Hydrolysis-Tolerant Hybrid Bonding in Ambient Atmosphere for 3D Integration

A. Shigetou, Tilo H. Yang, C. Kao
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Abstract

In this study, a heterogeneous bonding between organic and inorganic materials was realized at low temperature without vacuum atmosphere, by means of the vapor-assisted vacuum ultraviolet (VUV) surface modification method. In this method, an ultrathin bridge layer was created between the surfaces via the VUV irradiation in nitrogen atmosphere containing lower alcohol vapor. The radical species of H, OH, and CH sequentially enabled the initial surface cleaning, partial deoxidization of native oxide, and the formation of hydroxyl-terminated alkyl bridge with multidentate carboxylate on the inorganic material. Due to the dynamic competition of reversible hydrolysis of the multidentate carboxylate, the waterproof characteristic was expected to the bridge layer. The bridge layer was then bonded strongly to the modified organic material surface by hydrogen bond on the moment of contact at room temperature, which was followed by the dehydration condensation upon heating at 423.2 K around. Given polyether ether ketone (PEEK) and wiring metals as the typical materials in the fields of flexible electronics and structural materials, the evolution of chemical surface binding condition was analyzed to optimize the bridge formation. The bond interface showed cohesive fracture after the high humidity storage testing at 358.2 K and RH 85% for 1000 hours. Such the hybrid bonding with ultrathin bridge layer will be of the actual use in 3D flexible integration in near future.
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三维集成环境下耐水解杂化键
本研究采用蒸汽辅助真空紫外(VUV)表面改性方法,在低温无真空气氛下实现了有机与无机材料之间的非均相键合。该方法在含较低酒精蒸气的氮气气氛中,通过紫外辐射在表面之间形成超薄的桥接层。自由基H、OH和CH依次实现了初始的表面清洁、天然氧化物的部分脱氧以及与多齿羧酸盐在无机材料上形成端羟基烷基桥。由于多齿羧酸酯可逆水解的动态竞争,桥接层的防水特性被寄予了期望。在室温接触瞬间,桥层通过氢键与改性有机材料表面紧密结合,在423.2 K左右加热后发生脱水冷凝。针对聚醚醚酮(PEEK)和布线金属作为柔性电子和结构材料领域的典型材料,分析了化学表面结合条件的演变,以优化桥接结构。在358.2 K、85% RH条件下高湿保存1000 h后,粘结界面出现粘连断裂。这种具有超薄桥层的杂化键合将在不久的将来在三维柔性集成中得到实际应用。
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