Polymer compound, resist material and pattern formation method

1. A polymer compound comprising a first unit represented by a general formula of the following Chemical Formula 1 and a second unit represented by a general formula of the following Chemical Formula 2 and having a weight-average molecular weight not less than 1,000 and not more than 500,000:

wherein R 1 , R 2 and R 3 are the same or different and are a hydrogen atom, a fluorine atom, or a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20; R 4 is a straight-chain alkylene group or a branched or cyclic alkylene group with a carbon number not less than 0 and not more than 20; R 5 and R 6 are the same or different and are a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid; R 7 is a methylene group, an oxygen atom, a sulfur atom or —SO 2 —; R 8 , R 9 , R 10 and R 11 are the same or different and are a hydrogen atom, a fluorine atom, a hydroxyl group, —OR 13 , —CO 2 R 13 , —R 12 —OR 13 or —R 12 —CO 2 R 13 , at least one of R 8 , R 9 , R 10 and R 11 including —OR 13 , —CO 2 R 13 , —R 12 —OR 13 or —R 12 —CO 2 R 13 (wherein R 12 is a straight-chain alkylene group, a branched or cyclic alkylene group or a fluoridated alkylene group with a carbon number not less than 1 and not more than 20 and R 13 is a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid); 0<a<1; 0<b<1; and c is 0 or 1, and

wherein R 3 of said first unit is a trifluoromethyl group.

2. The polymer compound of claim 1 , further comprising a third unit represented by a general formula of the following Chemical Formula 3:

wherein R 16 , R 17 and R 18 are the same or different and are a hydrogen atom, a fluorine atom, or a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20; R 9 is a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid; and 0<c<1.

3. The polymer compound of claim 1 ,

wherein said protecting group released by an acid is an acetal group.

4. A resist material comprising a base polymer containing a polymer compound including a first unit represented by a general formula of the following Chemical Formula 4 and a second unit represented by a general formula of the following Chemical Formula 5:

wherein R 1 , R 2 and R 3 are the same or different and are a hydrogen atom, a fluorine atom, or a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20; R 4 is a straight-chain alkylene group or a branched or cyclic alkylene group with a carbon number not less than 0 and not more than 20; R 5 and R 6 are the same or different and are a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid; R 7 is a methylene group, an oxygen atom, a sulfur atom or —SO 2 —; R 8 , R 9 , R 10 and R 11 are the same or different and are a hydrogen atom, a fluorine atom, a hydroxyl group, —OR 13 , —CO 2 R 13 , —R 12 —OR 13 or —R 12 —CO 2 R 13 , at least one of R 8 , R 9 , R 10 and R 11 including —OR 13 , —CO 2 R 13 , —R 12 —OR 13 or —R 12 —CO 2 R 13 (wherein R 12 is a straight-chain alkylene group, a branched or cyclic alkylene group or a fluoridated alkylene group with a carbon number not less than 1 and not more than 20 and R 13 is a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid); 0<a<1; 0<b<1; and c is 0 or 1, and

wherein R 3 of said first unit is a trifluoromethyl group.

5. The resist material of claim 4 , further comprising an acid generator for generating an acid through irradiation with light.

6. The resist material of claim 4 ,

wherein said second unit is represented by the following Chemical Formula 6:

wherein R 13 is a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid; R 14 and R 15 are trifluoromethyl groups; and 0<b<1.

7. The resist material of claim 4 , further comprising a third unit represented by a general formula of the following Chemical Formula 7:

wherein R 16 , R 17 and R 18 are the same or different and are a hydrogen atom, a fluorine atom, or a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20; R 19 is a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid; and 0<c<1.

8. The resist material of claim 7 ,

wherein R 18 of said third unit is a trifluoromethyl group.

9. The resist material of claim 4 ,

wherein said protecting group released by an acid is an acetal group.

10. The resist material of claim 9 ,

wherein said acetal group is an alkoxyethyl group or an alkoxymethyl group.

11. The resist material of claim 10 ,

wherein said alkoxyethyl group is an adamantyloxyethyl group, a t-butyloxyethyl group, an ethoxyethyl group or a methoxyethyl group, and

said alkoxymethyl group is an adamantyloxymethyl group, a t-butyloxymethyl group, an ethoxymethyl group or a methoxymethyl group.

12. A pattern formation method comprising the steps of:

forming a resist film containing a base polymer including a polymer compound having a first unit represented by a general formula of the following Chemical Formula 8 and a second unit represented by a general formula of the following Chemical Formula 9;

irradiating selectively said resist film with exposing light of a wavelength not shorter than a 100 nm band and not longer than a 300 nm band or not shorter than a 1 nm band and not longer than a 30 nm band or electron beams; and

developing said resist film after the pattern exposure:

wherein R 1 , R 2 and R 3 are the same or different and are a hydrogen atom, a fluorine atom, or a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20; R 4 is a straight-chain alkylene group or a branched or cyclic alkylene group with a carbon number not less than 0 and not more than 20; R 5 and R 6 are the same or different and are a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid; R 7 is a methylene group, an oxygen atom, a sulfur atom or —SO 2 —; R 8 , R 9 , R 10 and R 11 are the same or different and are a hydrogen atom, a fluorine atom, a hydroxyl group, —OR 13 , —CO 2 R 13 , —R 12 —OR 13 or —R 12 —CO 2 R 13 , at least one of R 8 , R 9 , R 10 and R 11 including —OR 13 , —CO 2 R 13 , —R 12 —OR 13 or —R 12 —CO 2 R 13 (wherein R 12 is a straight-chain alkylene group, a branched or cyclic alkylene group or a fluoridated alkylene group with a carbon number not less than 1 and not more than 20 and R 13 is a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid); 0<a<1; 0<b<1; and c is 0 or 1, and

wherein R 3 of said first unit is a trifluoromethyl group.

13. The pattern formation method of claim 12 ,

wherein said resist material further includes an acid generator for generating an acid through irradiation with light.

14. The pattern formation method of claim 12 ,

wherein said resist material further includes a dissolution inhibitor for inhibiting dissolution of said base polymer.

15. The pattern formation method of claim 12 ,

wherein said second unit is represented by the following Chemical Formula 10:

wherein R 13 is a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid; R 14 and R 15 are trifluoromethyl groups; and 0<b<1.

16. The pattern formation method of claim 12 ,

wherein said polymer compound further includes a third unit represented by a general formula of the following Chemical Formula 11:

wherein R 16 , R 17 and R 18 are the same or different and are a hydrogen atom, a fluorine atom, or a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20; R 19 is a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid; and 0<c<1.

17. The pattern formation method of claim 12 ,

wherein said protecting group released by an acid is an acetal group.

18. The pattern formation method of claim 12 ,

wherein said exposing light is KrF laser, ArF laser, F 2 laser, Kr 2 laser, KrAr laser, Ar 2 laser or soft X-rays.

19. A pattern formation method comprising the steps of:

forming a resist film containing a base polymer including a polymer compound having a first unit represented by a general formula of the following Chemical Formula 12 and a second unit represented by a general formula of the following Chemical Formula 13;

supplying a liquid onto said resist film;

irradiating selectively said resist film, on which said liquid is provided, with exposing light of a wavelength not shorter than a 100 nm band and not longer than a 300 nm band or not shorter than a 1 nm band and not longer than a 30 nm band or electron beams; and

developing said resist film after the pattern exposure:

wherein R 1 , R 2 and R 3 are the same or different and are a hydrogen atom, a fluorine atom, or a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20; R 4 is a straight-chain alkylene group or a branched or cyclic alkylene group with a carbon number not less than 0 and not more than 20; R 5 and R 6 are the same or different and are a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid; R 7 is a methylene group, an oxygen atom, a sulfur atom or —SO 2 —; R 8 , R 9 , R 10 and R 11 are the same or different and are a hydrogen atom, a fluorine atom, a hydroxyl group, —OR 13 , —CO 2 R 13 , —R 12 —OR 13 or —R 12 —CO 2 R 13 , at least one of R 8 , R 9 , R 10 and R 11 including —OR 13 , —CO 2 R 13 , —R 12 —OR 13 or —R 12 —CO 2 R 13 (wherein R 12 is a straight-chain alkylene group, a branched or cyclic alkylene group or a fluoridated alkylene group with a carbon number not less than 1 and not more than 20 and R 13 is a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid); 0<a<1; 0<b<1; and c is 0 or 1, and

wherein R 3 of said first unit is a trifluoromethyl group.

20. The pattern formation method of claim 19 ,

wherein said resist material further includes an acid generator for generating an acid through irradiation with light.

21. The pattern formation method of claim 19 ,

wherein said resist material further includes a dissolution inhibitor for inhibiting dissolution of said base polymer.

22. The pattern formation method of claim 19 ,

wherein said second unit is represented by the following Chemical Formula 14:

wherein R 13 is a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid; R 14 and R 15 are trifluoromethyl groups; and 0<b<1.

23. The pattern formation method of claim 19 ,

wherein said polymer compound further includes a third unit represented by a general formula of the following Chemical Formula 15:

wherein R 16 , R 17 and R 18 are the same or different and are a hydrogen atom, a fluorine atom, or a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20; R 19 is a hydrogen atom, a straight-chain alkyl group, a branched or cyclic alkyl group or a fluoridated alkyl group with a carbon number not less than 1 and not more than 20, or a protecting group released by an acid; and 0<c<1.

24. The pattern formation method of claim 19 ,

wherein said protecting group released by an acid is an acetal group.

25. The pattern formation method of claim 19 ,

wherein said exposing light is KrF laser, ArF laser, F 2 laser, Kr 2 laser, KrAr laser, Ar 2 laser or soft X-rays.