Spin-on zeolite films deposited from Silicalite-1 nanocrystal suspensions prepared by hydrothermal treatment of clear solutions have the required properties for insulating media in microelectronics. However, on the scale of the feature sizes in on-chip interconnects of a few tens of nanometers, their homogeneity is still insufficient. We discovered a way to overcome this problem by combining the advantages of the clear solution approach of Silicalite-1 synthesis with a sol-gel approach. A combination of tetraethyl orthosilicate and methyltrimethoxysilane silica sources was hydrolyzed and cocondensed in the presence of an aqueous tetraalkylammonium hydroxide template. The resulting suspension of nanoparticles of a few nanometers in size together with residual oligomeric silica species were spun onto support. The final zeolite-inspired low-/cfilms (ZLK) with respect to pore size and homogeneity satisfied all requirements and presented excellent hydrophobicity, stiffness, and dielectric constant. The size and content of initially formed nanoparticles and the spatial hindrance promoted by occluded tetraalkylammonium molecules were found to be crucial elements in the definition of the final pore network.
Eslava, S., Urrutia, J., Busaworv, A. N., Baklanov, M. R., Iacopi, F., Aldea, S., ... Kirschhock, C. E. A. (2008). Zeolite-inspired low-k dielectrics overcoming limitations of zeolite films. Journal of the American Chemical Society, 130(51), 17528-17536. https://doi.org/10.1021/ja8066572