超低介电常数苯并噁嗪/氰酸酯纳米多孔复合材料的制备与性能

As the continuing development of the Ultra Large-Scale Integrated Circuits(ULSI), a new generation of low dielectric constant material urgently needs to be developed. In this project, we propose to prepare a novel ultra-low dielectric constant benzoxazine/cyanate ester nano-porous composite material based on the regulation of polyhedral oligomeric silsesquioxane (POSS). Due to the rearrangement reaction of POSS, different molecular sizes benzoxazinyl-POSSes will be controllably synthesized through the salicylaldehyde route. The effect of the molecular size and the amount of benzoxazinyl-POSS and the ratio of two resins to the nano-porous structures and the organic-inorganic crosslinked structures will be researched to control the microstructures of composite material. The impact of the nano-porous structure to the dielectric properties of composite material will be clarified. The dual effects of the nano-porous structures and the triazine ring structure to the decrease of dielectric constant will be evaluated. And the intrinsical link between the organic-inorganic crosslinked structures and the thermal, mechanical and other properties of composite material will be revealed. Then the relationships between composition- microstructures - macroscopic properties will be built. Finally, the macroscopic properties of composite material can be controlled to get a high-performance benzoxazine/cyanate ester composite material with the dielectric constant less than 2.0.

针对超大规模集成电路的快速发展对超低介电常数材料迫切需求，在前期工作的基础上，申请人拟开展基于笼型倍半硅氧烷（POSS）调控制备的超低介电常数苯并噁嗪/氰酸酯纳米多孔复合材料的研究。利用POSS的重排反应，通过水杨醛路线，实现不同分子尺寸苯并噁嗪基POSS的可控合成；研究苯并噁嗪基POSS分子尺寸、加入量以及树脂配比对复合材料的纳米多孔结构和有机-无机交联结构的影响，实现对复合材料微观结构的控制；阐明纳米多孔结构与复合材料介电性能的影响，评价纳米多孔结构与三嗪环结构的双重作用对降低复合材料介电性能的效果，揭示复合材料的有机-无机交联结构与热、力学等性能的内在联系；综合建立复合材料组成-微观结构-宏观性能间的关系，对宏观性能进行有效调控，以制备得到介电常数小于2.0的高性能苯并噁嗪/氰酸酯复合材料，并为其走向应用提供技术基础。

针对超大规模集成电路的快速发展对超低介电常数材料迫切需求，开展了基于笼型倍半硅氧烷（POSS）调控制备的超低介电常数苯并噁嗪/氰酸酯纳米多孔复合材料的研究。采用了一种新颖的无溶剂、一步法合成得到了苯并噁嗪基POSS，实现了苯并噁嗪基POSS的可控合成，并优化了合成工艺条件。通过多种表征手段，实现了对复合材料的纳米多孔结构以及有机-无机交联结构的控制，阐明了纳米多孔结构与复合材料介电性能的影响，评价了纳米多孔结构与三嗪环结构的双重作用对降低复合材料介电性能的效果，揭示了复合材料的有机-无机交联结构与热、力学等性能的内在联系，综合建立了复合材料组成-微观结构-宏观性能间的关系，对宏观性能进行了有效调控。研究结果表明：苯并噁嗪基POSS具有好的分散性，通过苯并噁嗪与树脂基体进行原位聚合反应，将POSS以化学键合的方式连接到聚合物的主链上，形成了真正意义上的有机/无机纳米杂化材料。苯并噁嗪基POSS的引入能有效降低氰酸酯的固化温度，使其可以在较低温度下固化并得到具有高热力学性能的复合材料。同时，苯并噁嗪基POSS在复合材料中形成纳米多孔结构，有效降低了纳米复合材料的介电常数。通过苯并噁嗪基POSS与氰酸酯共聚生成有机-无机交联结构，热稳定性提高，但随着苯并噁嗪用量增大，聚合物化学结构中三嗪环的含量减少，生成亚胺碳酸酯结构，从而使热性能及介电性能变差。本项目成功制备得到了介电常数为2.0的高性能苯并噁嗪/氰酸酯复合材料，并为其走向应用提供技术基础。