Block copolymers with high Flory-Huggins interaction parameters for block copolymer lithography
Block copolymers for use in block copolymer lithography, self-assembled films of the block copolymers and methods for polymerizing the block copolymers are provided. The block copolymers are characterized by high Flory-Huggins interaction parameters (χ). The block copolymers can be polymerized from protected hydroxystyrene monomers or from tert-butyl styrene and 2-vinylpyridine monomers.
1. A block copolymer comprising a first polymer block comprising polymerized hydroxystyrene and a second polymer block, the block copolymer having a Flory-Huggins interaction parameter of at least 0.15, wherein the polymer of the second polymer block is characterized in that it will degrade in a hydrochloric acid solution having a hydrochloric acid concentration that is sufficiently high to deprotect poly(4-tert-butoxystyrene) and convert it into poly(4-hydroxystyrene).
2. The block copolymer of claim 1 , having a Flory-Huggins interaction parameter of at least 1.
3. The block copolymer of claim 1 , wherein the polymer of the second polymer block has a Hildebrand solubility parameter of no greater than (16 J/cm 3 ) 1/2 ).
4. The block copolymer of claim 1 , wherein the second polymer block is polydimethylsiloxane.
5. The block copolymer of claim 1 , wherein the second polymer block comprises a substituted polystyrene.
6. The block copolymer of claim 1 , wherein the polymer of the second polymer block comprises a methacrylate polymer.
7. The block copolymer of claim 6 , wherein the methacrylate polymer is poly(isopropyl methacrylate).
8. A polymer film comprising the block copolymer of claim 1 self-assembled into a plurality of domains, wherein the domains have at least one spatial dimension that is no greater than 20 nm.
9. The block copolymer of claim 1 , wherein the mass ratio of the hydroxystyrene polymer block to the second polymer block is in the range from 20:1 to 1:1.
10. The polymer film of claim 8 , wherein the hydroxystyrene is 3-hydroxystyrene or 2-hydroxystyrene.
11. The polymer film of claim 10 having a Flory-Huggins interaction parameter of at least 1.
12. The polymer film of claim 10 , wherein the second polymer block is polydimethylsiloxane.
13. The polymer film of claim 10 , wherein the second polymer block comprises a substituted polystyrene.
14. The polymer film of claim 10 , wherein the polymer of the second polymer block comprises a methacrylate polymer.
15. A block copolymer comprising a first polymer block comprising polymerized hydroxystyrene and a second polymer block selected from poly(3,5-di t-butyl substituted styrene) and poly(4-trimethylsilylstyrene, the block copolymer having a Flory-Huggins interaction parameter of at least 0.15.
16. A block copolymer comprising a first polymer block comprising polymerized hydroxystyrene and a second polymer block comprising poly(methacrylisobutyl polyhedral oligomeric silsesquioxane), the block copolymer having a Flory-Huggins interaction parameter of at least 0.15.
17. A block copolymer comprising a first polymer block comprising polymerized hydroxystyrene and a second polymer block comprising poly(4-t-butylcyclohexyl methacrylate) or poly(4-t-butyl phenyl methacrylate).
18. A block copolymer comprising a first polymer block comprising polymerized 3-hydroxystyrene and a second polymer block, the block copolymer having a Flory-Huggins interaction parameter of at least 0.15.
19. The block copolymer of claim 18 , wherein the second polymer block is polyisoprene.
20. The block copolymer of claim 18 having a Flory-Huggins interaction parameter of at least 1.
21. The block copolymer of claim 18 , wherein the second polymer block is polydimethylsiloxane.
22. The block copolymer of claim 18 , wherein the second polymer block comprises a substituted polystyrene.
23. The block copolymer of claim 18 , wherein the polymer of the second polymer block comprises a methacrylate polymer.
24. The block copolymer of claim 18 , wherein the polymer of the second polymer block has a Hildebrand solubility parameter of no greater than 16 (J/cm 3 ) 1/2 .
25. A block copolymer comprising a first polymer block comprising polymerized 2-hydroxystyrene and a second polymer block, the block copolymer having a Flory-Huggins interaction parameter of at least 0.15.
26. The block copolymer of claim 25 having a Flory-Huggins interaction parameter of at least 1.
27. The block copolymer of claim 25 , wherein the second polymer block is polydimethylsiloxane.
28. The block copolymer of claim 25 , wherein the second polymer block comprises a substituted polystyrene.
29. The block copolymer of claim 25 , wherein the second polymer block is polyisoprene.
30. The block copolymer of claim 25 , wherein the polymer of the second polymer block comprises a methacrylate polymer.
31. The block copolymer of claim 25 , wherein the polymer of the second polymer block has a Hildebrand solubility parameter of no greater than 16 (J/cm 3 ) 1/2 .