Positive resist composition and pattern formation method using the same

1. A positive resist composition comprising:

(A) a resin comprising a repeating unit represented by the following formula (Ia) and a repeating unit represented by the following formula (Ib), which increases the solubility in an alkali developing solution by the action of an acid:

(B) a compound represented by the following formula (I), (II) or (III):

wherein Ra 1 each independently represents a hydrogen atom or an alkyl group, and A each independently represents a linkage group,

Ra 11 represents an alkyl group containing 1 to 4 carbon atoms, Z represents a group of atoms forming an alicyclic hydrocarbon group together with the carbon atom adjacent to Ra 11 ,

Ra 12 to Ra 14 each independently represents a hydrocarbon group, with the proviso that at least one among Ra 12 , Ra 13 and Ra 14 represents an alicyclic hydrocarbon group:

wherein R 1 to R 3 , which may be the same or different, each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an alkoxy group,

R 4 and R 5 , which may be the same or different, each represent a hydrogen atom, a cyano group, an alkyl group, an aryl group or an alkoxy group,

Y 1 and Y 2 , which may be the same or different, each represents an alkyl group, an aryl group, an aralkyl group or a hetero atom-containing aromatic group,

n represents an integer of 1 to 4, and with the proviso that when n is 2 or more, a plurality of R 1 s may be the same or different and a plurality of R 2 s may also be the same or different, any two or more among R 1 to R 3 , R 4 , R 5 , Y 1 and Y 2 may be bonded with each other to form a cyclic structure,

two or more of structures represented by formula (I) or (II) may be present by being bonded to each other via one or more of a linkage group at any sites of R 1 s, R 2 s, R 3 S, R 4 s, R 5 s, Y 1 s and Y 2 s,

X − represents a non-nucleophilic anion:

wherein Ar represents an aryl group or a hetero atom-containing aromatic group,

R 6 represents a hydrogen atom, a cyano group, an alkyl group or an aryl group,

R 7 represents an alkyl group or an aryl group,

Y 3 and Y 4 , which may be the same or different, each represents an alkyl group, an aryl group, an aralkyl group or a hetero atom-containing aromatic group, or Y 3 and Y 4 may be bonded with each other to form a ring,

Ar and at least either Y 3 or Y 4 may be bonded with each other to form a ring,

Ar and R 6 may be bonded with each other to form a ring, or two or more of structures represented by formula (III) may be present by being bonded to each other via one or more of a linkage group at Ar sites, either R 6 or R 7 sites, or either Y 3 or Y 4 sites, and

X − represents a non-nucleophilic anion, and

wherein the content of the compound represented by the formula (I) or (II) is from 0.1 to 20% by weight based on the content of the solids in the composition.

2. The composition according to claim 1 , wherein the compound (B) represented by formula (III) is a compound represented by the following formula (IV):

wherein R 8 to R 12 , which may be the same or different, each represents a hydrogen atom, a nitro group, a halogen atom, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an aryl group or an acylamino group, with the proviso that at least two of R 8 to R 12 may be bonded with each other to form a ring structure,

R 13 represents a hydrogen atom, a cyano group, an alkyl group or an aryl group,

R 14 represents an alkyl group or an aryl group,

Y 5 and Y 6 , which may be the same or different, each represents an alkyl group, an aryl group, an aralkyl group or a hetero atom-containing aromatic group, or Y 5 and Y 6 may be bonded with each other to form a ring, or at least one of R 8 to R 12 and at least either Y 5 or Y 6 may be bonded with each other to form a ring, or at least one of R 8 to R 12 may be bonded with R 13 to form a ring,

two or more of structures represented by formula (IV) may be present by being bonded to each other via one or more of a linkage group at any sites of R 8 s to R 14 s or at either Y 5 sites or Y 6 sites, and

X − represents a non-nucleophilic anion.

3. The composition according to claim 1 , further comprising (C) a fluorine-based and/or silicon-based surfactant.

4. The composition according to claim 1 , further comprising (D) an organic basic compound.

5. The composition according to claim 1 , wherein the component (B) includes: at least one of the compounds represented by the formulae (I) and (II); and the compound represented by the formula (III).

6. The composition according to claim 1 , wherein the amount of the repeating unit represented by the formula (Ia) and the repeating unit represented by the formula (Ib) is from 30 to 70 mole % based on the component (a).

7. A method for forming a pattern, which comprises forming a resist film comprising the composition described in claim 1 , exposing the resist film upon irradiation with the actinic rays or a radiation, and subsequently developing the resist film.

8. The method for forming a pattern according to claim 7 , wherein the compound (B) represented by formula (III) is a compound represented by the following formula (IV):

wherein R 8 to R 12 , which may be the same or different, each represents a hydrogen atom, a nitro group, a halogen atom, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an aryl group or an acylamino group, with the proviso that at least two of R 8 to R 12 may be bonded with each other to form a ring structure,

R 13 represents a hydrogen atom, a cyano group, an alkyl group or an aryl group,

R 14 represents an alkyl group or an aryl group,

Y 5 and Y 6 , which may be the same or different, each represents an alkyl group, an aryl group, an aralkyl group or a hetero atom-containing aromatic group, or Y 5 and Y 6 may be bonded with each other to form a ring, or at least one of R 8 to R 12 and at least either Y 5 or Y 6 may be bonded with each other to form a ring, or at least one of R 8 to R 12 may be bonded with R 13 to form a ring,

two or more of structures represented by formula (IV) may be present by being bonded to each other via one or more of a linkage group at any sites of R 8 s to R 14 s or at either Y 5 sites or Y 6 sites, and

X − represents a non-nucleophilic anion.

9. The method for forming a pattern according to claim 7 , wherein the composition further comprises (C) a fluorine-based and/or silicon-based surfactant.

10. The method for forming a pattern according to claim 7 , wherein the composition further comprises (D) an organic basic compound.

11. The method for forming a pattern according to claim 7 , wherein the component (B) includes: at least one of the compounds represented by the formulae (I) and (II); and the compound represented by the formula (III).

12. The method for forming a pattern according to claim 7 , wherein the amount of the repeating unit represented by the formula (Ia) and the repeating unit represented by the formula (Ib) is from 30 to 70 mole % based on the component (a).

13. A positive resist composition comprising:

(A) a resin comprising a repeating unit represented by the following formula (Ia) and a repeating unit represented by the following formula (Ib), which increases the solubility in an alkali developing solution by the action of an acid:

(B) a compound represented by the following formula (I), (II) or (III):

wherein Ra 1 each independently represents a hydrogen atom or an alkyl group, and A each independently represents a linkage group,

Ra 11 represents an alkyl group containing 1 to 4 carbon atoms, Z represents a group of atoms forming an alicyclic hydrocarbon group together with the carbon atom adjacent to Ra 11 ,

Ra 12 to Ra 14 each independently represents a hydrocarbon group, with the proviso that at least one among Ra 12 , Ra 13 and Ra 14 represents an alicyclic hydrocarbon group:

wherein R 1 to R 3 , which may be the same or different, each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an alkoxy group,

R 4 and R 5 , which may be the same or different, each represent a hydrogen atom, a cyano group, an alkyl group, an aryl group or an alkoxy group,

Y 1 and Y 2 , which may be the same or different, each represents an alkyl group, an aryl group, an aralkyl group or a hetero atom-containing aromatic group,

n represents an integer of 1 to 4, and with the proviso that when n is 2 or more, a plurality of R 1 s may be the same or different and a plurality of R 2 s may also be the same or different, any two or more among R 1 to R 3 , R 4 , R 5 , Y 1 and Y 2 may be bonded with each other to form a cyclic structure,

two or more of structures represented by formula (I) or (II) may be present by being bonded to each other via one or more of a linkage group at any sites of R 1 s, R 2 s, R 3 s, R 4 s, R 5 s, Y 1 s and Y 2 s,

X − represents a non-nucleophilic anion:

wherein Ar represents an aryl group or a hetero atom-containing aromatic group,

R 6 represents a hydrogen atom, a cyano group, an alkyl group or an aryl group,

R 7 represents an alkyl group or an aryl group,

Y 3 and Y 4 , which may be the same or different, each represents an alkyl group, an aryl group, an aralkyl group or a hetero atom-containing aromatic group, or Y 3 and Y 4 may be bonded with each other to form a ring,

Ar and at least either Y 3 or Y 4 may be bonded with each other to form a ring,

Ar and R 6 may be bonded with each other to form a ring, or two or more of structures represented by formula (III) may be present by being bonded to each other via one or more of a linkage group at Ar sites, either R 6 or R 7 sites, or either Y 3 or Y 4 sites, and

X − represents a non-nucleophilic anion;

wherein the component (B) includes: at least one of the compounds represented by the formulae (I) and (II); and the compound represented by the formula (III).

14. A method for forming a pattern, which comprises forming a resist film comprising the composition described in claim 13 , exposing the resist film upon irradiation with the actinic rays or a radiation, and subsequently developing the resist film.