Composition for forming fine pattern and method for forming fined pattern using same

1. A composition for forming a superfine pattern, comprising pure water and a water-soluble resin represented by the following formula (1):

—X p —Y q —Z r —  (1)

wherein

X, Y and Z are repeating units of

 respectively;

p, q and r are numbers of polymerization ratios of said repeating units X, Y and Z, respectively, provided that they satisfy the conditions of 0.60≦p+r≦0.95 and 0.05≦q≦0.40 and that each repeating unit may combine with each other either randomly or to form a block;

a in said repeating unit X or Y is an integer of 0 or 1;

L in said repeating unit Y is a divalent linking group selected from the group consisting of

—N═CH—,

—NH—CHR 0 —,

—NH—CH 2 —CHR 0 — and

—NH—CHR 0 —CH 2 —

where R 0 is selected from the group consisting of —H, —CH 3 , —COOH, —CH 2 COOH, —CH(CH 3 ) 2 and —COOC 2 H 5 ;

Ar in said repeating unit Y is a group represented by the following formula:

where b is an integer of 0 to 5; c is an integer of 0 to 5−b; R 1 is an organic group comprising elements selected from the group consisting of carbon, nitrogen, oxygen and fluorine; in the case where b is 2 or more, two R 1 s may combine with each other to form a ring structure; and R 2 is an acid group selected from the group consisting of —COOH, —CH 2 COOH, —CH(CH 3 )COOH, —OCH 2 COOH, —SO 3 H and —OH;

said repeating unit Y contains at least one acid group; and

each of said repeating units X and Y may be a combination of repeating units having different structures, respectively and further where r is non-zero and the Z unit is present.

2. The composition for forming a superfine pattern according to claim 1 , wherein b is an integer from 1 to 5, R 1 is selected from the group consisting of alkyl, alkoxy, hydroxy alkyl, substituted amino, non-substituted amino, alkylether, alkylester, alkylamido, fluorine atom and fluorinated alkoxy.

3. The composition for forming a superfine pattern according to claim 1 , wherein Ar is a group selected from the following groups:

4. The composition for forming a superfine pattern according to claim 1 , wherein said water-soluble resin has a weight average molecular weight of 3000 to 100000.

5. The composition for forming a superfine pattern according to claim 1 , wherein said water-soluble resin is contained in an amount of 0.1 to 10 wt % based on the total weight of the composition.

6. A method for forming a superfine resist pattern, comprising the step of

treating a resist pattern after development with the composition for forming a superfine pattern according to claim 1 , so as to reduce the effective size of the resist pattern after the development.

7. The method for forming a superfine resist pattern according to claim 6 , further comprising the step of

washing said resist pattern with pure water immediately before or after the treatment with the composition for forming a superfine pattern.

8. A composition for forming a superfine pattern, comprising pure water, an acid and a water-soluble resin represented by the following formula (1′):

—X p —Y′ q —Z r —  (1′)

wherein

X, Y′ and Z are repeating units of

 respectively;

p, q and r are numbers of polymerization ratios of said repeating units X, Y′ and Z, respectively, provided that they satisfy the conditions of 0.60≦p+r≦0.95 and 0.05≦q≦0.40 and that each repeating unit may combine with each other either randomly or to form a block;

a in said repeating unit X or Y′ is an integer of 0 or 1;

L′ in said repeating unit Y′ is a divalent linking group selected from the group consisting of

—N═CH—,

—NH—CHR 0′ —,

—NH—CH 2 —CHR 0′ — and

—NH—CHR 0′ —CH 2 —

where R 0′ is selected from the group consisting of —H, —CH 3 , —CH(CH 3 ) 2 and —COO 2 H 5 ;

Ar′ in said repeating unit Y′ is a group represented by the following formula:

where b is an integer of 0 to 5; R 1 is an organic group comprising elements selected from the group consisting of carbon, nitrogen, oxygen and fluorine; and in the case where b is 2 or more, two R 1 s may combine with each other to form a ring structure;

and

each of said repeating units X and Y′ may be a combination of repeating units having different structures, respectively and further where r is non-zero and the Z unit is present.

9. The composition for forming a superfine pattern according to claim 8 , wherein b is an integer from 1 to 5, R 1 is selected from the group consisting of alkyl, alkoxy, hydroxy alkyl, substituted amino, non-substituted amino, alkylether, alkylester, alkylamido, fluorine atom and fluorinated alkoxy.

10. The composition for forming a superfine pattern according to claim 8 , wherein Ar′ is a group selected from the following groups:

11. The composition for forming a superfine pattern according to claim 8 , wherein said acid is selected from the group consisting of nitric acid, sulfuric acid, acetic acid, benzene-sulfonic acid, p-toluenesulfonic acid, 2-naphthalenesulfonic acid, 1,3-benzenedisulfonic acid, 1,5-naphthalenedisulfonic acid and 2,7-naphthalenedisulfonic acid.

12. A composition for forming a superfine pattern, comprising pure water and a water-soluble resin; wherein

said water-soluble resin is a product of the reaction of a backbone polymer represented by the following formula (2):

—X 0 p0 —Z 0 r0 —  (2)

in which

X 0 and Z 0 are repeating units of

respectively;

p0 and r0 are numbers of polymerization ratios of said repeating units X 0 and Z 0 , respectively, provided that they satisfy the conditions of 0.05≦p0≦1 and 0≦r0≦0.95 and that each repeating unit may combine with each other either randomly or to form a block;

a0 in said repeating unit X 0 is an integer of 0 or 1; and

said repeating unit X 0 may be a combination of repeating units having different a0 integers;

with

at least one side-chain forming compound represented by the following formula (3A) or (3B):

in which b is an integer of 0 to 5; c is an integer of 0 to 5−b; W is a single bond or a divalent linking group selected from the group consisting of —CHR 0 — and —CHR 0 —CH 2 — where R 0 is selected from the group consisting of —H, —CH 3 ,—CH(CH 3 ) 2 , —COOH, —CH 2 COOH and —COOC 2 H 5 ; R 1 is an organic group comprising elements selected from the group consisting of carbon, nitrogen, oxygen and fluorine; in the case where b is 2 or more, two R 1 s may combine with each other to form a ring structure; R 2 is an acid group selected from the group consisting of —COOH, —CH 2 COOH, —CH(CH 3 )COOH, —OCH 2 COOH, —SO 3 H and —OH; and W or R 1 includes at least one acid group;

so that aromatic group-containing substituents derived from said side-chain forming compound are combined with 5 to 40% of nitrogen atoms in said backbone polymer and further where r0 is non-zero and the Z 0 unit is present.

13. The composition for forming a superfine pattern according to claim 12 , wherein said side-chain forming compound is selected from the group consisting of:

14. A composition for forming a superfine pattern, comprising pure water, an acid and a water-soluble resin;

wherein

said water-soluble resin is a product of the reaction of a backbone polymer represented by the following formula (2):

—X 0 p0 —Z 0 r0 —  (2)

in which X 0 and Z 0 are repeating units of

respectively;

p0 and r0 are numbers of polymerization ratios of said repeating units X 0 and Z 0 , respectively, provided that they satisfy the conditions of 0.05≦p0≦1 and 0≦r0≦0.95 and that each repeating unit may combine with each other either randomly or to form a block;

a0 in said repeating unit X 0 is an integer of 0 or 1; and

said repeating unit X 0 may be a combination of repeating units having different a0 integers;

with at least one side-chain forming compound represented by the following formula (3A′) or (3B′):

in which b is an integer of 0 to 5; W′ is a single bond or a divalent linking group selected from the group consisting of —CHR 0′ — and —CHR 0′ —CH 2 — where R 0′ is selected from the group consisting of —H, —CH 3 and —COOC 2 H 5 ; R 1 is an organic group comprising elements selected from the group consisting of carbon, nitrogen, oxygen and fluorine; and in the case where b is 2 or more, two R 1 s may combine with each other to form a ring structure;

so that aromatic group-containing substituents derived from said side-chain forming compound are combined with 5 to 40% of nitrogen atoms in said backbone polymer and further where r0 is non-zero and the Z 0 unit is present.

15. The composition for forming a superfine pattern according to claim 14 , wherein said side-chain forming compound is selected from the group consisting of:

16. The composition for forming a superfine pattern according to claim 14 , wherein said acid is selected from the group consisting of nitric acid, sulfuric acid, acetic acid, benzene-sulfonic acid, p-toluenesulfonic acid, 2-naphthalenesulfonic acid, 1,3-benzenedisulfonic acid, 1,5-naphthalenedisulfonic acid and 2,7-naphthalenedisulfonic acid.

17. A composition for forming a superfine pattern, comprising pure water and a water-soluble resin represented by the following formula (1):

—X p —Y q —Z r —  (1)

wherein

X, Y and Z are repeating units of

 respectively;

p, q and r are numbers of polymerization ratios of said repeating units X, Y and Z, respectively, provided that they satisfy the conditions of 0.60≦p+r≦0.95 and 0.05≦q≦0.40 and that each repeating unit may combine with each other either randomly or to form a block;

a in said repeating unit X or Y is an integer of 0 or 1;

L in said repeating unit Y is a divalent linking group selected from the group consisting of

—N═CH—,

—NH—CHR 0 —,

—NH—CH 2 —CHR 0 — and

—NH—CHR 0 —CH 2 —

where R 0 is selected from the group consisting of —H, —CH 3 , —COOH, —CH 2 COOH, —CH(CH 3 ) 2 and —COOC 2 H 5 ;

Ar in said repeating unit Y is a group represented by the following formula:

where b is an integer of 0 to 5; c is an integer of 0 to 5−b; R 1 is an organic group comprising elements selected from the group consisting of carbon, nitrogen, oxygen and fluorine; in the case where b is 2 or more, two R 1 s may combine with each other to form a ring structure; and R 2 is an acid group selected from the group consisting of —COOH, —CH 2 COOH, —CH(CH 3 )COOH, —OCH 2 COOH, —SO 3 H and —OH;

said repeating unit Y contains at least one acid group; and

each of said repeating units X and Y may be a combination of repeating units having different structures, respectively and further wherein b is an integer from 1 to 5, R 1 is selected from the group consisting of alkyl, alkoxy, hydroxy alkyl, substituted amino, non-substituted amino, alkylether, alkylester, alkylamido, fluorine atom and fluorinated alkoxy.

18. A composition for forming a superfine pattern, comprising pure water and a water-soluble resin; wherein

said water-soluble resin is a product of the reaction of a backbone polymer represented by the following formula (2):

—X 0 p0 —Z 0 r0 —  (2)

in which

X 0 and Z 0 are repeating units of

respectively;

p0 and r0 are numbers of polymerization ratios of said repeating units X 0 and Z 0 , respectively, provided that they satisfy the conditions of 0.05≦p0≦1 and 0≦r0≦0.95 and that each repeating unit may combine with each other either randomly or to form a block;

a0 in said repeating unit X 0 is an integer of 0 or 1; and

said repeating unit X 0 may be a combination of repeating units having different a0 integers;

with

at least one side-chain forming compound represented by the following formula (3A) or (3B):

in which b is an integer of 0 to 5; c is an integer of 0 to 5−b; W is a single bond or a divalent linking group selected from the group consisting of —CHR 0 — and —CHR 0 —CH 2 — where R 0 is selected from the group consisting of —H, —CH 3 , —CH(CH 3 ) 2 , —COOH, —CH 2 COOH and —COOC 2 H 5 ; R 1 is an organic group comprising elements selected from the group consisting of carbon, nitrogen, oxygen and fluorine; in the case where b is 2 or more, two R 1 s may combine with each other to form a ring structure; R 2 is an acid group selected from the group consisting of —COOH, —CH 2 COOH, —CH(CH 3 )COOH, —OCH 2 COOH, —SO 3 H and —OH; and W or R 1 includes at least one acid group;

so that aromatic group-containing substituents derived from said side-chain forming compound are combined with 5 to 40% of nitrogen atoms in said backbone polymer and further wherein said side-chain forming compound is selected from the group consisting of: