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The directed self-assembly (DSA) of block copolymers (BCPs) is a promising next-generation lithography technique for high-resolution patterning. However, achieving lithographically applicable BCP organization such as out-of-plane lamellae requires proper tuning of interfacial energies between the BCP domains and the substrate, which remains difficult to address effectively and efficiently with high-χ BCPs. Here, we present the successful generation of anisotropic wetting by plasma treatment on patterned spin-on-carbon (SOC) substrates and its application to the DSA of a high-χ Si-containing material, poly(1,1-dimethylsilacyclobutane)- block -polystyrene (PDMSB- b -PS), with a 9 nm half pitch. Exposing the SOC substrate to different plasma chemistries promotes the vertical alignment of the PDMSB- b -PS lamellae within the trenches. In particular, a patterned substrate treated with HBr/O 2 plasma gives both a neutral wetting at the bottom interface and a strong PS-affine wetting at the sidewalls of the SOC trenches to efficiently guide the vertical BCP lamellae. Furthermore, prolonged exposure to HBr/O 2 plasma enables an adjustment of the trench width and an increased density of BCP lines on the substrate. Experimental observations are in agreement with a free energy configurational model developed to describe the system. These advances, which could be easily implemented in industry, could contribute to the wider adoption of self-assembly techniques in microelectronics, and beyond to applications such as metasurfaces, surface-enhanced Raman spectroscopy, and sensing technologies.

In this work, we investigated the self-assembly of a lamellar block copolymer (BCP) under different wetting conditions. We explored the influence of the chemical composition of under-layers and top-coats on the thin film stability, self-assembly kinetics and BCP domain orientation. Three different chemistries were chosen for these surface affinity modifiers and their composition was tuned in order to provide either neutral wetting (i.e. an out-of-plane lamellar structure), or affine wetting conditions (i.e. an in-plane lamellar structure) with respect to a sub-10 nm PS- b -PDMSB lamellar system. Using such controlled wetting configurations, the competition between the dewetting of the BCP layer and the self-organization kinetics was explored. We also evaluated the spreading parameter of the BCP films with respect to the configurations of surface-energy modifiers and demonstrated that BCP layers are intrinsically unstable to dewetting in a neutral configuration. Finally, the dewetting mechanisms were evaluated with respect to the different wetting configurations and we clearly observed that the rigidity of the top-coat is a key factor to delay BCP film instability., (© 2023 IOP Publishing Ltd.)

Directed self-assembly of block copolymers (BCP) is a very attractive technique for the realization of functional nanostructures at high resolution. In this work, we developed full dry-etching strategies for BCP nanolithography using an 18 nm pitch lamellar silicon-containing block copolymer. Both an oxidizing Ar/O 2 plasma and a nonoxidizing H 2 /N 2 plasma are used to remove the topcoat material of our BCP stack and reveal the perpendicular lamellae. Under Ar/O 2 plasma, an interfacial layer stops the etch process at the topcoat/BCP interface, which provides an etch-stop but also requires an additional CF 4 -based breakthrough plasma for further etching. This interfacial layer is not present in H 2 /N 2 . Increasing the H 2 /N 2 ratio leads to more profound modifications of the silicon-containing lamellae, for which a chemistry in He/N 2 /O 2 rather than Ar/O 2 plasma produces a smoother and more regular lithographic mask. Finally, these features are successfully transferred into silicon, silicon-on-insulator, and silicon nitride substrates. This work highlights the performance of a silicon-containing block copolymer at 18 nm pitch to pattern relevant hard-mask materials for various applications, including microelectronics.