In this study, a series of perpendicular lamellae-forming poly(polyhedral oligomeric silsesquioxane methacrylate-block-2,2,2-trifluoroethyl methacrylate)s (PMAPOSS-b-PTFEMAs) was developed based on the bottom-up concept of creating a simple yet effective material by tailoring the chemical properties and molecular composition of the material. The use of silicon (Si)-containing hybrid high-χ block copolymers (BCPs) provides easy access to sub-10 nm feature sizes. However, as the surface free energies (SFEs) of Si-containing polymers are typically vastly lower than organic polymers, this tends to result in the selective segregation of the inorganic block onto the air interface and increased difficulty in controlling the BCP orientation in thin films. Therefore, by balancing the SFEs between the organic and inorganic blocks through the use of poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) on the organic block, a polymer with an SFE similar to Si-containing polymers, orientation control of the BCP domains in thin films becomes much simpler. Herein, perpendicularly oriented BCP thin films with a χ value of 0.45 were fabricated using simple spin-coating and thermal annealing processes under ambient conditions. The thin films displayed a minimum domain size of L = 11 nm, as observed via atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Furthermore, directed self-assembly (DSA) of the BCP on a topographically prepatterned substrate using the grapho-epitaxy method was used to successfully obtain perpendicularly oriented lamellae with a half pitch size of ca. 8 nm.

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Abstract. A contact hole shrink process using directed self-assembly lithography (DSAL) for sub-30 nm contact hole patterning is reported on. DSAL using graphoepitaxy and poly (styrene-block-methyl methacrylate) (PS-b-PMMA) a block copolymer (BCP) was demonstrated and characteristics of our process are spin-on-carbon prepattern and wet development. Feasibility of DSAL for semiconductor device manufacturing was investigated in terms of DSAL process window. Wet development process was optimized first; then critical dimension (CD) tolerance of prepattern was evaluated from three different aspects, which are DSA hole CD, contact edge roughness (CER), and hole open yield. Within 70 þ ∕ − 5 nm hole prepattern CD, 99.3% hole open yield was obtained and CD tolerance was 10 nm. Matching between polymer size and prepattern size is critical, because thick PS residual layer appears at the hole bottom when the prepattern holes are too small or too large and results in missing holes after pattern transfer. We verified the DSAL process on a 300-mm wafer at target prepattern CD and succeeded in patterning sub-30 nm holes on center, middle, and edge of wafer. Average prepattern CD of 72 nm could be shrunk uniformly to DSA hole pattern of 28.5 nm. By the DSAL process, CD uniformity was greatly improved from 7.6 to 1.4 nm, and CER was also improved from 3.9 to 0.73 nm. Those values represent typical DSAL rectification characteristics and are significant for semiconductor manufacturing. It is clearly demonstrated that the contact hole shrink using DSAL is a promising patterning method for next-generation lithography.

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