Positive photosensitive composition and method of forming pattern using the same

1. A positive photosensitive composition comprising:

a resin (A) whose dissolution rate in an alkaline developing solution increases by the

action of an acid, the resin (A) containing an acid decomposable repeating unit represented by a general formula (I), an acid nondecomposable repeating unit represented by a general formula (II), and a lactone group-containing repeating unit; and

a compound (B) capable of generating an acid upon irradiation with one of active rays and radiations:

wherein

Xa 1 represents one of a hydrogen atom, an alkyl group, a cyano group and a halogen atom,

A 1 represents one of a single bond and a divalent connecting group,

ALG represents an acid leaving hydrocarbon group,

Xa 2 represents one of a hydrogen atom, an alkyl group, a cyano group and a halogen atom,

A 2 represents one of a single bond and a divalent connecting group,

ACG represents an acid nonleaving hydrocarbon group composed of only carbon atoms and hydrogen atoms,

ACG in the general formula (II) has a polycyclic hydrocarbon structure, and ALG in the general formula (I) does not have a polycyclic hydrocarbon structure, and

the acid decomposable repeating unit represented by the general formula (I) is an acid decomposable repeating unit represented by a general formula (I-1):

wherein

Xa 1 represents one of a hydrogen atom, an alkyl group, a cyano group and a halogen atom, and

Rx 1 to Rx 3 each independently represents a linear or branched alkyl group, or a monocyclic alkyl group, and at least two of Rx 1 to Rx 3 may be taken together to form a monocyclic alkyl group, provided that at least one of Rx 1 to Rx 3 represents a monocyclic alkyl group, or at least two of Rx 1 to Rx 3 are taken together to form a monocyclic alkyl group.

2. The positive photosensitive composition according to claim 1 , wherein the acid decomposable repeating unit represented by the general formula (I-1) is an acid decomposable repeating unit containing a monocyclic alkyl group represented by one of formulae (I-1a) and (I-1b):

wherein

Xa 1 represents one of a hydrogen atom, an alkyl group, a cyano group and a halogen atom,

Rx 1 and Rx 2 each independently represent a linear or branched alkyl group, or a monocyclic alkyl group,

Rx 4 represents a linear or branched alkyl group, or a monocyclic alkyl group,

n 1 represents one of 4 and 5, and

n 2 represents from 0 to 3.

3. The positive photosensitive composition according to claim 1 , wherein the resin (A) is a resin (A2) in which the repeating unit represented by the general formula (I-1) is at least one kind of a repeating unit selected from a repeating unit represented by a general formula (1) and a repeating unit represented by a general formula (2); and the repeating unit represented by the general formula (II) is a repeating unit represented by a general formula (3):

wherein

Rb 100 represents one of a hydrogen atom and an alkyl group,

R 101 represents an alkyl group,

R 102 represents an alkyl group, provided that when plural R 102 s are present, the plural R 102 s may be the same or different, or may be taken together to form a ring,

R 103 represents a connecting group containing a tertiary carbon atom, with the tertiary carbon atom being bound to the cyclic structure in the general formula (2),

A represents a nonleaving group having a polycyclic structure which comprises a carbon atom and a hydrogen atom,

n represents an integer of from 0 to 5, and

m represents an integer of from 0 to (n+2).

4. The positive photosensitive composition according to claim 3 , wherein the resin component (A) further comprises a repeating unit represented by the following general formula (4):

wherein

Rb 100 represents one of a hydrogen atom and an alkyl group.

5. The positive photosensitive composition according to claim 3 , further comprising a basic compound (C).

6. A method of forming pattern comprising:

forming a photosensitive layer by the positive photosensitive composition according to claim 1 ; and

exposing and developing the photosensitive layer.

7. The positive photosensitive composition according to claim 1 , wherein the lactone group-containing repeating unit is represented by formula (AI):

wherein

Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having from 1 to 4 carbon atoms,

Ab represents a single bond, an alkylene group, a divalent connecting group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent connecting group composed of a combination thereof, and

V represents a group represented by any one of the general formulae (LC1-1) to (LC1-16):

wherein

Rb 2 represents an alkyl group having from 1 to 8 carbon atoms, a cycloalkyl group having from 4 to 7 carbon atoms, an alkoxy group having from 1 to 8 carbon atoms, an alkoxycarbonyl group having from 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid decomposable group, and

n 2 represents an integer of from 0 to 4 provided that when n 2 is 2 or more, the plural existing Rb 2 s may be the same or different, and the plural existing Rb 2 s may be taken together to form a ring.

8. The positive photosensitive composition according to claim 1 , wherein the acid nondecomposable repeating unit represented by the general formula (II) is an acid nondecomposable repeating unit represented by one of the following formulae:

wherein

Xa 2 represents one of a hydrogen atom, an alkyl group, a cyano group and a halogen atom.

9. The positive photosensitive composition according to claim 1 , wherein resin (A) further comprises at least one of the repeating units represented by formulae (AIIa), (AIIb), (AIIc) and (AIId):

wherein

R 1 c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and

R 2 c to R 4 c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group, provided that at least one of R 2 c to R 4 c represents a hydroxyl group or a cyano group.

10. A positive photosensitive composition comprising:

a resin (A) whose dissolution rate in an alkaline developing solution increases by the

action of an acid, the resin (A) containing an acid decomposable repeating unit represented by a general formula (I) and an acid nondecomposable repeating unit represented by a general formula (II); and

a compound (B) capable of generating an acid upon irradiation with one of active rays and radiations:

wherein

Xa 1 represents one of a hydrogen atom, an alkyl group, a cyano group and a halogen atom,

A 1 represents one of a single bond and a divalent connecting group,

ALG represents an acid leaving hydrocarbon group and does not have a polycyclic hydrocarbon structure,

Xa 2 represents one of a hydrogen atom, an alkyl group, a cyano group and a halogen atom,

A 2 represents one of a single bond and a divalent connecting group,

ACG represents an acid nonleaving hydrocarbon group composed of only carbon atoms and hydrogen atoms and has a polycyclic hydrocarbon structure, and

the acid decomposable repeating unit represented by the general formula (I) is an acid decomposable repeating unit represented by one of formulae (I-1a) and (I-1b):

wherein

Xa 1 represents one of a hydrogen atom, an alkyl group, a cyano group and a halogen atom,

Rx 1 and Rx 2 each independently represents a linear or branched alkyl group, or a monocyclic alkyl group,

Rx 4 represents a linear or branched alkyl group, or a monocyclic alkyl group,

n 1 represents one of 4 and 5, and

n 2 represents from 0 to 3.

11. The positive photosensitive composition according to claim 10 , wherein the acid nondecomposable repeating unit represented by the general formula (II) is an acid nondecomposable repeating unit represented by one of the following formulae:

wherein

Xa 2 represents one of a hydrogen atom, an alkyl group, a cyano group and a halogen atom.

12. The positive photosensitive composition according to claim 10 , wherein the resin (A) is a resin (A2) in which the repeating unit represented by the general formula (1) is at least one kind of a repeating unit selected from a repeating unit represented by a general formula (1) and a repeating unit represented by a general formula (2); and the repeating unit represented by the general formula (II) is a repeating unit represented by a general formula (3):

wherein

Rb 100 represents one of a hydrogen atom and an alkyl group,

R 101 represents an alkyl group,

R 102 represents an alkyl group, provided that when plural R 102 s are present, the plural R 102 s may be the same or different, or may be taken together to form a ring,

R 103 represents a connecting group containing a tertiary carbon atom, with the tertiary carbon atom being bound to the cyclic structure in the general formula (2),

A represents a nonleaving group having a polycyclic structure which comprises a carbon atom and a hydrogen atom,

n represents an integer of from 0 to 5, and

m represents an integer of from 0 to (n+2).

13. The positive photosensitive composition according to claim 12 , wherein the resin component (A) further comprises a repeating unit represented by the following general formula (4):

wherein

Rb 100 represents one of a hydrogen atom and an alkyl group.

14. The positive photosensitive composition according to claim 12 , further comprising a basic compound (C).

15. A method of forming pattern comprising:

forming a photosensitive layer by the positive photosensitive composition according to claim 10 ; and exposing and developing the photosensitive layer.

16. The positive photosensitive composition according to claim 1 , wherein the resin (A) consists essentially of a repeating unit represented by formula (I), a repeating unit represented by formula (II) and a lactone group-containing repeating unit.

17. The positive photosensitive composition according to claim 16 , wherein the lactone group-containing repeating unit is represented by formula (AI):

wherein

Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having from 1 to 4 carbon atoms,

Ab represents a single bond, an alkylene group, a divalent connecting group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent connecting group composed of a combination thereof, and

V is represented by formula (LC1-4):

wherein

Rb 2 represents an alkyl group having from 1 to 8 carbon atoms, a cycloalkyl group having from 4 to 7 carbon atoms, an alkoxy group having from 1 to 8 carbon atoms, an alkoxycarbonyl group having from 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid decomposable group, and

n 2 represents an integer of from 0 to 4 provided that when n 2 is 2 or more, the plural existing Rb 2 s may be the same or different, and the plural existing Rb 2 s may be taken together to form a ring.