Simultaneous fabrication of line and dot dual nanopatterns using miktoarm block copolymer with photocleavable linker.

Block copolymers with various nanodomains, such as spheres, cylinders, and lamellae, have received attention for their applicability to nanolithography. However, those microdomains are determined by the volume fraction of one block. Meanwhile, nanopatterns with multiple shapes are required for the next-generation nanolithography. Although various methods have been reported to achieve dual nanopatterns, all the methods need sophisticated processes using E-beam. Here, we synthesized a miktoarm block copolymer capable of cleavage of one block by ultraviolet. Original cylindrical nanodomains of synthesized block copolymer were successfully transformed to lamellar nanodomains due to the change of molecular architecture by ultraviolet. We fabricated dual nanopatterns consisting of dots and lines at desired regions on a single substrate. We also prepared dual nanopatterns utilizing another phase transformation from spheres to cylinders in a block copolymer with higher interaction parameter. Since our concept has versatility to any block copolymer, it could be employed as next-generation nanolithography.

Reduction of Line Edge Roughness of Polystyrene-block-Poly(methyl methacrylate) Copolymer Nanopatterns By Introducing Hydrogen Bonding at the Junction Point of Two Block Chains.

To apply well-defined block copolymer nanopatterns to next-generation lithography or high-density storage devices, small line edge roughness (LER) of nanopatterns should be realized. Although polystyrene-block-poly(methyl methacrylate) copolymer (PS-b-PMMA) has been widely used to fabricate nanopatterns because of easy perpendicular orientation of the block copolymer nanodomains and effective removal of PMMA block by dry etching, the fabricated nanopatterns show poorer line edge roughness (LER) due to relatively small Flory-Huggins interaction parameter (χ) between PS and PMMA chains. Here, we synthesized PS-b-PMMA with urea (U) and N-(4-aminomethyl-benzyl)-4-hydroxymethyl-benzamide (BA) moieties at junction of PS and PMMA chains (PS-U-BA-PMMA) to improve the LER. The U-BA moieties serves as favorable interaction (hydrogen bonding) sites. The LER of PS line patterns obtained from PS-U-BA-PMMA was reduced ∼25% compared with that obtained from neat PS-b-PMMA without BA and U moieties. This is attributed to narrower interfacial width induced by hydrogen bonding between two blocks, which is confirmed by small-angle X-ray scattering. This result implies that the introduction of hydrogen bonding into block copolymer interfaces offers an opportunity to fabricate well-defined nanopatterns with improved LER by block copolymer self-assembly, which could be a promising alternative to next-generation extreme ultraviolet lithography.

Highly asymmetric lamellar nanopatterns via block copolymer blends capable of hydrogen bonding.

Highly asymmetric lamellar microdomains, such as those required for many lithographic line patterns, cannot be straightforwardly achieved by conventional block copolymer self-assembly. We present a conceptually new and versatile approach to produce highly asymmetric lamellar morphologies by the use of binary blends of block copolymers whose components are capable of hydrogen bonding. We first demonstrate our strategy in bulk systems and complement the experimental results observed by transmission electron microscopy and small-angle X-ray scattering with theoretical calculations based on strong stretching theory to suggest the generality of the strategy. To illustrate the impact on potential lithographic applications, we demonstrate that our strategy can be transferred to thin film morphologies. For this purpose, we used solvent vapor annealing to prepare thin films with vertically oriented asymmetric lamellar patterns that preserve the bulk morphological characteristics. Due to the highly asymmetric lamellar microdomains, the line width is reduced to sub-10 nm scale, while its periodicity is precisely tuned.