表面氧含量对高纯硅粉高温氮化行为的影响
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摘要
研究了表面氧含量对高纯硅原料在氮氢气氛下直接氮化行为的影响,并合成高α相氮化硅。研究结果表明,硅粉在氮氢气氛下1 350℃保温3h,氮化产物中α-Si_3N_4含量随原料氧含量的增加呈先增加后减少的趋势,当硅原料表面氧含量为3.91%时,氮化产物中α-Si_3N_4含量可达97%以上,残留硅含量低于1%,产物中部氧含量为1.71%,在此环境下硅粉氮化主要以化学气相沉积的方式进行,产物形貌以杆状α-Si_3N_4晶须为主。硅原料表面氧含量低于4.38%时,氮化产物α-Si_3N_4含量均在95%以上,另有少量的β-Si_3N_4和残留硅,XRD测试精度范围内无氮氧化硅相存在。当硅原料氧含量高于5.61%时,产物中则出现氮氧化硅,随着原料氧含量增加,氮氧化硅含量明显上升。当硅原料氧含量低于5.61%时,残留硅含量随氧含量增加明显减少,说明原料中氧的增加可以显著加快氮化速率,降低氮化产物中残留硅的含量。
The effects of surface oxygen content on the nitridation of high-purity silicon powders were studied,high-αphase silicon nitride was prepared via direct nitridation process of silicon powders in the N_2/H_2 atmosphere.The results show that the content ofα-Si_3N_4 in nitridation products tended to increase first and then decrease with the increase of the oxygen content on the silicon surface.When the surface oxygen content of silicon powders was 3.91%,theα-Si_3N_4 content of nitridation products could reach97%,the residual silicon content was lower than 1%and the oxygen content in central region was 1.71%,the micrograph morphology of nitridation products mainly composed of rod shapedα-Si_3N_4 whisker which was formed by chemical vapor deposition at 1 350℃for 3 hours in the N2/H_2 atmosphere.When the surface oxygen content of silicon powders was lower than 4.38%,all the content of theα-Si_3N_4 in nitridation products was over 95%,a small amount ofβ-Si_3N_4 and residual silicon phase,which was examined by XRD,can be observed,but no silicon oxynitride.While the oxygen content of silicon powders was higher than 5.61%,the content of silicon oxynitride increased obviously with the increase of oxygen content.While the oxygen content of silicon powders was lower than 5.61%,the residual silicon of nitridation products decreased significantly with the increase of oxygen content,which showed that the increase of oxygen in silicon powders could accelerate the nitridation rate significantly and then reduce the content of residual silicon in nitridation products.
The effects of surface oxygen content on the nitridation of high-purity silicon powders were studied,high-αphase silicon nitride was prepared via direct nitridation process of silicon powders in the N_2/H_2 atmosphere.The results show that the content ofα-Si_3N_4 in nitridation products tended to increase first and then decrease with the increase of the oxygen content on the silicon surface.When the surface oxygen content of silicon powders was 3.91%,theα-Si_3N_4 content of nitridation products could reach97%,the residual silicon content was lower than 1%and the oxygen content in central region was 1.71%,the micrograph morphology of nitridation products mainly composed of rod shapedα-Si_3N_4 whisker which was formed by chemical vapor deposition at 1 350℃for 3 hours in the N2/H_2 atmosphere.When the surface oxygen content of silicon powders was lower than 4.38%,all the content of theα-Si_3N_4 in nitridation products was over 95%,a small amount ofβ-Si_3N_4 and residual silicon phase,which was examined by XRD,can be observed,but no silicon oxynitride.While the oxygen content of silicon powders was higher than 5.61%,the content of silicon oxynitride increased obviously with the increase of oxygen content.While the oxygen content of silicon powders was lower than 5.61%,the residual silicon of nitridation products decreased significantly with the increase of oxygen content,which showed that the increase of oxygen in silicon powders could accelerate the nitridation rate significantly and then reduce the content of residual silicon in nitridation products.
引文
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19 Campos-Loriz D,Riley F L.The effects of hydrogen on the nitridation of silicon[J].Journal of Materials Science,1979,14(4):1007.
20 Jovanovic Z,Kimura S.Use of two-phase standards of unknown compositions to determine calibration constants for powder XRD by linear regression[J].Journal of the American Ceramic Society,1994,77(8):2226.
21 Rakshit J,Das P K.Optimization of time-temperature schedule for nitridation of silicon compact on the basis of silicon and nitrogen reaction kinetics[J].Bulletin of Materials Science,2000,23(4):249.
22 Barsoum M,Kangutar P,Koczak M J.Nitridation mechanisms of silicon powder compacts[C]∥13th Annual Conference on Composites and Advanced Ceramic Materials,Part 1 of 2:Ceramic Engineering and Science Proceedings,Volume 10.John Wiley&Sons,2009:794.
23 Jennings H M.On reactions between silicon and nitrogen[J].Journal of Materials Science,1983,18(4):951.
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25 叶大伦.实用无机物热力学数据手册[M].北京:冶金工业出版社,2002:13.
2 Bocanegra-Bernal M H,Matovic B.Mechanical properties of silicon nitride-based ceramics and its use in structural applications at high temperatures[J].Materials Science and Engineering:A,2010,527(6):1314.
3 Riley F L.Silicon nitride and related materials[J].Journal of the American Ceramic Society,2000,83(2):245.
4 Ren H,Zhang L,Su K,et al.Thermodynamic study on the chemical vapor deposition of silicon nitride from the SiCl4-NH3-H2system[J].Computational and Theoretical Chemistry,2015,1051:93.
5 Sahu B B,Shin K S,Han J G.Integrated approach for low-temperature synthesis of high-quality silicon nitride films in PECVD using RF-UHF hybrid plasmas[J].Plasma Sources Science and Technology,2016,25(1):015017.
6 Ziegenbalg G,Breuel U,Ebrecht E,et al.Synthesis ofα-silicon nitride powder by gas-phase ammonolysis of CH3SiCl3[J].Journal of the European Ceramic Society,2001,21(7):947.
7 Park Y J,Park M J,Kim J M,et al.Sintered reaction-bonded silicon nitrides with high thermal conductivity:The effect of the starting Si powder and Si3N4diluents[J].Journal of the European Ceramic Society,2014,34(5):1105.
8 Pavarajarn V,Kimura S.Catalytic effects of metals on direct nitridation of silicon[J].Journal of the American Ceramic Society,2001,84(8):1669.
9 Dervi2begovic H,Riley F L.The role of hydrogen in the nitridation of silicon powder compacts[J].Journal of Materials Science,1981,16(7):1945.
10 Pigeon R G,Varma A,Miller A E.Some factors influencing the formation of reaction-bonded silicon nitride[J].Journal of Materials Science,1993,28(7):1919.
11 Yao G,Li Y,Jiang P,et al.Formation mechanisms of Si3N4and Si2N2O in silicon powder nitridation[J].Solid State Sciences,2017,66:50.
12 Vongpayabal P,Kimura S.Kinetics of SiO vapor ammonolysis for nano-sized silicon nitride powder synthesis[J].Powder technology,2005,156(2):73.
13 Lin D,Kimura S.Kinetics of silicon monoxide ammonolysis for nanophase silicon nitride synthesis[J].Journal of the American Ceramic Society,1996,79(11):2947.
14 Wen Y,Xia D,Xuan W.Modeling for particle size prediction and mechanism of silicon nitride nanoparticle synthesis by chemical vapor deposition[J].Aerosol Science and Technology,2017,51(7):845.
15 Parikh R S,Lightfoot A,Haggerty J S,et al.Effects of trace O2levels on the nitriding kinetics of high-purity silicon powders[J].Journal of the American Ceramic Society,1999,82(10):2626.
16 Campos-Loriz D,Riley F L.The effect of silica on the nitridation of silicon[J].Journal of Materials Science,1976,11(1):195.
17 Rahaman M N,Moulson A J.The removal of surface silica and its effect on the nitridation of high-purity silicon[J].Journal of Materials Science,1984,19(1):189.
18 Shaw N J.The combined effects of Fe and H2on the nitridation of silicon[J].Journal of Materials Science Letters,1982,1(8):337.
19 Campos-Loriz D,Riley F L.The effects of hydrogen on the nitridation of silicon[J].Journal of Materials Science,1979,14(4):1007.
20 Jovanovic Z,Kimura S.Use of two-phase standards of unknown compositions to determine calibration constants for powder XRD by linear regression[J].Journal of the American Ceramic Society,1994,77(8):2226.
21 Rakshit J,Das P K.Optimization of time-temperature schedule for nitridation of silicon compact on the basis of silicon and nitrogen reaction kinetics[J].Bulletin of Materials Science,2000,23(4):249.
22 Barsoum M,Kangutar P,Koczak M J.Nitridation mechanisms of silicon powder compacts[C]∥13th Annual Conference on Composites and Advanced Ceramic Materials,Part 1 of 2:Ceramic Engineering and Science Proceedings,Volume 10.John Wiley&Sons,2009:794.
23 Jennings H M.On reactions between silicon and nitrogen[J].Journal of Materials Science,1983,18(4):951.
24 Riley F L.Reaction bonded silicon nitride[C]∥Materials Science Forum.Trans Tech Publications,1989,47:70.
25 叶大伦.实用无机物热力学数据手册[M].北京:冶金工业出版社,2002:13.