碱金属氧化物对低介电封接玻璃结构与性能的影响研究

硅酸盐通报 ›› 2021, Vol. 40 ›› Issue (11): 3807-3812.

碱金属氧化物对低介电封接玻璃结构与性能的影响研究

李金威^1,2, 王巍巍^1,2, 仲召进^1,2, 王萍萍^1,2, 石丽芬^1,2, 官敏³, 于涛³, 曹欣^1,2

1.浮法玻璃新技术国家重点实验室,蚌埠 233000;
2.硅基材料安徽省实验室,蚌埠 233000;
3.中国建材国际工程集团有限公司,上海 200063

收稿日期:2021-05-26 修回日期:2021-06-21 出版日期:2021-11-15 发布日期:2021-12-08
通讯作者: 曹欣,博士,教授级高工。E-mail:dargoncao@126.com
作者简介:李金威(1991—),男。主要从事特种玻璃的研究。E-mail:lijinwei06@126.com
基金资助:
安徽省重点研究和开发计划(1804a09020071,202004a05020036);上海市科技创新行动计划(18520731300)

Effects of Alkali Metal Oxides on Structure and Properties of Sealing Glass with Low-Dielectric Constant

LI Jinwei^1,2, WANG Weiwei^1,2, ZHONG Zhaojin^1,2, WANG Pingping^1,2, SHI Lifen^1,2, GUAN Min³, YU Tao³, CAO Xin^1,2

1. State Key Laboratory of Advanced Technology for Float Glass Technology, Bengbu 233000, China;
2. Laboratory in Anhui Province of Silicon-Based Materials, Bengbu 233000, China;
3. China Triumph International Engineering Company, Limited, Shanghai 200063, China

Received:2021-05-26 Revised:2021-06-21 Online:2021-11-15 Published:2021-12-08

摘要/Abstract

摘要： 玻璃由于优异的电学性能在电子封接领域的应用越来越广泛。本文以硼铝硅酸盐玻璃为基础玻璃体系,采用高温熔融法制备了低介电封接玻璃。通过拉曼光谱、热膨胀系数测定仪、密度计、弯曲梁低温测试仪、精密阻抗分析仪等对样品性能进行表征,研究了碱金属氧化物对低介电玻璃的结构与性能的影响。研究结果表明:碱金属氧化物R₂O总量保持不变,随着Li₂O取代量的增加,玻璃结构中[BO₃]含量先降低后增加,同时[AlO₄]增加、[AlO₆]降低;玻璃的热膨胀系数先降低后升高,密度变化趋势与之相反,且均在LN-3(Na₂O与Li₂O质量比为1.0:1.0)组出现极值;特征温度先升高后降低,最后Na₂O被完全取代后呈现再次升高的趋势;玻璃介电常数和介电损耗先降低后升高,且混合碱金属玻璃的介电常数和介电损耗均低于单一碱金属玻璃。

关键词: 碱金属氧化物, 封接玻璃, 玻璃网络结构, 热膨胀系数, 介电常数, 介电损耗, 密度

Abstract: Glass is widely used in the field of electronic sealing due to its excellent electrical properties. The low dielectric sealing glass was prepared by high temperature melting method under aluminoborosilicate glass. The properties of the samples were characterized by Raman spectroscopy, thermal expansion coefficient tester, densitometer, bending beam low temperature tester and precision impedance analyzer. The effect of alkali metal oxides on the structure and properties of low dielectric glass was studied. The result shows that when the total content of R₂O remains unchanged, with the increase of Li₂O content, the content of [BO₃] in the glass structure decreases first and then increases, the content of [AlO₄] increases and the content of [AlO₆] decreases. The thermal expansion coefficient of glass decreases first and then increases, and the trend of density change is opposite to the thermal expansion coefficient. All of the above variables have extreme values in the LN-3 (the mass ratio of Na₂O and Li₂O is 1.0:1.0) group. The characteristic temperature of glass increases first and then decreases, and finally increases again when Na₂O is completely replaced. The dielectric constant and dielectric loss of glass decrease first and then increase, and the dielectric constant and dielectric loss of the glass containing mixed alkali metals are lower than that of the glass containing single alkali metal.

Key words: alkali metal oxide, sealing glass, network structure of glass, thermal expansion coefficient, dielectric constant, dielectric loss, density

中图分类号:

TQ171

李金威, 王巍巍, 仲召进, 王萍萍, 石丽芬, 官敏, 于涛, 曹欣. 碱金属氧化物对低介电封接玻璃结构与性能的影响研究[J]. 硅酸盐通报, 2021, 40(11): 3807-3812.

LI Jinwei, WANG Weiwei, ZHONG Zhaojin, WANG Pingping, SHI Lifen, GUAN Min, YU Tao, CAO Xin. Effects of Alkali Metal Oxides on Structure and Properties of Sealing Glass with Low-Dielectric Constant[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2021, 40(11): 3807-3812.

参考文献

[1] 周鹏,王衍行,祖成奎,等.低介电玻璃的研究进展[J].材料导报,2016,30(s1):290-293.
ZHOU P, WANG Y H, ZU C K, et al. Research on low dielectric glass[J]. Materials Review, 2016, 30(s1): 290-293 (in Chinese).
[2] 周毅,李永明,孙旭东,等.B₂O₃添加磷玻璃的制备、介电与力学性能的研究[J].材料科学,2020,10(3):127-134.
ZHOU Y, LI Y M, SUN X D, et al. Investation of preparation, dielectric and mechanical properties of phosphate glass with B₂O₃ addition[J]. Materials Science, 2020, 10(3): 127-134 (in Chinese).
[3] 王巍巍,杨小菲,曹欣,等.Al₂O₃对低介电封接玻璃结构与性能的影响研究[J].玻璃搪瓷与眼镜,2020,48(4):1-5.
WANG W W, YANG X F, CAO X, et al. Effects of Al₂O₃ content on structure and properties of low-dielectric sealing glass[J]. Glass Enamel & Ophthalmic Optics, 2020, 48(4): 1-5 (in Chinese).
[4] 沈阳,姜宏,何文琦,等.低介电高硼硅酸盐玻璃的性能研究[J].功能材料,2015,46(21):21050-21053.
SHEN Y, JIANG H, HE W Q, et al. Effect of high content B₂O₃ on the structure and properties of silicate glass[J]. Journal of Functional Materials, 2015, 46(21): 21050-21053 (in Chinese).
[5] 操芳芳,马立云,曹欣,等.SiO₂/B₂O₃质量比对低介电封接玻璃性能的影响[J].材料导报,2019,33(s1):199-201+210.
CAO F F, MA L Y, CAO X, et al. Effect of SiO₂/B₂O₃ mass ratio on properties of sealing glasses with low dielectric[J]. Materials Reports, 2019, 33(s1): 199-201+210 (in Chinese).
[6] HE D F, GAO C. Effect of boron on crystallization, microstructure and dielectric properties of CBS glass-ceramics[J]. Ceramics International, 2018, 44(14): 16246-16255.
[7] 朱奎.高硼硅防火玻璃的组成、结构和性能的研究[D].武汉:武汉理工大学,2017.
ZHU K. Study on the composition, structure and properties of borosilicate fire-resistance glass[D]. Wuhan: Wuhan University of Technology, 2017 (in Chinese).
[8] TOMOZAWA M. The mixed alkali effect and thermodynamic state of glasses[J]. Solid State Ionics, 1998, 105(1/2/3/4): 249-255.
[9] 许靖琨,宁伟,汪庆卫,等.Li₂O对ZnO-B₂O₃-SiO₂系统玻璃的热膨胀性能影响[J].东华大学学报(自然科学版),2013,39(6):716-719.
XU J K, NING W, WANG Q W, et al. Effect of Li₂O on the thermal expansion properties of ZnO-B₂O₃-SiO₂ system glasses[J]. Journal of Donghua University (Natural Science), 2013, 39(6): 716-719 (in Chinese).
[10] AGARWAL A, SETH V P, SANGHI S, et al. Mixed alkali effect in optical properties of lithium-potassium bismuth borate glass system[J]. Materials Letters, 2004, 58(5): 694-698.
[11] 鲁鹏,夏文宝,姜宏,等.高铝硅酸盐玻璃的红外、拉曼光谱分析[J].硅酸盐通报,2015,34(3):878-881+887.
LU P, XIA W B, JIANG H, et al. Analysis of high alumina silicate glass with infrared and Raman spectroscopy[J]. Bulletin of the Chinese Ceramic Society, 2015, 34(3): 878-881+887 (in Chinese).
[12] PENG S, KE Z K, CAO X, et al. A novel type of borosilicate glass with excellent chemical stability and high ultraviolet transmission[J]. Journal of Non-Crystalline Solids, 2020, 528: 119735.
[13] 崔介东,曹欣,马立云,等.特种玻璃的Raman光谱分析及其浮法成型工艺研究[J].硅酸盐通报,2019,38(8):2688-2694+2700.
CUI J D, CAO X, MA L Y, et al. Raman spectroscopy analysis and study on float forming process of special glasses[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(8): 2688-2694+2700 (in Chinese).
[14] 朱奎,程金树,陆平,等.Al₂O₃对硼硅酸盐玻璃结构和性能的影响[J].硅酸盐通报,2017,36(1):396-400.
ZHU K, CHENG J S, LU P, et al. Effect of Al₂O₃ on structure and properties of borosilicate glass[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(1): 396-400 (in Chinese).
[15] 田英良,孙诗兵.新编玻璃工艺学[M].北京:中国轻工业出版社,2009.
TIAN Y L, SUN S B. New glass technology[M]. Beijing: China Light Industry Press, 2009 (in Chinese).
[16] 房玉.硼硅酸盐玻璃组成、结构与性能的研究[D].武汉:武汉理工大学,2012.
FANG Y. Study on the component, structure and properties of borosilicate glass[D]. Wuhan: Wuhan University of Technology, 2012 (in Chinese).
[17] 万军鹏,程金树,汤李缨,等.耐热高强硼硅酸盐玻璃中混合碱的研究[J].武汉理工大学学报,2008,30(4):40-42.
WAN J P, CHENG J S, TANG L Y, et al. Research on the mixed alkali of heat-resistant borosilicate glass[J]. Journal of Wuhan University of Technology, 2008, 30(4): 40-42 (in Chinese).
[18] SHAN Z T, LIU S J, TAO H Z, et al. Mixed alkaline-earth effects on several mechanical and thermophysical properties of aluminate glasses and melts[J]. Journal of the American Ceramic Society, 2019, 102(3): 1128-1136.
[19] 胡一晨,余芳,赵雪辰,等.碱金属氧化物对低损耗玻璃工艺性能及电学性能的影响[J].玻璃与搪瓷,2005,33(4):42-46.
HU Y C, YU F, ZHAO X C, et al. Study on effects of alkalis on electrical and technological properties of low dielectric loss glasses[J]. Glass & Enamel, 2005, 33(4): 42-46 (in Chinese).