Positive resist composition and method of pattern formation with the same

1. A positive resist composition comprising:

(A) a resin which comes to have an enhanced solubility in an alkaline developing solution by an action of an acid and which has no fluorine atom;

(B) a compound which generates an acid upon irradiation with actinic rays or a radiation;

(C) a fluorine-containing compound having a molecular weight of 1,000 to 100,000 and containing (y) a group which decomposes by an action of an alkaline developing solution to enhance a solubility in an alkaline developing solution and (z) a group which decomposes by an action of an acid; and

(F) a solvent,

wherein the amount of the fluorine-containing compound (C) in the composition is 0.1-30% by mass, based on all solid components of the resist composition, and

the total solids concentration in the positive resist composition is from 1.0 to 6.0% by mass.

2. The positive resist composition according to claim 1 , wherein the fluorine-containing compound (C) is a fluorine-containing compound further containing (x) an alkali-soluble group.

3. The positive resist composition according to claim 1 , wherein the group (y) which decomposes by an action of an alkaline developing solution to enhance a solubility in an alkaline developing solution has a lactone structure.

4. The positive resist composition according to claim 1 , wherein the resin (A) is a resin having a group having a lactone ring.

5. The positive resist composition according to claim 4 , wherein the group having a lactone ring is a group having a lactone structure represented by the following formula (LC1-4) or (LC1-5):

wherein in the above formula, Rb 2 represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group or an acid decomposable group; n 2 represents an integer of 0 to 4; when n 2 is 2 or more, a plurality of Rb 2 's may be same or different, and a plurality of Rb 2 's may be bonded to each other to form a ring.

6. The positive resist composition according to claim 1 , wherein the resin (A) has a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following formula (pI):

wherein in the formula (pI),

R 11 represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a sec-butyl group, and Z represents an atomic group necessary for forming a cycloalkyl group in cooperation with the carbon atom.

7. The positive resist composition according to claim 6 , wherein, in the formula (pI), the cycloalkyl group formed by Z and the carbon atom is a monocyclic cycloalkyl group.

8. The positive resist composition according to claim 1 , wherein the resin (A) has a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following formula (pII):

wherein in the formula (pII),

R 12 to R 14 each independently represents a linear or branched alkyl group or a cycloalkyl group, provided that at least one of R 12 to R 14 represents a cycloalkyl group.

9. The positive resist composition according to claim 1 ,

wherein the fluorine-containing compound (C) is an alkali-soluble compound containing an alkyl group having a fluorine atom and 1 to 4 carbon atoms, a cycloalkyl group having a fluorine atom or an aryl group having a fluorine atom.

10. The positive resist composition according to claim 1 ,

wherein the fluorine-containing compound (C) has an alcoholic hydroxyl group, and an alcohol moiety for the alcoholic hydroxyl group is a fluorinated alcohol.

11. The positive resist composition according to claim 1 ,

wherein the amount of the fluorine-containing compound (C) is from 0.1 to 10% by mass, based on all solid components of the resist composition.

12. The positive resist composition according to claim 1 ,

wherein the amount of the fluorine-containing compound (C) is from 0.1 to 5% by mass, based on all solid components of the resist composition.

13. The positive resist composition according to claim 1 , wherein when a film is provided, water has a receding contact angle of 65° or larger to the film.

14. The positive resist composition according to claim 1 , wherein when a film is provided, water has a receding contact angle of 70° or larger to the film.

15. The positive resist composition according to claim 1 ,

wherein the resin (A) contains a repeating unit having a polycyclic hydrocarbon group substituted by a hydroxyl group or a cyano group.

16. The positive resist composition according to claim 1 ,

wherein the resin (A) is a copolymer comprising at least three components: a (meth)acrylate repeating unit having a lactone ring; a (meth)acrylate repeating unit having an organic group having at least one of a hydroxyl group and a cyano group; and a (meth)acrylate repeating unit having an acid-decomposable group.

17. The positive resist composition according to claim 1 ,

wherein the compound (B) which generates an acid upon irradiation with actinic rays or a radiation is a compound represented by the following formula (ZI):

wherein in the formula (ZI),

R 201 , R 202 , and R 203 each independently represents an organic group, and X − represents a non-nucleophilic anion.

18. The positive resist composition according to claim 17 ,

wherein in the formula (ZI), all of R 201 , R 202 , and R 203 represent an aryl group.

19. The positive resist composition according to claim 18 ,

wherein the compound (B) which generates an acid upon irradiation with actinic rays or a radiation is a triphenylsulfonium salt compound having an alkyl or cycloalkyl residue which has not been substituted by fluorine in a cation part.

20. The positive resist composition according to claim 17 ,

wherein the non-nucleophilic anion X − is represented by the following formula:

Rc 1 —SO 3 −

wherein in the formula,

Rc 1 represents an alkyl and an aryl group, or group comprising a plurality of these groups connected to each other through a single bond, —O—, —CO 2 —, —S—, —SO 3 —, or —SO 2 N(Rd 1 )—, where Rd 1 represents a hydrogen atom or alkyl group.

21. The positive resist composition according to claim 17 ,

wherein the non-nucleophilic anion X- is represented by the following formula:

Rc 3 SO 2 —N − —SO 2 Rc 4

wherein in the formula,

Rc 3 and Rc 4 each independently represents an alkyl group, an aryl group, or group comprising a plurality of these groups connected to each other through a single bond, —O—, —CO 2 —, —S—, —SO 3 —, or —SO 2 N(Rd 1 )—, where Rd 1 represents a hydrogen atom or alkyl group, and Rc 3 and Rc 4 may be bonded to each other to form a ring.

22. The positive resist composition according to claim 1 ,

wherein the compound (B) which generates an acid upon irradiation with actinic rays or a radiation is a compound which generates an acid having a fluoroalkyl chain or a benzenesulfonic acid having a fluorine atom upon irradiation with actinic rays.

23. The positive resist composition according to claim 1 ,

wherein the solvent (F) is a mixed solvent comprising two or more solvents including propylene glycol monomethyl ether acetate.

24. The positive resist composition according to claim 1 , which further comprises at least one of a fluorochemical surfactant and a silicone surfactant.

25. A resist film which is formed by the resist composition claimed in claim 1 .

26. A method of pattern formation, which comprises:

forming a resist film from the positive resist composition claimed in claim 1 ;

exposing the resist film to light; and

developing the resist film.

27. The method of pattern formation according to claim 26 ,

wherein the resist film is exposed to light having a wavelength of from 1to 200 nm.

28. The method of pattern formation according to claim 26 ,

wherein the exposure is immersion exposure in which the resist film is exposed to light through an immersion liquid.

29. A positive resist composition comprising:

(A) a resin which comes to have an enhanced solubility in an alkaline developing solution by an action of an acid and which has no fluorine atom;

(B) a compound which generates an acid upon irradiation with actinic rays or a radiation;

(C) a fluorine-containing compound having a molecular weight of 1,000 to 100,000 and containing (y) a group which decomposes by an action of an alkaline developing solution to enhance a solubility in an alkaline developing solution and (z) a group which decomposes by an action of an acid; and

(F) a solvent,

wherein the amount of the fluorine-containing compound (C) in the composition is 0.1-30% by mass, based on all solid components of the resist composition, and

the solvent (F) is a mixed solvent comprising two or more solvents including propylene glycol monomethyl ether acetate.

30. The positive resist composition according to claim 29 , wherein the group (y) which decomposes by an action of an alkaline developing solution to enhance a solubility in an alkaline developing solution has a lactone structure.

31. The positive resist composition according to claim 30 , wherein the resin (A) has a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following formula (pI):

wherein in the formula (pI),

R 11 represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a sec-butyl group, and Z represents an atomic group necessary for forming a cycloalkyl group in cooperation with the carbon atom.

32. The positive resist composition according to claim 31 ,

wherein the amount of the fluorine-containing compound (C) is from 0.1 to 10% by mass, based on all solid components of the resist composition.

33. A method for filtrating a composition, comprising:

filtering the composition using a filter,

wherein the composition contains:

(A) a resin which comes to have an enhanced solubility in an alkaline developing solution by an action of an acid and which has no fluorine atom;

(B) a compound which generates an acid upon irradiation with actinic rays or a radiation;

(C) a fluorine-containing compound having a molecular weight of 1,000 to 100,000 and containing (y) a group which decomposes by an action of an alkaline developing solution to enhance a solubility in an alkaline developing solution and (z) a group which decomposes by an action of an acid; and

(F) a solvent,

wherein the amount of the fluorine-containing compound (C) in the composition is 0.1-30% by mass, based on all solid components of the resist composition, and

the total solids concentration in the composition is from 1.0 to 6.0% by mass.

34. A resist film on a substrate, the resist film being obtained from a resist composition,

wherein the resist composition contains:

(A) a resin which comes to have an enhanced solubility in an alkaline developing solution by an action of an acid and which has no fluorine atom;

(B) a compound which generates an acid upon irradiation with actinic rays or a radiation;

(C) a fluorine-containing compound having a molecular weight of 1,000 to 100,000 and containing (y) a group which decomposes by an action of an alkaline developing solution to enhance a solubility in an alkaline developing solution and (z) a group which decomposes by an action of an acid; and

(F) a solvent,

wherein the amount of the fluorine-containing compound (C) in the composition is 0.1-30% by mass, based on all solid components of the resist composition, and

the total solids concentration in the resist composition is from 1.0 to 6.0% by mass.