A 3‐aminopropyltrimethoxysilane‐derived self‐assembled monolayer (NH2SAM) is investigated as a barrier against copper diffusion for application in back‐end‐of‐line (BEOL) technology. The essential characteristics studied include thermal stability to BEOL processing, inhibition of copper diffusion, and adhesion to both the underlying SiO2 dielectric substrate and the Cu over‐layer. Time‐of‐flight secondary ion mass spectrometry and X‐ray spectroscopy (XPS) analysis reveal that the copper over‐layer closes at 1–2‐nm thickness, comparable with the 1.3‐nm closure of state‐of‐the‐art Ta/TaN Cu diffusion barriers. That the NH2SAM remains intact upon Cu deposition and subsequent annealing is unambiguously revealed by energy‐filtered transmission electron microscopy supported by XPS. The SAM forms a well‐defined carbon‐rich interface with the Cu over‐layer and electron energy loss spectroscopy shows no evidence of Cu penetration into the SAM. Interestingly, the adhesion of the Cu/NH2SAM/SiO2 system increases with annealing temperature up to 7.2 J m−2 at 400 °C, comparable to Ta/TaN (7.5 J m−2 at room temperature). The corresponding fracture analysis shows that when failure does occur it is located at the Cu/SAM interface. Overall, these results demonstrate that NH2SAM is a suitable candidate for subnanometer‐scale diffusion barrier application in a selective coating for copper advanced interconnects.

The RC delay and power restrictions imposed by the interconnect system can contribute to poor circuit performance in an increasingly severe manner as dimensions shrink. Resistances are increasing faster than the scale factor of the technology and capacitance improvements are constrained by mechanical requirements of the assembled stack. Collectively, these cause a bottleneck in both local and global information transfer on a chip. Novel deposition methods and novel conductor materials are being explored as means to increase conductive cross sectional area. Molecular ordering is an opportunity to simultaneously deliver capacitance and mechanical strength. Despite these improvement paths, a more holistic approach to interconnect design is needed, where the application and micro architecture are more tolerant of RC scaling constraints.

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An alternative bottom-up Cu electroless deposition (ELD) method without other catalyst material activation is the focus of this paper. The process consists of reducing the Cu ions in a solution via standard reducing agents such as dimethylamine borane. The reaction pH and ionic strength values can be modulated to impart to the metallic Cu particle surface an opposite charge with respect to the deposition substrate functionalized by the 3-aminopropyltrimethoxysilane (APTS) self-assembled monolayer used as a diffusion barrier. At neutral pH, the negatively charged Cu particles are electrostatically attracted by the positively charged NH2 groups, and they can form strong interfacial complexes if the required activation energy budget is supplied. A design of the experiment is carried out to optimize the critical deposition parameters such as temperature, time, Cu ion concentration, and pH. The formed ELD Cu nuclei positioned preferentially on the APTS layer, showing a wetting behavior that is accentuated upon anneal, leading to a decrease in surface roughness that corresponds to an increase in film closure. The observed debonding energy of the ELD Cu/APTS surface is ca. 2.2J/normalm2 before anneal, while it reaches ca. 4.5 and 8J/normalm2 after a 10 min anneal under forming gas at 300 and 450°C , respectively.