【摘要】 在半导体元器件的制造成本中，封装材料成本是仅次于硅晶片的重要开支，超过了引线框架和光刻胶所占的成本比例。先进封装向着高密度集成、高功率负载、微型化发展，封装结构变得更加复杂，对封装材料提出了更高的要求。环氧胶粘剂收缩率小、耐热性好、耐紫外老化、与锡铅焊料相比环境友好，是使用最广泛的一类封装材料。但其存在升温热膨胀系数高、固有的脆性和易开裂问题，影响封装器件的结构稳定性和服役可靠性，如何改善环氧胶粘剂的脆性和热膨胀性，提升其综合性能成为近年的研究热点。在环氧胶粘剂中引入纳米粒子和橡胶可以改善其脆性和热膨胀性。纳米粒子的刚性增强效应可极大提升环氧胶粘剂的强度和玻璃化转变温度，橡胶增韧环氧胶粘剂可显著改善其韧性，但会损失一定的强度和热机械性能。纳米粒子和橡胶的单一改性不能满足先进封装对环氧胶粘剂材料力学性能的苛刻要求，二者的复合改性可同时兼顾韧性和强度且不影响其他所需性能。通过刚性纳米粒子的表面功能化改性以及橡胶的末端结构设计改善改性物质与环氧基体的界面结合强度、促进改性物质在基体中的均匀分散是提升胶粘剂综合力学性能的关键。此外，环氧胶粘剂中刚性纳米粒子的存在降低了体系中自由体积所占的比例，以及刚性纳米粒子的紧密结合作用共同抑制了聚合物链的热膨胀；橡胶改善了胶粘剂的韧性，使得体系的热应力可以更好地消散，膨胀的驱动力也随之减小。环氧胶粘剂的配方复杂，结合机器学习的多尺度建模高通量计算，对其结构与力学性能关系进行模拟预测，可极大缩短先进环氧胶粘剂的研发周期。本文综述了近年来新型碳纳米粒子和橡胶改善环氧胶粘剂脆性和热膨胀性的研究进展，分析了环氧胶粘剂中添加刚性纳米粒子和橡胶带来的结构变化以及相应的改性机理，其中改性物质的均匀分散以及与环氧基体的界面结合强度是影响力学性能的关键因素，结合机器学习对环氧胶粘剂的微观结构与力学性能进行模拟预测，对推进先进环氧胶粘剂的发展具有重要意义。更多还原

【Abstract】 In the manufacturing cost of semiconductor components, the spending of packaging materials are second only to silicon wafers, and morethan the cost of lead frame and photoresist. The effects of adhesive materials are the major facts on the packaging functionality. Epoxy adhesives are widely used in electronics assembly and packaging. They combine numerous desirable properties including low shrinkage, thermal stability, anti-UV properties and more environmentally friendly than lead-containing solder. Advanced packaging is developing towards high-density integration, high-power load and miniaturization, and more complicated packaging structures, which meet the needs for adhesives with more excellent performances. Epoxies may undermine the stability and reliability of packaged devices, because of high thermal expansion coefficient,inherent brittleness and easy cracking. How to improve the brittleness and thermal expansion of epoxy adhesives, to achieve comprehensive properties become a research hotspot in recent years． Through the additives of novel carbon nanoparticles and rubber, the brittleness and thermal expansion of epoxy adhesives can be altered and tailored for specific applications. Due to the rigidity-enhancing effect of nanoparticles, the strength and glass transition temperature of epoxy adhesive can be greatly improved;the toughness of epoxy adhesive can be significantly modified by rubber, but it may lose some strength and thermomechanical properties. Only rigid nanoparticles or rubber modification could not meet the stringent requirements of advanced packaging on mechanical properties of epoxy adhesives. In recent years, the effects of common impact modifiers rigid nanoparticles and liquid rubber on the mechanical properties of filled epoxy adhesives have attracted considerable attention, the composites of which were endowed with better properties of toughness and strength without weakening other performances. In addition, the ratio of free volume in the adhesive reduced by the interaction of rigid nanoparticles and epoxy resins, and the thermal expansion of polymer chain restrained by the tight binding of nanoparticles, both of which could markedly decrease the thermal expansion coefficient of epoxy adhesive. For epoxy/rubber nanocomposite adhesive system, because of the toughening of epoxy resin with rubber, is able to dissipate stresses and dampen the driving force of expansion. The interfacial bonding strength between the modified material and epoxy matrix can be improved through the surface functional modification of rigid nanoparticles and the design of the terminal structure of rubber, and promoting the uniform dispersion of the modified substance in the matrix is the key to promote the improvement of mechanical properties. The formulation of epoxy adhesive is intricate, combined with multi-scale modeling and high-throughput calculation of machine learning, the relationship between its structure and mechanical properties can be simulated and predicted, which will greatly shorten the research and development cycle of advanced epoxy adhesives． The recent developments for the improvement of the brittleness and thermal expansion of epoxy adhesives with the novel carbon nanoparticles and rubber were reviewed in this paper. The structural changes and corresponding modification mechanism caused by the addition of rigid nanoparticles and rubber in epoxy adhesive were investigated. Among them, the uniform dispersion of modified materials and the interfacial bonding strength with epoxy matrix were the key factors affecting the mechanical properties. To simulate the microstructure and predict mechanical properties of epoxy adhesives by the machine learning is of great significance for the development of advanced epoxy adhesives.更多还原