Chemical-resistant protective film

1 . A composition for forming a protective film against a wet etching liquid for semiconductor or a resist underlayer film-forming composition, the composition comprising:

(A) a polymer having a unit structure represented by the following formula (1-1):

wherein Ar represents a benzene ring, a naphthalene ring, or an anthracene ring; R 1 represents a hydroxy group, a mercapto group optionally protected by a methyl group, an amino group optionally protected by a methyl group, a halogeno group, or an alkyl group having 1 to 10 carbon atoms and being optionally substituted with or interrupted by a heteroatom and optionally substituted with a hydroxy group; n1 represents an integer of 0 to 3; L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms; E represents an epoxy group; and, when n2 is 1, T 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms and being optionally interrupted by an ether linkage, ester linkage, or amide linkage; and, when n2 is 2, T 1 represents a nitrogen atom or an amide linkage;

(B) a compound or polymer having a phenolic hydroxy group other than catechol, wherein the compound or polymer (B) is represented by the following formula (2-1):

wherein each of R 2 and T 2 independently represents a halogeno group, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group optionally substituted with an alkyl group having 1 to 3 carbon atoms, a hydroxy group, or an alkyl group having 1 to 10 carbon atoms and being optionally substituted with a halogeno group; each of A 1 and A 2 independently is an alkylene group having 1 to 10 carbon atoms, a divalent organic group derived from a bicyclo-ring compound, a biphenylene group, a divalent organic group represented by —CT 2 T 3 -, or a combination thereof, wherein T 3 represents a hydrogen atom or a monovalent group represented by (formula 2-1-a):

wherein, in (formula 2-1-a), * represents a bonding site to the carbon atom to which T 3 is bonded, and a represents an integer of 1 to 6;

each of n3 to n5 independently represents an integer of 0 to 2; r2 represents an integer of 0 to 3; and

each of m1 and m2 independently represents a number of 0 to 10,000,000;

(C) a thermal acid generator; and

(D) a solvent.

2 . The composition f according to claim 1 , wherein m1, n3 to n5, and r2 are 0; and m2 is 1.

3 . A composition for forming a protective film against a wet etching liquid for semiconductor or a resist underlayer film-forming composition, the composition comprising:

(A) a polymer having a unit structure represented by the following formula (1-1):

wherein Ar represents a benzene ring, a naphthalene ring, or an anthracene ring; R 1 represents a hydroxy group, a mercapto group optionally protected by a methyl group, an amino group optionally protected by a methyl group, a halogeno group, or an alkyl group having 1 to 10 carbon atoms and being optionally substituted with or interrupted by a heteroatom and optionally substituted with a hydroxy group; n1 represents an integer of 0 to 3; L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms; E represents an epoxy group; and, when n2 is 1, T 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms and being optionally interrupted by an ether linkage, ester linkage, or amide linkage; and, when n2 is 2, T 1 represents a nitrogen atom or an amide linkage;

(B) a compound or polymer having a phenolic hydroxy group other than catechol, wherein the compound or polymer (B) is a compound represented by the following formula (2-2):

wherein R 3 represents a halogeno group, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group optionally substituted with an alkyl group having 1 to 3 carbon atoms, a hydroxy group, or an alkyl group having 1 to 10 carbon atoms and being optionally substituted with a halogeno group; Q 1 represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an imino group, an arylene group having 6 to 40 carbon atoms, or an alkylene group having 1 to 10 carbon atoms and being optionally substituted with a halogeno group; a represents an integer of 1 to 6; n6 represents an integer of 0 to 2; and r3 represents an integer of 0 to 3;

(C) a thermal acid generator; and

(D) a solvent.

4 . A composition for forming a protective film against a wet etching liquid for semiconductor or a resist underlayer film-forming composition, the composition comprising:

(A) a polymer having a unit structure represented by the following formula (1-1):

wherein Ar represents a benzene ring, a naphthalene ring, or an anthracene ring; R 1 represents a hydroxy group, a mercapto group optionally protected by a methyl group, an amino group optionally protected by a methyl group, a halogeno group, or an alkyl group having 1 to 10 carbon atoms and being optionally substituted with or interrupted by a heteroatom and optionally substituted with a hydroxy group; n1 represents an integer of 0 to 3; L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms; E represents an epoxy group; and, when n2 is 1, T 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms and being optionally interrupted by an ether linkage, ester linkage, or amide linkage; and, when n2 is 2, T 1 represents a nitrogen atom or an amide linkage;

(B) a compound or polymer having a phenolic hydroxy group other than catechol, wherein the compound or polymer (B) is a polymer having a unit structure represented by the following formula (3-1):

wherein T 4 represents a hydrogen atom in addition to the alkyl group having 1 to 10 carbon atoms and being optionally substituted with a halogeno group; R 4 represents a halogeno group, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group optionally substituted with an alkyl group having 1 to 3 carbon atoms, a hydroxy group, or an alkyl group having 1 to 10 carbon atoms and being optionally substituted with a halogeno group; r4 represents an integer of 0 to 3; n7 represents an integer of 0 to 2; and a represents an integer of 1 to 6;

(C) a thermal acid generator; and

(D) a solvent.

5 . A protective film against a wet etching liquid for semiconductor, which is a baked product of an applied film comprising the composition for forming a protective film according to claim 1 .

6 . A resist underlayer film, which is a baked product of an applied film comprising the resist underlayer film-forming composition according to claim 1 .

7 . A method for producing a substrate having a protective film, for use in the manufacture of a semiconductor, comprising the steps of:

applying the composition for forming a protective film according to claim 1 onto a stepped semiconductor substrate, and

baking the applied composition to form a protective film.

8 . A method for producing a substrate having a resist pattern, for use in the manufacture of a semiconductor, comprising the steps of:

applying the composition according to claim 1 onto a semiconductor substrate, and baking the applied composition to form a protective film as a resist underlayer film, and

forming a resist film on the protective film and then subjecting the resist film to exposure and development to form a resist pattern.

9 . A method for producing a semiconductor device, comprising the steps of:

forming a protective film on a semiconductor substrate optionally having an inorganic film formed on a surface thereof using the composition for forming a protective film according to claim 1 ,

forming a resist pattern on the protective film,

subjecting the protective film to dry etching using the formed resist pattern as a mask so as to expose a surface of the semiconductor substrate or inorganic film, and

using the dry-etched protective film as a mask, subjecting the semiconductor substrate or inorganic film to wet etching using a wet etching liquid for semiconductor, and then to washing.

10 . A method for producing a semiconductor device, comprising the steps of:

forming a resist underlayer film on a semiconductor substrate optionally having an inorganic film formed on a surface thereof using the resist underlayer film-forming composition according to claim 1 ,

forming a resist pattern on the resist underlayer film,

subjecting the resist underlayer film to dry etching using the formed resist pattern as a mask so as to expose a surface of the semiconductor substrate or inorganic film, and

using the dry-etched resist underlayer film as a mask, subjecting the semiconductor substrate or inorganic film to etching.

11 . A protective film against a wet etching liquid for semiconductor, which is a baked product of an applied film comprising the composition for forming a protective film according to claim 3 .

12 . A resist underlayer film, which is a baked product of an applied film comprising the resist underlayer film-forming composition according to claim 3 .

13 . A method for producing a substrate having a protective film, for use in the manufacture of a semiconductor, comprising the steps of:

applying the composition for forming a protective film according to claim 3 onto a stepped semiconductor substrate, and

baking the applied composition to form a protective film.

14 . A method for producing a substrate having a resist pattern, for use in the manufacture of a semiconductor, comprising the steps of:

applying the composition according to claim 3 onto a semiconductor substrate, and baking the applied composition to form a protective film as a resist underlayer film, and

forming a resist film on the protective film and then subjecting the resist film to exposure and development to form a resist pattern.

15 . A method for producing a semiconductor device, comprising the steps of:

forming a protective film on a semiconductor substrate optionally having an inorganic film formed on a surface thereof using the composition for forming a protective film according to claim 3 ,

forming a resist pattern on the protective film,

subjecting the protective film to dry etching using the formed resist pattern as a mask so as to expose a surface of the semiconductor substrate or inorganic film, and

using the dry-etched protective film as a mask, subjecting the semiconductor substrate or inorganic film to wet etching using a wet etching liquid for semiconductor, and then to washing.

16 . A method for producing a semiconductor device, comprising the steps of:

forming a resist underlayer film on a semiconductor substrate optionally having an inorganic film formed on a surface thereof using the resist underlayer film-forming composition according to claim 3 ,

forming a resist pattern on the resist underlayer film,

subjecting the resist underlayer film to dry etching using the formed resist pattern as a mask so as to expose a surface of the semiconductor substrate or inorganic film, and

using the dry-etched resist underlayer film as a mask, subjecting the semiconductor substrate or inorganic film to etching.

17 . A protective film against a wet etching liquid for semiconductor, which is a baked product of an applied film comprising the composition for forming a protective film according to claim 4 .

18 . A resist underlayer film, which is a baked product of an applied film comprising the resist underlayer film-forming composition according to claim 4 .

19 . A method for producing a substrate having a protective film, for use in the manufacture of a semiconductor, comprising the steps of:

applying the composition for forming a protective film according to claim 4 onto a stepped semiconductor substrate, and

baking the applied composition to form a protective film.

20 . A method for producing a substrate having a resist pattern, for use in the manufacture of a semiconductor, comprising the steps of:

applying the composition according to claim 4 onto a semiconductor substrate, and baking the applied composition to form a protective film as a resist underlayer film, and

forming a resist film on the protective film and then subjecting the resist film to exposure and development to form a resist pattern.

21 . A method for producing a semiconductor device, comprising the steps of:

forming a protective film on a semiconductor substrate optionally having an inorganic film formed on a surface thereof using the composition for forming a protective film according to claim 6 ,

forming a resist pattern on the protective film,

subjecting the protective film to dry etching using the formed resist pattern as a mask so as to expose a surface of the semiconductor substrate or inorganic film, and

using the dry-etched protective film as a mask, subjecting the semiconductor substrate or inorganic film to wet etching using a wet etching liquid for semiconductor, and then to washing.

22 . A method for producing a semiconductor device, comprising the steps of:

forming a resist underlayer film on a semiconductor substrate optionally having an inorganic film formed on a surface thereof using the resist underlayer film-forming composition according to claim 4 ,

forming a resist pattern on the resist underlayer film,

subjecting the resist underlayer film to dry etching using the formed resist pattern as a mask so as to expose a surface of the semiconductor substrate or inorganic film, and

using the dry-etched resist underlayer film as a mask, subjecting the semiconductor substrate or inorganic film to etching.