单晶α-Si3N4纳米线宏量制备研究

doi:10.15541/jim20180381

无机材料学报 ›› 2019, Vol. 34 ›› Issue (6): 667-672.DOI: 10.15541/jim20180381

单晶α-Si₃N₄纳米线宏量制备研究

雷超^1,²,魏飞²

^1. 广东省科学院广东省材料与加工研究所, 广州 510650
^2. 清华大学化工系, 绿色反应工程与工艺北京市重点实验室, 北京100084

收稿日期:2018-08-31 修回日期:2018-10-03 出版日期:2019-06-20 网络出版日期:2019-05-23
作者简介:雷超(1988-), 男, 博士. E-mail:chleijob@163.com
基金资助:
广东省科学院实施创新驱动发展能力建设专项(2018GDASCX-0964);广东省科学院科研平台环境与能力建设专项(2016GDASPT-0209);广东省科学院科研平台环境与能力建设专项(2016GDASPT-0321);广东省科学院院属骨干科研机构创新能力建设专项(2017GDASCX- 0117);广东省科学院院属骨干科研机构创新能力建设专项(22018GDASCX-0117);广州市科技计划项目(ZWY201704003);广东省材料与加工研究所创新能力建设项目(2017A070701029);广东省公益研究与能力建设专项(2017A070702019);广东省省级科技计划项目(2017A050503004)

Mass Production of α-silicon Nitride Single-crystalline Nanowires

Chao LEI^1,²,Fei WEI²

^1. Guangdong Institute of Materials and Processing, Guangdong Academy of Sciences, Guangzhou 510650, China
^2. Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Received:2018-08-31 Revised:2018-10-03 Published:2019-06-20 Online:2019-05-23
Supported by:
GDAS’ Project of Science and Technology Development(2018GDASCX-0964);GDAS’ Project of Research Environment and Capacity Building(2016GDASPT-0209);GDAS’ Project of Research Environment and Capacity Building(2016GDASPT-0321);Guangdong Academy of Sciences Project(2017GDASCX- 0117);Guangdong Academy of Sciences Project(22018GDASCX-0117);Guangzhou Science and Technology Planning Project(ZWY201704003);Guangdong Institute of Materials and Processing Innovation Capacity Building Project(2017A070701029);Project for Public Welfare Research and Capacity Building of Guangdong Province(2017A070702019);Science and Technology Planning Project of Guangdong Province(2017A050503004)

摘要/Abstract

摘要：

本研究提出了一种宏量制备单晶α-Si₃N₄纳米线的方法。以造粒硅粉为原料, 通过在N₂-H₂混合气氛中直接氮化, 得到具有核壳结构的氮化产物(Si₃N₄纳米线@多孔Si₃N₄微米粉体), 氮化产物经过破碎、研磨、分离后即可获得Si₃N₄纳米线。检测结果表明, 制备的Si₃N₄纳米线直径为80~150 nm, 长径比为20~50, 其中纳米线含量>95wt%, α相/β相比为17.6, 收率为3.1%。进一步研究表明, 原料中微量Fe元素在还原气氛下具有催化作用, 纳米线由典型的气-液-固(VLS)生长机制控制。实验中对原料硅粉造粒后再氮化具有三大优点: 数量级地增大了Si₃N₄纳米线生长空间; 纳米线生长分布集中, 有利于后续高效分离; 显著提高了氮化速率。

关键词: 氮化硅, 纳米线, 直接氮化, 造粒, VLS机制

Abstract:

α-silicon nitride single-crystalline nanowires were prepared by direct nitridation of granulation Si powders in N₂-H₂mixture gas. The nitridation product has the core-shell structure (Si₃N₄nanowires @porous Si₃N₄ powders), where Si₃N₄nanowires can be effectively separated by crushing and grinding. The results show that the as-prepared α-Si₃N₄nanowires are straight and uniform with diameters of 80-150 nm, length to diameter ratios of 20-50, purity higher than 95wt%, and yield of 3.1%. Further study indicates that growth of Si₃N₄nanowires is controlled by the Vapor-Liquid-Solid (VLS) mechanism, where the trace Fe elements serves as catalyst in the reduction atmosphere. In this study, The process of the raw silicom powder granulation after nitriding shows three advantages: 1) remarkably increasing growth space of nanowires; 2) leading to concentrated distribution of nanowire, tacilitating subsequent separation; 3) remarkably increasing the nitridation rate.

Key words: Si₃N₄, nanowires, direct nitridation, granulation, VLS mechanism

中图分类号:

TB32

雷超, 魏飞. 单晶α-Si₃N₄纳米线宏量制备研究[J]. 无机材料学报, 2019, 34(6): 667-672.

Chao LEI, Fei WEI. Mass Production of α-silicon Nitride Single-crystalline Nanowires[J]. Journal of Inorganic Materials, 2019, 34(6): 667-672.

图/表 9

图1 不同样品的 SEM照片和实物照片

Fig. 1 SEM images and photograph of different samples (a) SEM image of Si raw materials; (b) SEM images of Granulation Si powders; (c) SEM image of granulation Si powders after 3 h nitridation; (d) Photograph of Si3N4/ alcohol mixture after stratification

图2 Si粉原料、Si3N4粉体、Si3N4纳米线的XRD图谱

Fig. 2 XRD patterns of Si raw materials, Si3N4 powders, Si3N4 nanowires

表1 杂质元素的分析结果

Table 1 Impurity elements analysis results

Element/wt%	Fe	Ca	Al	O	C
Si raw materials	0.008	0.013	0.012	0.14	-
Si₃N₄nanowires	0.011	0.007	0.031	1.56	-
Si₃N₄particles	0.006	0.014	0.049	1.07	-

图3 Si3N4纳米线的形貌照片 (a-b) SEM images; (c) TEM imag; (d) SAED pattern

Fig. 3 Morphologies of Si3N4 nanowires

表2 纳米线表面的EDS元素分析结果

Table 2 Elemental analysis results of Si3N4 nanowires

Spectrum	Element/at%
Spectrum	Si	N	O	Fe
1	41.42	55.43	3.16	0
2	49.17	46.22	4.17	0.45

图4 不同倍率下Si3N4微米粉体的形貌照片 (a) Broken particle; (b) Unbroken particle

Fig. 4 Morphologies under different magnifications for Si3N4 particles

图5 硅粉球表面纳米线的形貌照片

Fig. 5 Morphologies of nanowires on the granulation Si powder surface (a-b) 15 min nitridation in the 90vol% N2-10vol% H2 mixture gas; (c) 3 h nitridation in N2

图6 不同硅在1350 ℃, 90vol% N2+10vol% H2混合气氛下氮化3 h后的SEM照片

Fig. 6 SEM images of different Si powders after 3 h nitridation in the 90vol% N2+10vol% H2 mixture gas (a) Raw Si powders; (b) Inside of the granulation Si powders

图7 不同气氛下, 造粒硅粉球的氮化速率

Fig. 7 Nitridation rate of granulation Si powders at different atmospheres

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单晶α-Si₃N₄纳米线宏量制备研究

Mass Production of α-silicon Nitride Single-crystalline Nanowires

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