Silicon (Si) on-chip metallization was carried out through surface functionalization and electroless deposition of copper (Cu). Surface functionalization of Si was performed by grafting an amine (NH₂)-terminated organosilane, 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (ETAS), as a nanoscaled bridge linker to adsorb catalytic polyvinylpyrrolidone-capped palladium nanoclusters (PVP-nPd) through complex reaction. The ETAS molecules bear three methoxy groups that can transform into the hydroxyl groups through hydrolysis and attach to the SiO₂/Si substrate by hydrogen bonding. Through rapid thermal annealing (RTA) treatment, the dehydration reaction occurred and led to the formation of the covalent bonding of siloxane (Si–O–Si) between ETAS and SiO₂/Si. The increase of the RTA temperature to 673 and 773 K caused the increase of the Si–O–Si bonding which improved the grafting orientation of ETAS as suggested by the molecular simulation. The adhesion strength of electrolessly deposited Cu film on SiO₂/Si is boosted to 4 MPa (673 K) and 5.6 MPa (773 K) which is 60–124% enhancement compared to the sample without the RTA treatment (2.5 MPa). This shows its high feasibility induced by the organosilane nanolayer as molecular adhesive for next-generation Si metallization.

中文翻译：

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胺基终止的有机硅氧烷单层作为用于硅金属化的粘合剂

芯片上的硅（Si）金属化是通过表面功能化和化学沉积铜（Cu）进行的。Si的表面官能化是通过接枝胺（NH ₂）封端的有机硅烷3- [2-（2-氨基乙基氨基）乙基氨基]丙基三甲氧基硅烷（ETAS）作为纳米级桥连接剂来吸附催化聚乙烯吡咯烷酮封端的钯纳米簇（PVP） -nPd）通过复杂的反应。ETAS分子带有三个甲氧基，可通过水解转变为羟基并通过氢键连接到SiO ₂ / Si衬底上。通过快速热退火（RTA）处理，发生了脱水反应，并导致ETAS和SiO ₂之间形成硅氧烷（Si–O–Si）共价键/ Si。分子模拟表明，RTA温度升高至673和773 K导致Si–O–Si键的增加，从而改善了ETAS的接枝方向。与未经RTA处理的样品（2.5 MPa）相比，化学沉积的Cu膜在SiO ₂ / Si上的附着强度提高到4 MPa（673 K）和5.6 MPa（773 K），提高了60–124％。这表明由有机硅烷纳米层作为下一代Si金属化的分子胶粘剂具有很高的可行性。