Block copolymers with high Flory-Huggins interaction parameters for block copolymer lithography

Patent metadata

Field	Value
Publication number	US-9587136-B2
Application number	US-201314048766-A
Country	US
Kind code	B2
Filing date	Oct 8, 2013
Priority date	Oct 8, 2013
Publication date	Mar 7, 2017
Grant date	Mar 7, 2017

Abstract

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.

First claim

What is claimed is:

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 .

Assignees

• Wisconsin Alumni Res Found

Inventors

• Gopalan Padma
• Sweat Daniel Patrick
• Yu Xiang
• Kim Myungwoong

Classifications

• Y10T428/268

  Monolayer with structurally defined element · CPC title

• C08F297/02

  using a catalyst of the anionic type · CPC title

• G03F7/0002

  Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping · CPC title

• C08F12/22

  Oxygen · CPC title

• C09D153/00 Primary

  Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers · CPC title