Actinic-ray- or radiation-sensitive resin composition, actinic-ray- or radiation-sensitive film therefrom and method of forming pattern

1. An actinic-ray- or radiation-sensitive resin composition comprising:

a resin (Aa) containing at least one repeating unit (Aa1) derived from monomers of general formula (aa1-1) below and at least one repeating unit (Aa2) derived from monomers of general formula (aa2-1) below, the content of the resin (Aa) being in the range of 0.01 to 20 mass % based on the total solids of the composition;

a resin (Ab) that when acted on by an acid, changes its alkali solubility, the resin (Ab) comprising a repeating unit containing a phenolic hydroxyl group; and

a compound that when exposed to actinic rays or radiation, generates an acid,

in general formula (aa1-1),

Q 1 represents an organic group containing a polymerizable group,

each of L 1 and L 2 independently represents a single bond or a bivalent connecting group, and

Rf represents an organic group containing a fluorine atom, and

in general formula (aa2-1),

Rb represents a hydrogen atom, an optionally substituted alkyl group, or a halogen atom,

S 1a , represents a group selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, a halogen atom, a cyano group, an organic group containing a silicon atom, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a hydroxyl group, a nitro group, a sulfonylamino group, an alkylthio group, an arylthio group and an aralkylthio group, or represents a group resulting from bonding of the selected group to a bivalent connecting group, provided that when two or more S1as exist, the S1as may be identical to or different from each other, and

p is an integer of 0 to 5.

2. The composition according to claim 1 , wherein the resin (Aa) contains at least one of repeating units of general formulae (aa1-2-1) and (aa1-3-1) below as the repeating unit (Aa1) derived from monomers of general formula (aa1-1) above,

in general formulae (aa1-2-1) and (aa1-3-1),

each of Ra 1 and Ra 2 independently represents a hydrogen atom or an alkyl group,

each of L 21 and L 22 independently represents a single bond or a bivalent connecting group, and

each of Rf 1 and Rf 2 independently represents an organic group containing a fluorine atom.

3. The composition according to claim 1 , wherein the resin (Aa) contains at least one of repeating units of general formulae (aa1-2-2) and (aa1-3-2) below as the repeating unit (Aa1) derived from monomers of general formula (aa1-1) above,

in general formulae (aa1-2-2) and (aa1-3-2),

each of Ra 1 and Ra2 independently represents a hydrogen atom or an alkyl group,

each of R 1 , R 2 , R 3 and R 4 independently represents a hydrogen atom or an alkyl group,

each of m 1 and m 2 independently is an integer of 0 to 5, and

each of Rf 1 and Rf 2 independently represents an organic group containing a fluorine atom.

4. The composition according to claim 1 , wherein the resin (Aa) contains at least one of repeating units of general formulae (aa1-2-3) and (aa1-3-3) below as the repeating unit (Aa1) derived from monomers of general formula (aa1-1) above,

in general formulae (aa1-2-3) and (aa1-3-3),

Ra 1 represents a hydrogen atom or a methyl group, and

each of Rf 1 and Rf 2 independently represents an organic group containing a fluorine atom.

5. The composition according to claim 1 , wherein in general formula (aa2-1) above, Rb represents a hydrogen atom; S 1a represents an optionally substituted alkyl group, an organic group containing a silicon atom, or a halogen atom; and p is an integer of 1 to 5.

6. The composition according to claim 1 , wherein in general formula (aa2-1) above, S 1a represents an alkyl group, an alkyl group substituted with a halogen atom or an organic group containing a silicon atom.

7. The composition according to claim 1 , wherein in general formula (aa2-1) above, S1a represents an alkyl group or any of groups of general formula (S-1) below,

in which

each of R 11 , R 21 and R 31 independently represents an alkyl group, and

L 1 represents a single bond or a bivalent connecting group.

8. The composition according to claim 1 , wherein the resin (Ab) comprises a repeating unit (B) containing a structural moiety that when exposed to actinic rays or radiation, generates an acid.

9. The composition according to claim 1 , wherein the resin (Ab) comprises at least one of repeating units (A) of general formula (A) below,

in which

n is an integer of 1 to 5, and m is an integer of 0 to 4 satisfying the relationship 1≦m+n≦5, and

S 1 represents a group selected from the group consisting of an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, a sulfonylamino group, an alkylthio group, an arylthio group and an aralkylthio group, provided that when m is 2 or greater, two or more S 1 s may be identical to or different from each other.

10. The composition according to claim 9 , wherein the resin (Ab) comprises at least a repeating unit of formula below as the at least one of repeating units (A) of general formula (A) above.

11. The composition according to claim 1 , wherein the resin (Aa) is contained in an amount of 0.01 to 20 mass % based on total solids of the composition.

12. The composition according to claim 11 , wherein the resin (Aa) is contained in an amount of 0.01 to 10 mass % based on total solids of the composition.

13. The composition according to claim 12 , wherein the resin (Aa) is contained in an amount of 0.01 to 5 mass % based on total solids of the composition.

14. The composition according to claim 1 , wherein the resin (Ab) comprises at least one of repeating units of general formulae (A1) and (A2) below,

in general formula (A1)

n is an integer of 1 to 5, and m is an integer of 0 to 4 satisfying the relationship 1≦m+n≦5,

S 1 represents a group selected from the group consisting of an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, a sulfonylamino group, an alkylthio group, an arylthio group and an aralkylthio group, provided that when m is 2 or greater, two or more S 1 s may be identical to or different from each other, and

A 1 represents a hydrogen atom or a group that when acted on by an acid, is cleaved, provided that at least one A 1 represents a group that when acted on by an acid, is cleaved, and that when n is 2 or greater, two or more A 1 s may be identical to or different from each other, and

in general formula (A2)

X represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, a carboxyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group or an aralkyl group, and

A 2 represents a group that when acted on by an acid, is cleaved.

15. The composition according to claim 14 , wherein the resin (Ab) comprises any of groups of formula —C(L 1 )(L 2 )-O—Z 2 as the group that when acted on by an acid, is cleaved,

in which each of L 1 and L 2 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aralkyl group, and

Z 2 represents an alkyl group, a cycloalkyl group or an aralkyl group, provided that Z 2 and L 1 may be bonded to each other to thereby form a 5-membered or 6-membered ring.

16. The composition according to claim 14 , wherein the resin (Ab) comprises any of repeating units of general formula (A1).

17. An actinic-ray- or radiation-sensitive film formed from the composition according to claim 1 .

18. A method of forming a pattern, comprising forming the composition according to claim 1 into a film, exposing the film to light, and developing the exposed film.

19. The method according to claim 18 , wherein the exposure is performed using EUV.

20. An actinic-ray- or radiation-sensitive resin composition comprising:

a resin (Aa) containing at least one repeating unit (Aa1) derived from monomers of general formula (aa1-1) below and at least one repeating unit (Aa2) derived from monomers of general formula (aa2-1) below;

a resin (Ab) that when acted on by an acid, changes its alkali solubility; and

a compound that when exposed to actinic rays or radiation, generates an acid,

in general formula (aa1-1),

Q 1 represents an organic group containing a polymerizable group,

each of L 1 and L 2 independently represents a single bond or a bivalent connecting group, and

Rf represents an organic group containing a fluorine atom, and

in general formula (aa2-1),

Rb represents a hydrogen atom, an optionally substituted alkyl group, or a halogen atom,

S 1a represents any of groups of general formula (S-1) below and when two or more S 1a s exist, the S 1a s may be identical to or different from each other, and

p is an integer of 0 to 5,

in which

each of R 11 , R 21 and R 31 independently represents an alkyl group, and

L 1 represents a single bond or a bivalent connecting group.

21. An actinic-ray- or radiation-sensitive resin composition comprising:

a resin (Aa) containing at least one repeating unit (Aa1) derived from monomers of general formula (aa1-1) below and at least one repeating unit (Aa2) derived from monomers of general formula (aa2-1) below, and

a resin (Ab) that when acted on by an acid, changes its alkali solubility, the resin (Ab) comprising a repeating unit (B) containing a structural moiety that when exposed to actinic rays or radiation, generates an acid,

in general formula (aa1-1),

Q 1 represents an organic group containing a polymerizable group,

each of L 1 and L 2 independently represents a single bond or a bivalent connecting group, and

Rf represents an organic group containing a fluorine atom, and

in general formula (aa2-1),

Rb represents a hydrogen atom, an optionally substituted alkyl group, or a halogen atom,

S 1a represents any of groups of general formula (S-1) below and when two or more S 1a s exist, the S 1a s may be identical to or different from each other, and

p is an integer of 0 to 5,

in which

each of R 11 , R 21 and R 31 independently represents an alkyl group, and

L 1 represents a single bond or a bivalent connecting group.

22. An actinic-ray- or radiation-sensitive resin composition comprising:

a resin (Aa) containing at least one repeating unit (Aa1) derived from monomers of general formula (aa1-1) below and at least one repeating unit (Aa2) derived from monomers of general formula (aa2-1) below, the content of the resin (Aa) being in the range of 0.01 to 20 mass % based on the total solids of the composition; and

a resin (Ab) that when acted on by an acid, changes its alkali solubility, the resin (Ab) comprising a repeating unit (B) containing a structural moiety that when exposed to actinic rays or radiation, generates an acid,

in general formula (aa1-1),

Q 1 represents an organic group containing a polymerizable group,

each of L 1 and L 2 independently represents a single bond or a bivalent connecting group, and

Rf represents an organic group containing a fluorine atom, and

in general formula (aa2-1),

Rb represents a hydrogen atom, an optionally substituted alkyl group, or a halogen atom,

S 1a represents a group selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, a halogen atom, a cyano group, an organic group containing a silicon atom, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a hydroxyl group, a nitro group, a sulfonylamino group, an alkylthio group, an arylthio group and an aralkylthio group, or represents a group resulting from bonding of the selected group to a bivalent connecting group, and when two or more S 1a s exist, the S 1a s may be identical to or different from each other, and

p is an integer of 0 to 5.