复合烧结助剂对Si3N4陶瓷力学性能和热导率的影响

doi:10.15541/jim20220101

无机材料学报 ›› 2022, Vol. 37 ›› Issue (9): 947-953.DOI: 10.15541/jim20220101

复合烧结助剂对Si₃N₄陶瓷力学性能和热导率的影响

付师¹^,²(), 杨增朝¹, 李宏华¹(), 王良¹, 李江涛¹^,²()

1.中国科学院理化技术研究所, 低温重点实验室, 北京 100190
2.中国科学院大学材料与光电研究中心, 北京 100049

收稿日期:2022-03-02 修回日期:2022-04-29 出版日期:2022-09-20 网络出版日期:2022-05-27
通讯作者: 李江涛, 研究员. E-mail: lijiangtao@mail.ipc.ac.cn;
李宏华, 助理研究员. E-mail: lihonghua@mail.ipc.ac.cn
作者简介:付师(1995-), 男, 博士研究生. E-mail: fushi18@mails.ucas.ac.cn
基金资助:
国家重点研发计划(2017YFB0310303);国家自然科学基金(52072381);国家自然科学基金(U1904217)

Mechanical Properties and Thermal Conductivity of Si₃N₄ Ceramics with Composite Sintering Additives

FU Shi¹^,²(), YANG Zengchao¹, LI Honghua¹(), WANG Liang¹, LI Jiangtao¹^,²()

1. Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Science, Beijing 100190, China
2. Center of Materials Science and Optoelectronics Engineering, University of the Chinese Academy of Science, Beijing 100049, China

Received:2022-03-02 Revised:2022-04-29 Published:2022-09-20 Online:2022-05-27
Contact: LI Jiangtao, professor. E-mail: lijiangtao@mail.ipc.ac.cn;
LI Honghua, lecturer. E-mail: lihonghua@mail.ipc.ac.cn
About author:FU Shi, male, PhD candidate. E-mail: fushi18@mails.ucas.ac.cn
Supported by:
National Key Research and Development Program of China(2017YFB0310303);National Natural Science Foundation of China(52072381);National Natural Science Foundation of China(U1904217)

摘要/Abstract

摘要：

Si₃N₄陶瓷因兼具优异的力学和热学性能, 成为第三代半导体陶瓷基板的首选材料之一。本研究以7种不同离子半径的稀土氧化物(RE₂O₃, RE=Sc、Lu、Yb、Y、Gd、Nd、La)与非氧化物(MgSiN₂)作复合烧结助剂, 通过热压烧结和退火热处理制备了高强、高热导Si₃N₄陶瓷, 并系统研究了复合烧结助剂中RE₂O₃种类对Si₃N₄陶瓷物相组成、微结构、力学性能和热导率的影响规律。热压后Si₃N₄陶瓷力学性能优越, 其中添加Nd₂O₃-MgSiN₂的样品弯曲强度达到(1115±49) MPa。退火处理后Si₃N₄陶瓷的热导率得到大幅提升, 呈现出随稀土离子半径减小而逐渐增大的规律, 其中添加Sc₂O₃-MgSiN₂的样品退火后的热导率从54.7 W·m^-1·K^-1提升至80.7 W·m^-1·K^-1, 提升了47.6%。该结果表明, 相较于国际上通用的Y₂O₃-MgSiN₂和Yb₂O₃-MgSiN₂烧结助剂组合, Sc₂O₃-MgSiN₂有望成为制备高强度、高热导Si₃N₄陶瓷的新型复合助剂。

关键词: 氮化硅, 复合烧结助剂, 退火处理, 热导率

Abstract:

Si₃N₄ceramics have become one of the most promising materials for third-generation semiconductor’s ceramic substrates due to its excellent mechanical and thermal properties. In this work, seven rare earth oxides (RE₂O₃, RE=Sc, Lu, Yb, Y, Gd, Nd, La) and non-oxides (MgSiN₂) were used as composite sintering additives to prepare Si₃N₄ ceramics with high strength and high thermal conductivity by hot pressing sintering and annealing. The effects of RE₂O₃ types in the composite additives on the phase composition, microstructure, mechanical properties, and thermal conductivity of Si₃N₄ ceramics were systematically studied. The mechanical properties of Si₃N₄ ceramics after hot pressing sintering were superior to that without hot pressing, and the bending strength of the sample with Nd₂O₃-MgSiN₂ additive reached (1115±49) MPa. After annealing, the thermal conductivity of Si₃N₄ceramics increased significantly, and gradually increased with the decrease of the rare earth ion’s radius. The thermal conductivity of the sample with Sc₂O₃-MgSiN₂ additive increased from 54.7 W·m^-1·K^-1to 80.7 W·m^-1·K^-1 (increased by 47.6%) after annealing. The results indicate that Sc₂O₃-MgSiN₂is expected to be a new composite additive for the preparation of high strength and high thermal conductivity Si₃N₄ceramics as compared to the internationally accepted combination of Y₂O₃-MgSiN₂ and Yb₂O₃-MgSiN₂ additives.

Key words: silicon nitride, composite sintering additives, annealing, thermal conductivity

中图分类号:

TQ174

付师, 杨增朝, 李宏华, 王良, 李江涛. 复合烧结助剂对Si₃N₄陶瓷力学性能和热导率的影响[J]. 无机材料学报, 2022, 37(9): 947-953.

FU Shi, YANG Zengchao, LI Honghua, WANG Liang, LI Jiangtao. Mechanical Properties and Thermal Conductivity of Si₃N₄ Ceramics with Composite Sintering Additives[J]. Journal of Inorganic Materials, 2022, 37(9): 947-953.

图/表 7

图1 不同助剂体系热压烧结制备Si3N4陶瓷的XRD图谱

Fig. 1 XRD patterns of Si3N4 ceramics with different additive systems prepared by hot pressing sintering

图2 不同助剂体系热压烧结制备Si3N4陶瓷抛光面的SEM照片

Fig. 2 SEM images of the polished surfaces of Si3N4 ceramics with different additive systems prepared by hot pressing sintering (a) LuM; (b) YbM; (c) YM; (d) GdM; (e) NdM; (f) LaM

表1 热压烧结制备Si3N4陶瓷样品的性能

Table 1 Properties of Si3N4 ceramic samples prepared by hot pressing sintering

Sample	Ionic radius/nm	Relative density/%	Grain size/μm	Vickers’ hardness/GPa	Flexural strength/MPa	Fracture toughness/ (MPa·m^1/2)	Thermal conductivity/ (W·m^-1·K^-1)
ScM	0.073	99.36	0.72±0.32	14.58±0.25	905±36	8.21±0.09	54.7
LuM	0.085	99.53	0.9±0.40	14.75±0.20	785±25	8.01±0.12	49.6
YbM	0.086	99.49	0.97±0.47	14.75±0.27	759±20	8.03±0.16	49.7
YM	0.089	99.73	1.03±0.46	14.64±0.29	819±10	8.65±0.11	51.1
GdM	0.094	99.89	1.01±0.48	14.57±0.22	792±34	7.62±0.47	54.6
NdM	0.100	99.37	0.95±0.42	14.79±0.27	1115±49	7.19±0.10	53.9
LaM	0.106	99.21	0.9±0.41	15.37±0.33	978±39	7.25±0.10	52.8

图3 退火处理后不同助剂体系Si3N4陶瓷的XRD图谱

Fig. 3 XRD patterns of Si3N4 ceramics with different additive systems after annealing

图4 退火处理后不同助剂体系Si3N4陶瓷抛光面的SEM照片

Fig. 4 SEM images of the polished surfaces of Si3N4 ceramics with different additive systems after annealing (a) LuMH; (b) YbMH; (c) YMH; (d) GdMH; (e) NdMH; (f) LaMH

图5 退火处理前后Si3N4陶瓷的(a)平均晶粒尺寸、(b)弯曲强度、(c)断裂韧性和(d)热导率随稀土离子半径的变化

Fig. 5 (a) Average grain size, (b) bending strength, (c) fracture toughness, and (d) thermal conductivity changing with radius of rare earth ion of Si3N4 ceramics before and after annealing

图6 退火处理前后Si3N4陶瓷样品微观结构形貌

Fig. 6 Microstructures of Si3N4 ceramic samples before and after annealing (a) ScM and (d) ScMH etched by molten NaOH; Fracture surfaces of (b) YM, (e) YMH, (c) YbM and (f) YbMH

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复合烧结助剂对Si₃N₄陶瓷力学性能和热导率的影响

Mechanical Properties and Thermal Conductivity of Si₃N₄ Ceramics with Composite Sintering Additives

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