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A Top Coat with Solvent Annealing Enables Perpendicular Orientation of Sub‐10 nm Microdomains in Si‐Containing Block Copolymer Thin Films
Authors:Eunjin Kim  Wonjung Kim  Kwang Hee Lee  Caroline A. Ross  Jeong Gon Son
Affiliation:1. Photo‐Electronic Hybrids Research Center, Korea Institute of Science and Technology (KIST), Seoul, Korea;2. Department of Polymer Science and Engineering, Inha University, Incheon, Korea;3. Department of Mechanical Engineering, Sogang University, Seoul, Korea;4. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA
Abstract:Achieving sub‐10 nm high‐aspect‐ratio patterns from diblock copolymer self‐assembly requires both a high interaction parameter (χ, which is determined by the incompatibility between the two blocks) and a perpendicular orientation of microdomains. However, these two conditions are extremely difficult to achieve simultaneously because the blocks in a high‐χ copolymer typically have very different surface energies, favoring in‐plane microdomain orientations. A fully perpendicular orientation of a high‐χ block copolymer, poly(styrene‐block‐dimethylsiloxane) (PS‐b‐PDMS) is realized here using partially hydrolyzed polyvinyl alcohol (PVA) top coats with a solvent annealing process, despite the large surface energy differences between PS and PDMS. The PVA top coat on the block copolymer films under a solvent vapor atmosphere significantly reduces the interfacial energy difference between two blocks at the top surface and provides sufficient solvent concentration gradient in the through‐thickness direction and appropriate solvent evaporation rates within the film to promote a perpendicular microdomain orientation. The effects of interfacial energy differences and the swellability of PVA top coats controlled by the degree of hydrolysis on the orientation of micro­domains are examined. The thickness of the BCP film and top coats also affects the orientation of the BCP film.
Keywords:block copolymers  self‐assembly  perpendicular orientation  solvent annealing  top coats
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