沉积温度及热处理对低压化学气相沉积氮化硅涂层的影响

doi:10.15541/jim20190035

摘要/Abstract

摘要：

以SiCl₄-NH₃-H₂为前驱体, 在750~1250 ℃范围内通过低压化学气相沉积技术于碳纤维布上制备氮化硅涂层, 系统研究了沉积温度对氮化硅涂层的生长动力学、形貌、化学组成和结合态的影响。研究结果表明, 在沉积温度低于1050 ℃的情况下, 随着沉积温度的升高, 沉积速率单调增大。而当沉积温度高于1050 ℃时, 沉积速率随温度升高逐渐下降。在整个沉积温度范围内, 随着沉积温度的升高, 涂层表面形态逐渐向菜花状转变, 同时涂层表面变得愈加粗糙。涂层的最佳沉积温度在750~950 ℃之间。随着沉积温度的升高, 涂层中氮含量先降低后升高, 而硅含量不断增加, 氧含量在整个温度范围内逐渐降低。原始沉积涂层均呈无定形态, 经高于1300 ℃热处理后实现晶化, 并伴随着表面形貌的显著变化。此时涂层仅由a-Si₃N₄构成, 不存在任何b-Si₃N₄相。

关键词: 氮化硅涂层, 生长动力学, 沉积温度, 化学组成, 热处理

Abstract:

Silicon nitride coatings on carbon fiber cloth were prepared by Low Pressure Chemical Vapor Deposition (LPCVD) from gas mixtures of SiCl₄-NH₃-H₂ at temperatures ranging from 750 ℃to 1250 ℃. The effects of deposition temperature on the growth kinetics, morphologies, chemical composition and bonding state of the coatings were investigated. The results showed that deposition rate increased monotonously with temperature up to 1050 ℃, then it reversely decreased. In the whole temperature range, the coating surface morphology became gradually coarse with cauliflower-like grains as the deposition temperature increased. The optimal deposition temperature for infiltration was in the range between 750 and 950 ℃. Chemical composition analysis demonstrated that the nitrogen content of the coating firstly decreased and then increased with temperature increase, while the silicon content continuously increased and the oxygen content gradually decreased in the whole temperature range. Heat treatment at 1300 ℃ and above crystallized the coating. Concurrently, a significant change in its surface morphology was observed. All heat-treated coatings were exclusively composed of a-Si₃N₄, without the presence of any b-Si₃N₄.

Key words: silicon nitride coating, growth kinetic, deposition temperature, chemical composition, heat treatment

中图分类号:

TQ174

廖春景, 董绍明, 靳喜海, 胡建宝, 张翔宇, 吴惠霞. 沉积温度及热处理对低压化学气相沉积氮化硅涂层的影响[J]. 无机材料学报, 2019, 34(11): 1231-1237.

LIAO Chun-Jing, DONG Shao-Ming, JIN Xi-Hai, HU Jian-Bao, ZHANG Xiang-Yu, WU Hui-Xia. Deposition Temperature and Heat Treatment on Silicon Nitride Coating Deposited by LPCVD[J]. Journal of Inorganic Materials, 2019, 34(11): 1231-1237.

图/表 8

Fig. 1 Deposition rate as a function of temperature for SiCl4-NH3-H2 system

Fig. 2 Surface morphologies of silicon nitride coatings coated carbon fiber cloth at different temperatures (a, b) Original; (c, d) 750 ℃; (e, f) 950 ℃; (g, h) 1150 ℃

Fig. 3 Fracture morphologies of silicon nitride deposited on the carbon fiber cloth at different temperatures The left figures show outer coating morphologies of carbon fiber cloth while the right figures show their corresponding inner coating morphologies: (a) 750 ℃; (b) 850 ℃; (c) 950 ℃; (d) 1050 ℃; (e) 1150 ℃

Table 1 Chemical composition of silicon nitride deposited at different temperatures

Deposition temperature/℃	Elemental type and elemental contents/at%
Deposition temperature/℃	N	Si	O
750	53.21	30.78	16.01
850	46.92	43.25	9.82
950	43.67	43.49	12.84
1050	50.43	43.60	5.97
1150	49.88	46.87	3.24

Fig. 4 N1s and Si2P XPS spectra of silicon nitride coatings deposited at different temperatures (a-b) 750 ℃; (c-d) 950 ℃; (e-f) 1150 ℃; (a, c, e) NIS spectra; (b, d,f) Si2P spectra

Fig. 5 FT-IR spectra of silicon nitride coatings heat-treated at different temperatures (a) As-deposited; (b) 1300 ℃; (b) 1400 ℃; (d) 1500 ℃

Fig. 6 XRD patterns of as-deposited coatings heat-treated at different temperatures (a) 1300 ℃; (b) 1400 ℃; (c) 1500 ℃

Fig. 7 Surface morphology of silicon nitride coating deposited at 850 ℃ followed by heat treatment at 1500 ℃ for 2.5 h in Ar

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