fig. 9 Gas-phase concentrations changes during deposition process of BN at 650℃ (a) and 850℃ (b)^(7 kPa, 0.5 s, nBCl3 : nNH3 : nH2 : nN2=1 : 3 : 1 : 6)

图10 4 s滞留时间内BN沉积过程的气相浓度变化

Fig. 10 Gas-phase concentrations changes during the deposition process of BN at 0.4 s of residence time^(650℃, 10 kPa, nBCl3 : nNH3 : nH2=1 : 3 : 1)

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BCl₃-NH₃-H₂-N₂前驱体化学气相沉积法制备氮化硼涂层

Preparation of Boron Nitride Coating from BCl₃-NH₃-H₂-N₂ Precursor by Chemical Vapor Deposition

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