【作者】 王家俊；

【导师】 益小苏；

【作者基本信息】 浙江大学 ， 高分子材料， 2001， 博士

【摘要】 现代信息产业中电子、微电子和光电子元件的高功率化、高密度化、高集成化与高运行速度，迫切需要新一代同时具有高热导、低介电常数、低介电损耗、热膨胀小、高绝缘等优异性能的基板材料、封装材料和绝缘介质材料。氮化铝具有很高的导热性，同时介电性能好、热膨胀系数小，是先进集成电路优异的候选材料。聚酰亚胺是目前聚合物中最耐高温、高强度的品种之一，它还具有低介电、高绝缘、热膨胀小等优点，在微电子行业被广泛用作层间介质、封装材料、印刷电路板等。聚酰亚胺/氮化铝复合材料结合了聚酰亚胺和氮化铝的各自优点，而且还具有聚合物基复合材料重量轻、易加工成各种复杂的形状、化学稳定性好和性能可调节等特点，应用于现代微电子领域前景良好。 本文首先研究了聚酰亚胺/氮化铝复合材料的制备方法，用原位聚合法和PMR工艺法分别制备了两大类聚酰亚胺/氮化铝复合材料，并用DSC、H-NMR、FTIR、SEM、TG等对单体、制备过程、最终复合材料进行了分析和表征。制备了不同氮化铝含量、不同偶联剂用量、原位聚合工艺的系列原位聚合法聚酰亚胺/氮化铝复合材料和不同氮化铝含量、不同球磨工艺和热压工艺、偶联剂的系列PMR聚酰亚胺/氮化铝复合材料。分析了PMR工艺法的制备条件，通过自制模具和边加热器，创造性地实现了在普通热压机上制备PMR聚酰亚胺/氮化铝复合材料。应用高能球磨混合和PMR工艺方法，成功制得氮化铝含量达80Wt％（体积含量达62vol.％）、致密的PMR聚酰亚胺/氮化铝复合材料。 复合材料的导热行为较复杂，描述粒子分散在基体中的复合材料的导热系数常用Maxwell方程，但粒子的形状、高含量时粒子的相互作用、特别是界面热阻的存在将严重影响复合材料的导热系数，使Maxwell方程出现很大的偏差，因此许多研究者提出了考虑不同因素的改进方程。但还没有人提出同时考虑上述诸多因素、适用面更广的复合材料导热系数方程。本文提出并验证了同时考虑粒子形状和界面热阻、适用全范围粒子含量的复合材料导热系数新改进方程。 对PMR聚酰亚胺/氮化铝复合材料的性能研究表明：高能球磨工艺主要通过使氮化铝粒子形状变化而影响复合材料的导热系数；热压成型工艺主要通过使 浙江大学博上论文PMR聚酚亚胺基体和复合材料的界面变化而影响复合材料的导热系数；偶联剂可以改善复合材料的界面从而提高导热系数；PMR聚酚亚胺／氮化铝复合材料的介电常数小门叶左右）、介电损耗小＊3．SX10”3）、热膨胀系数小，符合微电于材料的要求。 原位聚合法聚酚亚胺／氮化铝复合材料的正交试验研究表明：氮化铝含量和偶联剂用量对导热系数有显著影响：氮化铝含量对介电常数有高度显著影响；没有因素对介电损耗有显著影响。原位聚合法聚酚亚胺／氮化铝复合材料性能进一步研究表明：导热系数随氮化铝含量的增加而显著提高，规律基本符合Maxwell方程，但更符合新改进方程：复合材料的介电常数小、介电损耗小，并具有优异的电绝缘性。更多还原

【Abstract】 In the trend of high power, density, integrating, and speed of the electronic, microelectronic, and photoelectron components in modern information industry, it is an urgent demand of new generation microelectronic materials used in substrates, package materials, and interlayer dielectrics with high performance of high thermal conductivity, low dielectric constant and dielectric loss, low thermal expansion coefficient, and excellent insulation. A1N with its very high thermal conductivity, combined with excellent dielectric properties and , low thermal expansion coefficient, is especially useful as substrates in advanced IC. Polyimide which has unique properties of low dielectric constant and loss, low thermal expansion, and high insulation, is one kind of the high strength, thermal stable polymers, and is widely used as interlayer dielectrics, packaging materials, and circuit boards. Polyimide/AIN composite materials are expected to have an attractive combination of properties of polyimide and A1N, and have the advantages of light weight, ease of processing, high chemical stability, and adjustability of properties in polymer composites.The preparation of PI/A1N composite materials is discussed firstly in the dissertation. Two types of PI/A1N composite materials are prepared by in-situ polymerization and PMR method. A series of in-situ polymerized PI/A1N composite materials are prepared with varied in A1N fractions, coupling agents, and polymerizing conditions. A series of PMR PI/A1N composite materials are prepared with varied in A1N fractions, mechanical milling and moulding conditions, and coupling agents. DSC, H-NMR, FTIR, SEM, and TG are used in analysis of monomers, processing, and final composites. Based on the analysis of PMR technique, the PMR PI/A1N composite materials are moulded in normal moulding machine with modified in die and an additional heater. The fully dense PMR PI/A1N composite materials up to 80wt % (62vol %) A1N contents are prepared successfully by the combination of PMR technique and mechanical milling.The thermal conduct behavior of composites is complex. Maxwell equation isoften used in calculation of the thermal conductivity of composite materials composed by particles dispersed in a matrix. However, there are lager divergences by Maxwell equation when the shape of particles is not sphere, the fraction of particles is high, or boundary resistance exists in the interface of composites. Several researchers have modified Maxwell equation in the above effects respectively. A new modified equation, which considers all factors simultaneously and therefore more useful, is proposed and testified in this dissertation.The research on the properties of PMR PI/A1N composite materials reveals: the thermal conductivity is varied by the mechanical milling with the change in particle shape, and by the compress moulding with the change in polyimide matrix and composite interface; coupling agents can increase the thermal conductivity by modifying interface; PMR PI/A1N composite materials is low dielectric constant (about 2~4), low dielectric loss (<3.5xlO?, and low thermal expansion coefficient.The research on the properties of the in-situ PI/A1N composite materials reveals: the thermal conductivity is notably affected by the A1N fractions and coupling agent contents, the dielectric constant is high notably affected by the A1N fractions. The properties of the in-situ PI/A1N composite materials are: high thermal conductivity (increased with the A1N fraction), low dielectric constant, low dielectric loss and excellent insulation.更多还原