AlN表面处理及级配填充对覆铜板绝缘层性能的影响规律与机制研究

doi:10.15541/jim20200639

无机材料学报 ›› 2021, Vol. 36 ›› Issue (8): 847-855.DOI: 10.15541/jim20200639

AlN表面处理及级配填充对覆铜板绝缘层性能的影响规律与机制研究

张维维¹(), 陆晨¹, 应国兵¹, 张建峰¹(), 江莞²

1.河海大学力学与材料学院, 南京 211100
2.东华大学材料科学与工程学院, 上海 201620

收稿日期:2020-11-09 修回日期:2020-12-09 出版日期:2021-08-20 网络出版日期:2020-12-30
通讯作者: 张建峰, 教授. E-mail: jfzhang_sic@163.com
作者简介:张维维(1996-), 女, 硕士研究生. E-mail: zwwbob@163.com
基金资助:
国家重点研发计划(2018YFC1508704);国家自然科学基金(11872171);中央高校业务费(B200202117)

Effect and Mechanism of the Surface Treatment and Gradation Filling of AlN on the Performance of Insulation Layer of Copper Clad Laminate

ZHANG Weiwei¹(), LU Chen¹, YING Guobing¹, ZHANG Jianfeng¹(), JIANG Wan²

1. College of Mechanics of Materials, Hohai University, Nanjing 211100, China
2. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China

Received:2020-11-09 Revised:2020-12-09 Published:2021-08-20 Online:2020-12-30
Contact: ZHANG Jianfeng, professor. E-mail: jfzhang_sic@163.com
About author:ZHANG Weiwei(1996-), female, Master candidate. E-mail: zwwbob@163.com
Supported by:
National Key R&D Program of China(2018YFC1508704);National Natural Science Foundation of China(11872171);Fundamental Research Funds for the Central Universities(B200202117)

摘要/Abstract

摘要：

在覆铜板绝缘层基体中添加导热陶瓷填料是提高其导热性能的一种有效方法。AlN是一种导热率高、绝缘性好的陶瓷填料, 但其易水解的性质限制了实际应用。此外, 相比于陶瓷填料-树脂基体复合材料体系, 有关填料填充型覆铜板产品性能的系统研究较少。本研究通过对AlN进行磷酸酸洗, 获得了抗水解性能优异的pAlN, 进一步研究了不同pAlN粒径和填充量对覆铜板导热性、剥离强度、介电性能和其他性能的影响。为了获得更有效的填料分布网络, 采取了不同粒径pAlN级配填充策略, 探究了多种级配方案对覆铜板性能的影响, 获得了最优级配和综合性能优异的覆铜板。在最优级配为pAlN-50 μm60%-5 μm5%时, 覆铜板绝缘层的热导率增大至0.757 W/(m·K), 相比纯树脂覆铜板提高160%, 具有优异的力学性能(剥离强度为1.012 N/mm, 弯曲强度为335 MPa)和介电性能(介电常数为4.499, 介电损耗为6.668×10^-3), 同时吸水率低至0.53%。同时探讨了AlN填料在覆铜板应用中存在的问题和解决方法, 系统研究了不同填充方案对覆铜板绝缘层性能的影响, 对其实际应用具有指导意义。

关键词: 氮化铝, 导热填料, 抗水解, 级配填充, 覆铜板

Abstract:

Introducing thermally conductive ceramic fillers to the copper clad laminate (CCL) resin matrix is an effective way to improve its thermal conductivity. AlN is a kind of ceramic filler with high thermal conductivity and good insulation, but its easy hydrolysis has limited its practical application. In addition, compared with the ceramic filler-resin matrix composite system, systematic research on the properties of the filler filled CCL is relatively rare. In this study, AlN was treated with phosphoric acid to obtain pAlN with excellent hydrolysis resistance. Then, the effects of different pAlN particle sizes and filling amount on the thermal conductivity, peeling strength, dielectric properties and other properties of AlN-filled CCLs were investigated. Finally, the pAlN gradation filling strategy of different particle sizes was adopted to explore the influence of different gradation schemes on the performance of the CCLs, of which the CCL with the best gradation and excellent comprehensive performance was obtained. The results show that the thermal conductivity of CCL insulating layer increases to 0.757 W/(m·K), 160% higher than that of pure resin CCL under the optimal gradation of pAlN-50 μm60%-5 μm5%. It displays excellent mechanical properties ( peel strength of 1.012 N/mm and bending strength of 335 MPa), dielectric properties (dielectric constant of 4.499 and dielectric loss of 6.668×10^-3), and the water absorption which is as low as 0.53%. All these data could be a promising guidence for CCL application.

Key words: AlN, thermal conductive filler, hydrolysis resistance, gradation filling, copper clad laminate

中图分类号:

TB332

张维维, 陆晨, 应国兵, 张建峰, 江莞. AlN表面处理及级配填充对覆铜板绝缘层性能的影响规律与机制研究[J]. 无机材料学报, 2021, 36(8): 847-855.

ZHANG Weiwei, LU Chen, YING Guobing, ZHANG Jianfeng, JIANG Wan. Effect and Mechanism of the Surface Treatment and Gradation Filling of AlN on the Performance of Insulation Layer of Copper Clad Laminate[J]. Journal of Inorganic Materials, 2021, 36(8): 847-855.

图/表 12

图1 (a)磷酸抗水解机理和(b)覆铜板制备流程示意图

Fig. 1 Schematic diagrams of (a) the anti-hydrolysis mechanism of phosphoric acid on AlN and (b) the preparation process of CCL

图2 AlN的(a~d)粒径分布曲线及(e~h)SEM照片

Fig. 2 (a-d) Particle size distribution curves and (e-h) SEM images of AlN with different particle sizes (a) 1 μm AlN; (b) 5 μm AlN; (c) 50 μm AlN; (d) 80 μm AlN; (e-h) SEM images of the AlN corresponding to (a-d)

图3 样品水解前后的XRD图谱

Fig. 3 XRD patterns of samples before and after hydrolysis (a) AlN; (b) AlN after treatment with phosphoric acid (pAlN)

图4 相同比例, 不同粒径pAlN填充的覆铜板的(a~d)截面和(e~h)表面的SEM照片

Fig. 4 SEM images of (a-d) cross-sections and (e-h) surfaces of CCLs filled with pAlN of same filling ratio but different sizes (a) pAlN-1 μm; (b) pAlN-5 μm; (c) pAlN-50 μm; (d) pAlN-80 μm; (e-h) SEM images corresponding to the surfaces of (a-d) CCLs

图5 填充不同比例pAlN覆铜板的截面SEM照片((a)无填料, (b)pAlN-50 μm-20%, (c) pAlN-50 μm-60%, (d) pAlN-50 μm60%-5 μm5%))、(e)EDS扫描选区(插图为元素分布)、(f)全元素扫描图和(g~j)分别对应 Al、N、Si、C元素分布

Fig. 5 SEM images of the cross-section of CCLs with different filling ratios of pAlN((a) no filler; (b) pAlN-50 μm-20%; (c) pAlN-50 μm-60%; (d) pAlN-50 μm60%-5 μm5%); (e) EDS scan selection area with the inset showing the element distribution; (f) the full element scan image; (g-j) corresponding element distributions of Al, N, Si, C

图6 不同填充方式覆铜板的导热机理示意图

Fig. 6 Heat conduction mechanism diagram of CCLs under different filling schemes (a) Without filler; (b) With single-size filler; (c) With graded filler

图7 (a)不同粒径、不同填充量的pAlN和(b)级配填充(pAlN-50 μm x%-5 μm y%, x=0~60, y=0~15, 下同)对覆铜板导热性能的影响

Fig. 7 (a) Effects of pAlN with different sizes, different filling amounts and (b) gradation filling (pAlN-50 μm x%-5 μm y%, x=0-60, y=0-15, same below) on the thermal conductivity of CCLs

表1 AlN磷酸抗水解处理对覆铜板的性能影响

Table 1 Effect of phosphoric acid treatment of AlN on the performance of CCLs

Treatment	Thermal conductivity/ (W·m^-1·K^-1)	Peel strength/ (N·mm^-1)	Dielectric constant	Dielectric loss/×10^-3	Bending strength/MPa	Water absorption/%
Without fillers	0.291	0.949	3.90	5.41	220	0.40
AlN-1 μm60%	0.390	0.380	5.10	9.10	208	0.76
pAlN-1 μm60%	0.610	0.980	4.55	9.04	282	0.47

图8 (a)不同粒径及不同填充量的pAlN和(b)级配填充对覆铜板剥离强度的影响

Fig. 8 (a) Effects of pAlN with different sizes, different filling amounts and (b) gradation filling on the peel strength of CCLs

图9 (a)不同粒径及不同填充量的pAlN和(b)级配填充对覆铜板弯曲强度的影响

Fig. 9 (a) Effects of pAlN with different sizes, different filling amounts and (b) gradation filling on the bending strength of CCLs

图10 不同粒径及不同填充量的pAlN对覆铜板介电常数(a)和介电损耗(b)的影响; 级配填充对覆铜板介电常数(c)和介电损耗(d)的影响

Fig. 10 Effect of pAlN with different size and filling amount on the dielectric constant (a) and dielectric loss (b) of the CCLs; Influence of gradation filling on the dielectric constant (c) and dielectric loss (d) of corresponding CCLs

图11 不同粒径、不同填充量的pAlN (a)和级配填充(b)对覆铜板吸水率的影响

Fig. 11 (a) Effect of pAlN with different size and different filling amount and (b) gradation filling on the water absorption of CCLs

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AlN表面处理及级配填充对覆铜板绝缘层性能的影响规律与机制研究

Effect and Mechanism of the Surface Treatment and Gradation Filling of AlN on the Performance of Insulation Layer of Copper Clad Laminate

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