Methods for manufacturing protective film composition, protective film, resist underlayer film composition, substrate with resist pattern, and semiconductor device.

Abstract

The present invention provides a protective film forming composition that provides good shielding (protection) function for wet etching solution during semiconductor substrate processing, has a low dry etching rate, and thus has good coverage and embedding properties even for stepped substrates, with small film thickness difference after embedding, and can form a flat film. It also provides a method for manufacturing a protective film, a resist underlayer film, a substrate with resist pattern, and a semiconductor device using the composition. A protective film forming composition for a wet etching solution for semiconductors comprises (A) a polymer having a unit structure represented by the following formula (1-1): (in formula (1-1), Ar represents a benzene ring, a naphthyl ring, or an anthracene ring; R1 represents a hydroxyl group, a methyl-protected mercapto group, a methyl-protected amino group, a halogen group, or an alkyl group with 1 to 10 carbon atoms that can be substituted or interrupted by heteroatoms or hydroxyl groups; n1 represents an integer from 0 to 3; L1 represents a single bond or an alkyl group with 1 to 10 carbon atoms; E represents an epoxy group; when T1 is n2=1, it represents a single bond or an alkyl group with 1 to 10 carbon atoms that can be interrupted by ether bonds, ester bonds, or amide bonds; when T1 is n2=2, it represents a nitrogen atom or an amide bond); (B) a compound or polymer having a phenolic hydroxyl group other than catechol; (C) a hot acid generating agent; and (D) a solvent.

Description

Technical Field

[0001] This invention relates to lithography processes in semiconductor manufacturing, and particularly to a composition for forming a protective film with excellent resistance to wet etching solutions for semiconductors. Furthermore, it relates to a method for manufacturing a protective film formed from the aforementioned composition and a substrate with a resist pattern applied to the protective film, and a method for manufacturing a semiconductor device. Prior Technology

[0002] In semiconductor manufacturing, a photolithography process is widely known in which a resist underlayer film is disposed between a substrate and a resist film formed thereon to form a resist pattern of a desired shape. Although substrate processing is performed after the resist pattern is formed, while dry etching is mainly used as a step, wet etching is sometimes used on the substrate. Patent Document 1 discloses a resist underlayer film material that is resistant to alkaline hydrogen peroxide water. [Previous Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2018-173520 Summary of the Invention

[0004] [The problem the invention aims to solve]

[0005] Using a protective film to form a composition, a protective film is formed on a semiconductor substrate. When the substrate is processed by wet etching, the protective film is used as an etching mask. The protective film is required to have good masking function for wet etching solution for semiconductors (that is, the masked part can protect the substrate).

[0006] Furthermore, even for so-called stepped substrates, good coverage and small thickness difference after embedding are required to form a protective film composition that can form a flat film.

[0007] Previously, in order to demonstrate resistance to one type of wet etching solution, SC-1 (ammonia-hydrogen peroxide solution), the method of using low molecular weight compounds (such as gallic acid) as additives has been used, but there are still limitations in solving the above problems.

[0008] Furthermore, the protective film used for the above purposes is expected to function as a resisting underlayer film to solve problems (such as poor shape) during resisting pattern formation.

[0009] The purpose of this invention is to solve the aforementioned problems. [Methods used to solve problems]

[0010] This invention includes the following.

[0011] [1] A protective film forming composition for a wet etching solution for semiconductors, comprising (A) a polymer having a unit structure represented by the following formula (1-1): (In formula (1-1), Ar represents a benzene ring, a naphthyl ring, or an anthracene ring; R1 represents a hydroxyl group, a methyl-protected mercapto group, a methyl-protected amino group, a halogen group, or an alkyl group with 1 to 10 carbon atoms that can be substituted or interrupted by a heteroatom, or can be substituted by a hydroxyl group; n1 represents an integer from 0 to 3; L1 represents a single bond or an alkyl group with 1 to 10 carbon atoms; E represents an epoxy group; when T1 is n2=1, it represents a single bond or an alkyl group with 1 to 10 carbon atoms that can be interrupted by an ether bond, ester bond, or amide bond; when T1 is n2=2, it represents a nitrogen atom or an amide bond.) (B) Compounds or polymers containing phenolic hydroxyl groups other than catechol; (C) Thermal acid generating agents and (D) Solvent.

[0012] [2] The protective film forming composition as described in [1], wherein the aforementioned (B) compound or polymer has two or more phenolic hydroxyl groups.

[0013] [3] The protective film forming composition as described in [1] or [2], wherein the aforementioned compound (B) or polymer is represented by the following formula (2-1), (In the formula, R2 and T2 each independently represent a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, and alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group; A1 and A2 each independently represent an alkyl group with 1 to 10 carbon atoms, a divalent organogroup derived from a ring compound, a divalent organogroup represented by a phenyl group or -CT2T3-, or a combination thereof; T3 represents a hydrogen atom or a monovalent group represented by (Formula 2-1-a):) In (Equation 2-1-a), * indicates the bonding site with the carbon atom bonded to T3; a represents an integer from 1 to 6; n3~n5 each independently represent integers from 0 to 2; r2 represents integers from 0 to 3; m1 and m2 each independently represent numbers from 0 to 10,000,000.

[0014] [4] As described in [3], the protective film forming composition, wherein m1, n3~n5 and r2 are 0 and m2 is 1.

[0015] [5] The protective film forming composition as described in [1] or [2], wherein the aforementioned compound (B) or polymer is a compound represented by the following formula (2-2): (In the formula, R3 represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, and alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group; Q1 represents an alkyl group with 1 to 10 carbon atoms that can be substituted by a single bond, oxygen atom, sulfur atom, sulfonyluyl group, carbonyl group, imino group, aryl group with 6 to 40 carbon atoms, or alkyl group that can be substituted by a halogen group; a represents an integer from 1 to 6; n6 represents an integer from 0 to 2; r3 represents an integer from 0 to 3).

[0016] [6] The protective film forming composition as described in [1] or [2], wherein the aforementioned compound or polymer (B) is a polymer comprising the unit structure represented by the following formula (3-1): (In the formula, T4 represents an alkyl group with 1 to 10 carbon atoms that can be substituted by a halogen group; R4 represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, or alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group. r4 represents an integer from 0 to 3; n7 represents an integer from 0 to 2; a represents an integer from 1 to 6).

[0017] [7] A protective film for a wet etching solution for semiconductors, characterized in that it is a sintered product of a coating film composed of a protective film forming composition as described in any one of [1] to [6].

[0018] [8] A resistive underlayer film forming composition comprising (A) a polymer having a unit structure represented by the following formula (1-1): (In formula (1-1), Ar represents a benzene ring, a naphthyl ring, or an anthracene ring; R1 represents a hydroxyl group, a methyl-protected mercapto group, a methyl-protected amino group, a halogen group, or an alkyl group with 1 to 10 carbon atoms that can be substituted or interrupted by a heteroatom, or can be substituted by a hydroxyl group; n1 represents an integer from 0 to 3; L1 represents a single bond or an alkyl group with 1 to 10 carbon atoms; E represents an epoxy group; when T1 is n2=1, it represents a single bond or an alkyl group with 1 to 10 carbon atoms that can be interrupted by an ether bond, ester bond, or amide bond; when T1 is n2=2, it represents a nitrogen atom or an amide bond.) (B) Compounds or polymers containing phenolic hydroxyl groups other than catechol; (C) Thermal acid generating agents and (D) Solvent.

[0019] [9] A resistive underlayer film, characterized in that it is a sintered product of a coated film consisting of a resistive underlayer film forming composition as described in [8].

[0020]

[10] A method for manufacturing a substrate with a protective film, characterized in that it is used in the manufacture of semiconductors, and includes the step of coating a protective film forming composition as described in any one of [1] to [6] onto a semiconductor substrate having a step and firing it to form a protective film.

[0021]

[11] A method for manufacturing a substrate with a resist pattern, characterized by comprising the steps of coating a protective film composition as described in any one of [1] to [6] or a resist underlayer film forming composition as described in [8] onto a semiconductor substrate and firing it to form a protective film as a resist underlayer film, forming a resist film on the protective film, and then exposing and developing it to form a resist pattern, and using it in the manufacture of semiconductors.

[0022]

[12] A method for manufacturing a semiconductor device includes forming a protective film on a semiconductor substrate on which an inorganic film can be formed on its surface using a protective film forming composition as described in any one of [1] to [6], forming a resist pattern on the protective film, using the resist pattern as a mask, dry etching the protective film to expose the surface of the inorganic film or the semiconductor substrate, using the dry-etched protective film as a mask, wet etching and cleaning the inorganic film or the semiconductor substrate using a semiconductor wet etching solution.

[0023]

[13] A method for manufacturing a semiconductor device includes the following steps: forming a resist lower layer film using a resist lower layer film forming composition as described in [8] on a semiconductor substrate on which an inorganic film can be formed; forming a resist pattern on the resist lower layer film; using the resist pattern as a mask; dry etching the resist lower layer film to expose the surface of the inorganic film or the semiconductor substrate; using the dry-etched resist lower layer film as a mask; and etching the inorganic film or the semiconductor substrate. [Invention Effects]

[0024] The protective film forming composition of the present invention is required to have, for example, the following characteristics in a well-balanced manner in the lithography process of semiconductor manufacturing: (1) good masking function for wet etching solution during substrate processing; (2) further, by means of low dry etching speed, reducing damage to the protective film or resist underlayer film during substrate processing; (3) excellent planarization of stepped substrates; and (4) excellent embedding of fine trench patterned substrates. By having these properties (1) to (4) in a well-balanced manner, fine processing of semiconductor substrates can be easily performed. Implementation

[0025] <Content for forming protective film in wet etching solutions for semiconductors>

[0026] The protective film forming composition for wet etching solution for semiconductors of the present invention comprises: (A) Polymers having a unit structure represented by the following formula (1-1): (In formula (1-1), Ar represents a benzene ring, a naphthyl ring, or an anthracene ring; R1 represents a hydroxyl group, a methyl-protected mercapto group, a methyl-protected amino group, a halogen group, or an alkyl group with 1 to 10 carbon atoms that can be substituted or interrupted by a heteroatom, or can be substituted by a hydroxyl group; n1 represents an integer from 0 to 3; L1 represents a single bond or an alkyl group with 1 to 10 carbon atoms; E represents an epoxy group; when T1 is n2=1, it represents a single bond or an alkyl group with 1 to 10 carbon atoms that can be interrupted by an ether bond, ester bond, or amide bond; when T1 is n2=2, it represents a nitrogen atom or an amide bond.) (B) Compounds or polymers containing phenolic hydroxyl groups other than catechol; (C) Thermal acid generating agents and (D) Solvent.

[0027] <Polymer (A)> The polymer (A) used in this invention is a polymer having a unit structure represented by the following formula (1-1): (In formula (1-1), Ar represents a benzene ring, naphthalene ring, or anthracene ring; R1 represents a hydroxyl group, a methyl-protected mercapto group, a methyl-protected amino group, a halogen group, or an alkyl group with 1 to 10 carbon atoms that can be substituted or interrupted by a heteroatom or can be substituted by a hydroxyl group as a substituent for the hydrogen atom contained in the aforementioned benzene ring, naphthalene ring, or anthracene ring; n1 represents an integer from 0 to 3; L1 represents a single bond or an alkyl group with 1 to 10 carbon atoms; E represents an epoxy group; when T1 is n2=1, it represents a single bond or an alkyl group with 1 to 10 carbon atoms that can be interrupted by an ether bond, ester bond, or amide bond; when T1 is n2=2, it represents a nitrogen atom or an amide bond).

[0028] Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-Dimethyl-cyclopropyl, 1-Ethyl-cyclopropyl, 2-Ethyl-cyclopropyl, n-Hexyl, 1-Methyl-n-pentyl, 2-Methyl-n-pentyl, 3-Methyl-n-pentyl, 4-Methyl-n-pentyl, 1,1-Dimethyl-n-butyl, 1,2-Dimethyl-n-butyl, 1,3-Dimethyl-n-butyl, 2,2-Dimethyl-n-butyl, 2,3-Dimethyl-n-butyl, 3,3-Dimethyl-n-butyl, 1-Ethyl-n-butyl, 2-Ethyl-n-butyl, 1,1,2-Trimethyl-n-propyl, 1,2,2-Trimethyl-n-propyl, 1-Ethyl- 1-Methyl-n-propyl, 1-Ethyl-2-methyl-n-propyl, Cyclohexyl, 1-Methyl-cyclopentyl, 2-Methyl-cyclopentyl, 3-Methyl-cyclopentyl, 1-Ethyl-cyclobutyl, 2-Ethyl-cyclobutyl, 3-Ethyl-cyclobutyl, 1,2-Dimethyl-cyclobutyl, 1,3-Dimethyl-cyclobutyl, 2,2-Dimethyl-cyclobutyl, 2,3-Dimethyl-cyclobutyl, 2,4-Dimethyl-cyclobutyl, 3,3-Dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl -Cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, decyl, methoxy, ethoxy, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, methylamino, dimethylamino, diethylamino, aminomethyl, 1-aminoethyl, 2-aminoethyl, methylthio, ethylthio, mercaptomethyl, 1-mercaptoethyl, 2-mercaptoethyl, etc.

[0029] Examples of alkyl groups with 1 to 10 carbon atoms include methylene, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isopropyl, s-butyl, t-butyl, cyclopropyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclopropyl, 2 -Methyl-cyclohexyl, 3-methyl-cyclohexyl, 1,2-dimethyl-cyclohexylpropyl, 2,3-dimethyl-cyclohexylpropyl, 1-ethyl-cyclohexylpropyl, 2-ethyl-cyclohexylpropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1- Ethyl-n-extrin-butyl, 2-ethyl-n-extrin-butyl, 1,1,2-trimethyl-n-extrin-propyl, 1,2,2-trimethyl-n-extrin-propyl, 1-ethyl-1-methyl-n-extrin-propyl, 1-ethyl-2-methyl-n-extrin-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl 2,4-Dimethyl-cyclopropyl, 3,3-Dimethyl-cyclopropyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, n-heptanyl, n-octylyl, n-nonylyl or n-decylyl.

[0030] The aforementioned R 1 can be an alkoxy group with 1 to 10 carbon atoms.

[0031] Examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl -n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2,-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy, n-heptyloxy, n-octyloxy, and n-nonyloxy, etc.

[0032] The unit structure represented by the aforementioned formula (1-1) can be of one type or a combination of two or more types. For example, Ar can be a copolymer having multiple unit structures of the same type. For example, Ar can be a unit structure containing a benzene ring or a unit structure containing a naphthalene ring. Copolymers with multiple unit structures of different types of Ar are not excluded from the scope of this application.

[0033] The aforementioned "can be interrupted" refers to the fact that, when the alkyl group has 2 to 10 carbon atoms, any carbon-carbon bond between any of the aforementioned alkyl groups can be interrupted by a heteroatom (i.e., an ether bond when oxygen is present, and a sulfur bond when sulfur is present), an ester bond, or a amide bond. Specifically, it refers to the presence of a heteroatom (i.e., an ether bond when oxygen is present, and a sulfur bond when sulfur is present), an ester bond, or a amide bond in any of the carbon atoms of the alkyl group with 1 carbon atom (i.e., the methylene group).

[0034] When T1 is n2=1, it represents an alkyl group with 1 to 10 carbon atoms that can be interrupted by a single bond, ether bond, ester bond, or amide bond. However, it is more preferably a combination of an ether bond and a methylene group (that is, when "-T1-(E)n2" in formula (1-1) is a glycidyl ether group), a combination of an ester bond and a methylene group, or a combination of an amide bond and a methylene group.

[0035] The term "alkyl group with 1 to 10 carbon atoms that can be replaced by heteroatoms" refers to an alkyl group with 1 to 10 carbon atoms in which one or more hydrogen atoms are replaced by heteroatoms (preferably halogen groups).

[0036] Although the aforementioned L 1 represents a single bond or an alkyl group having 1 to 10 carbon atoms, it is preferred to represent it using the following formula (1-2). (In formula (1-2), R2 and R3 independently represent hydrogen atoms, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, and cyclobutyl, and R2 and R3 can be bonded to each other to form a ring with 3 to 6 carbon atoms). Among these, it is preferred that R2 and R3 are both hydrogen atoms (i.e., -(CR2R3)- is a methylene group).

[0037] The aforementioned halogen group refers to a halogen that has been replaced by hydrogen. -X(F, Cl, Br, I).

[0038] There are no particular limitations on the aforementioned polymer (A) if it has a unit structure that satisfies the aforementioned formula (1-1). It can be manufactured using methods known to the public. Commercially available products can be used. Examples of commercially available products include the heat-resistant epoxy phenolic varnish resin EOCN (registered trademark) series (manufactured by Nippon Kayaku Co., Ltd.) and the epoxy phenolic varnish resin DEN (registered trademark) series (manufactured by Dow Chemical Japan Co., Ltd.).

[0039] The weight average molecular weight of the aforementioned polymer (A) is 100 or more, 500 to 200,000, 600 to 50,000, or 700 to 10,000.

[0040] As for the polymer (A) in this case, examples of polymers with the following unit structures can be listed.

[0041]

[0042] <(B) Compounds or polymers having phenolic hydroxyl groups other than catechol> The aforementioned compound or polymer (B) having phenolic hydroxyl groups other than catechol is not specifically limited if it does not impair the effect of the invention. Furthermore, the aforementioned compound or polymer (B) having phenolic hydroxyl groups other than catechol is different from the aforementioned polymer (A).

[0043] The weight-average molecular weight of the aforementioned compounds or polymers (B) having phenolic hydroxyl groups other than catechol is not particularly limited, but may be, for example, 300 to 50,000.

[0044] The aforementioned compound or polymer (B) is preferably having two or more phenolic hydroxyl groups.

[0045] [1] Compounds or polymers represented by formula (2-1) The aforementioned compound (B) is preferably represented by the following formula (2-1): (In the formula, R2 and T2 each independently represent a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, and alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group. A1 and A2 each independently represent an alkyl group with 1 to 10 carbon atoms, a divalent organogroup derived from a ring compound, a divalent organogroup represented by a phenyl group or -CT2T3-, or a combination thereof. T3 represents a hydrogen atom or a monovalent group represented by (Formula 2-1-a). The * in (Formula 2-1-a) indicates the bonding site with the carbon atom of T3. a represents an integer from 1 to 6. n3 to n5 each independently represent an integer from 0 to 2. r2 represents an integer from 0 to 3. m1 and m2 each independently represent 0 to 10,000,000). Preferably, m1, n3~n5 and r2 are 0, and m2 is 1.

[0046] The descriptions of the halogen group, alkoxy group, and alkyl group in the aforementioned formula (2-1) are as described above.

[0047] Examples of the aforementioned bicyclic compounds include dicyclopentadiene, substituted dicyclopentadiene, tetracyclo[4.4.0.12,5.17,10]dodecyl-3,8-diene, or substituted tetracyclo[4.4.0.12,5.17,10]dodecyl-3,8-diene. The aforementioned substitution refers to the substitution of one or more hydrogen atoms of an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 40 carbon atoms, where one or more hydrogen atoms of the aforementioned bicyclic compound can be independently replaced by a halogen group, nitro group, amino group, or hydroxyl group or such a group. The term "divalent organogroup derived from the bicyclic compound" refers to a group having two bonding portions derived by removing any two hydrogen atoms from the aforementioned bicyclic compound.

[0048] Examples of aryl groups with 6 to 40 carbon atoms include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, and 9-phenanthyl.

[0049] As specific examples of compounds represented by the aforementioned formula (2-1), the following compounds can be listed.

[0050] The compounds (B) above that have phenolic hydroxyl groups other than catechol can be the compounds shown below.

[0051]

[0052] [2] Compounds represented by formula (2-2) The aforementioned compound (B) is a compound having a phenolic hydroxyl group other than catechol. Although not particularly limited, it is preferred that the aforementioned compound (B) be represented by the following formula (2-2) if it does not impair the effect of the invention. (In the formula, R3 represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, and alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group. Q1 represents a single bond, oxygen atom, sulfur atom, sulfonyluyl group, carbonyl group, imino group, aryl group with 6 to 40 carbon atoms, and aryl group with 1 to 10 carbon atoms that can be substituted by a halogen group. a represents an integer from 1 to 6. n6 represents an integer from 0 to 2. r3 represents an integer from 0 to 3.) The alkoxy, alkyl, and halogen groups in formula (2-2) are explained as described above.

[0053] Examples of aryl groups with 6 to 40 carbon atoms include arylphenyl, o-methylarylphenyl, m-methylarylphenyl, p-methylarylphenyl, o-chloroarylphenyl, m-chloroarylphenyl, p-chloroarylphenyl, o-fluoroarylphenyl, p-fluoroarylphenyl, o-methoxyarylphenyl, p-methoxyarylphenyl, p-nitroarylphenyl, p-cyanoarylphenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anethyl, 2-anethyl, 9-anethyl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, and 9-phenanthyl.

[0054] Examples of alkyl groups with 1 to 10 carbon atoms include methylene, ethyl alkyl, n-propyl alkyl, isopropyl alkyl, cyclopropyl alkyl, n-butyl alkyl, isopropyl alkyl, s-butyl alkyl, t-butyl alkyl, cyclopropyl alkyl, 1-methyl-cyclopropyl alkyl, 2-methyl-cyclopropyl alkyl, n-pentyl alkyl, 1-methyl-n-butyl alkyl, 2-methyl-n-butyl alkyl, 3-methyl-n-butyl alkyl, 1,1-dimethyl-n-propyl alkyl, 1,2-dimethyl-n-propyl alkyl, 2,2-dimethyl-n-propyl alkyl, 1-ethyl-n-propyl alkyl, cyclopentyl alkyl, 1-methyl-cyclopropyl alkyl, 2-methyl alkyl-n-propyl alkyl, ethyl-n-propyl alkyl, cyclopropyl alkyl, 1-methyl-cyclopropyl alkyl, 2-methyl alkyl-n-propyl alkyl, ethyl alkyl, cyclopropyl alkyl, 1-methyl-cyclopropyl alkyl, 2-methyl alkyl-n-propyl alkyl, ethyl alkyl, cyclopropyl alkyl, 1-methyl-cyclopropyl alkyl, 2-methyl alkyl, ethyl ... 1,2-Dimethyl-cyclohexyl, 3-methyl-cyclohexyl, 1,2-dimethyl-cyclohexylpropyl, 2,3-dimethyl-cyclohexylpropyl, 1-ethyl-cyclohexylpropyl, 2-ethyl-cyclohexylpropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl... 1,1,2-trimethyl-n-epynyl, 2-ethyl-n-epynyl, 1,2,2-trimethyl-n-epynyl, 1-ethyl-1-methyl-n-epynyl, 1-ethyl-2-methyl-n-epynyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl 2,4-Dimethyl-cyclopropyl, 3,3-Dimethyl-cyclopropyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, n-heptanyl, n-octylyl, n-nonylyl or n-decylyl.

[0055] As specific examples of compounds represented by the aforementioned formula (2-2), the following compounds can be listed.

[0056] The aforementioned compound (B) can be represented by the following formula (4-1): (In the formula, R5 represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, or alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group. In the formula, n8 represents an integer of 4, 5, 6, or 8). The explanations for the terms used above are as described above.

[0057] Specific examples of compounds represented by formula (4-1) are shown below.

[0058] The aforementioned compound (B) can be of the following formulas (5-1) and (5-1-a): (In the formula, n9 and n10 represent integers of 0 or 1, respectively; R6 represents halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by alkyl group with 1 to 3 carbon atoms, and alkyl group with 1 to 10 carbon atoms that can be substituted by hydroxyl or halogen group. a represents integers of 1 to 6. n11 represents integers of 1 or 2. r5 represents integers of 0 to 3. * represents the bonding site between the compound of formula (5-1) and the compound of formula (5-1-a).) The explanations for the terms used above are as described above.

[0059] Specific examples of compounds represented by formulas (5-1) and (5-1-a) are shown below.

[0060] The compounds mentioned in (B) that have phenolic hydroxyl groups other than catechol can be the compounds shown below.

[0061]

[0062] [3] Polymers containing phenolic hydroxyl groups other than catechol The aforementioned compound or polymer (B) having phenolic hydroxyl groups other than catechol can be defined as a polymer (B) having phenolic hydroxyl groups other than catechol. However, if it is a polymer that does not impair the effect of the invention, it is not specifically limited.

[0063] The aforementioned polymer (B) preferably has a structure with at least 3 repeating units.

[0064] The weight average molecular weight of the aforementioned polymer (B) is not particularly limited, but is, for example, 1,000 to 50,000.

[0065] The aforementioned polymer (B) preferably comprises a unit structure represented by the following formula (3-1): (In the formula, T4 represents an alkyl group with 1 to 10 carbon atoms that can be substituted by a halogen group. R4 represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, or alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group. r4 represents an integer from 0 to 3. n7 represents an integer from 0 to 2. a represents an integer from 1 to 6.) The descriptions of the aforementioned halogen groups, alkyl groups, and alkoxy groups are as described above.

[0066] The polymer represented by the aforementioned formula (3-1) may be a polymer containing one unit structure represented by formula (3-1), or it may be a copolymer containing two or more types.

[0067] As a specific example of the polymer (B) represented by the aforementioned formula (3-1), polymers containing the unit structures described below can be listed.

[0068] (In the above formula, m and n, which are repeated horizontally, represent the mole ratio of copolymerization).

[0069] <Hot Acid Generator> The protective film forming composition in this case may further include a hot acid generating agent.

[0070] Examples of heat-generating agents include pyridinium-p-toluenesulfonate, pyridinium-trifluoromethanesulfonate, pyridinium-p-phenolsulfonate, K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, and TAG2689 (all manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

[0071] These hot acid generating agents can be used in combination of one or more.

[0072] When the protective film forming composition of this case contains a hot acid generating agent, its content relative to the total solid content of the protective film forming composition is 0.0001 to 20% by mass, preferably 0.01 to 15% by mass, and even more preferably 0.1 to 10% by mass.

[0073] Solvent The protective film forming composition of the present invention can be prepared by dissolving the aforementioned components in a solvent, preferably in an organic solvent, and used in a homogeneous solution state.

[0074] As the organic solvent for the protective film forming composition of the present invention, any organic solvent that can dissolve the aforementioned compounds or solid components such as acid catalysts described below may be used without particular restriction. In particular, since the protective film forming composition of the present invention is used in a homogeneous solution state, it is recommended to use a commonly used organic solvent in the photolithography step when considering its coating performance.

[0075] Examples of organic solvents mentioned above include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, and 2-hydroxyisobutyric acid. Methyl acetate, ethyl 2-hydroxyisobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0076] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0077] The solid component of the protective film forming composition of the present invention is typically defined as 0.1 to 70% by mass, and preferably 0.1 to 60% by mass. The solid component refers to the proportion of all components in the protective film forming composition after removing the solvent. The proportion of the polymer represented by the aforementioned formula (1-1) in the solid component is preferably in the order of 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass.

[0078] <Inhibitor Underlayer Film Formation Composition> The inhibitor lower film forming composition of the present invention comprises (A) a polymer having a unit structure represented by the following formula (1-1): (In formula (1-1), Ar represents a benzene ring, a naphthyl ring, or an anthracene ring; R1 represents a hydroxyl group, a methyl-protected mercapto group, a methyl-protected amino group, a halogen group, or an alkyl group with 1 to 10 carbon atoms that can be substituted or interrupted by a heteroatom, or can be substituted by a hydroxyl group; n1 represents an integer from 0 to 3; L1 represents a single bond or an alkyl group with 1 to 10 carbon atoms; E represents an epoxy group; when T1 is n2=1, it represents a single bond or an alkyl group with 1 to 10 carbon atoms that can be interrupted by an ether bond, ester bond, or amide bond; when T1 is n2=2, it represents a nitrogen atom or an amide bond.) (B) Compounds or polymers containing phenolic hydroxyl groups other than catechol; (C) Thermal acid generating agents and (D) Solvent. The description of the terminology used in this case regarding the inhibitor lower film forming composition is the same as that used in the description of the aforementioned protective film forming composition.

[0079] <Manufacturing Method of Protective Film, Resistor Underlayer Film, Resistor Patterned Substrate, and Semiconductor Device> The following describes a method for manufacturing a substrate with a resist pattern using the protective film forming composition (resistor underlayer film forming composition) of the present invention, and a method for manufacturing a semiconductor device.

[0080] The substrate with the resist pattern of the present invention can be manufactured by coating the aforementioned protective film forming composition (resist underlayer film forming composition) onto a semiconductor substrate and firing it.

[0081] Semiconductor substrates for coating the protective film forming composition (resistor underlayer film forming composition) of the present invention can include, for example, silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0082] When used in semiconductor substrates for forming inorganic films on their surfaces, these inorganic films are formed using methods such as ALD (Atomic Layer Deposition), CVD (Chemical Vapor Deposition), reactive sputtering, ion plating, vacuum evaporation, and spin-on-glass (SOG). Examples of such inorganic films include polysilicon films, silicon oxide films, silicon nitride films, silicon oxynitride films, BPSG (Boro-Phospho Silicate Glass) films, titanium nitride films, titanium oxynitride films, tungsten nitride films, gallium nitride films, and gallium arsenide films. The semiconductor substrate can be a stepped substrate with so-called "vias," "trenches," etc. For example, a "via" is slightly circular when viewed from above, with a diameter of, for example, 2 nm to 20 nm and a depth of, 50 nm to 500 nm. A "trench," for example, a trench (a recess in the substrate), has a width of 2 nm to 20 nm and a depth of 50 nm to 500 nm. The protective film forming composition (resistor underlayer film forming composition) in this case has small weight average molecular weight and average particle size of the compounds contained in the composition. As mentioned above, there are no defects such as voids (pores) in the stepped substrate, and the composition can be embedded in the composition. For the next step in semiconductor manufacturing (wet etching / dry etching of semiconductor substrate, resist pattern formation), the absence of defects such as voids is an important characteristic.

[0083] On such a semiconductor substrate, the protective film forming composition (resistor underlayer film forming composition) of the present invention is coated using a suitable coating method such as a spinner or coating machine. Then, the protective film (resistor underlayer film) is formed by baking using a heating means such as a hot plate. The baking conditions can be appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes; more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes. The thickness of the formed protective film is, for example, 0.001 μm to 10 μm, preferably 0.002 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm. When the baking temperature is lower than the aforementioned range, the cross-linking may not be sufficient, making it difficult to obtain the protective film (resistor underlayer film formation composition) with resistance to resistor solvents or alkaline hydrogen peroxide aqueous solutions. On the other hand, when the baking temperature is higher than the aforementioned range, the protective film (resistor underlayer film) may decompose due to heat.

[0084] Exposure is performed using a mask (reticle) to form a specified pattern, such as an i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam). For development, an alkaline developer is used, with a development temperature ranging from 5°C to 50°C and a development time from 10 seconds to 300 seconds appropriately selected. Examples of alkaline developers include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alkanolamines such as dimethylethanolamine and triethanolamine; fourth-order ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; cyclic amines such as pyrrole and piperidine; and aqueous solutions of other alkaline bases. Furthermore, an appropriate amount of surfactants such as isopropyl alcohol or nonionic surfactants can be added to the aforementioned aqueous solution of alkaline substances. Among these, the developer is preferably a quaternary ammonium salt, and more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers. Alternatively, an alternative alkaline developer can be used, employing an organic solvent such as butyl acetate for development, to address the portion of the photoresist that cannot be improved by increasing the alkaline dissolution rate.

[0085] Next, using the formed resist pattern as a mask, the aforementioned protective film (resist underlayer film formation composition) is dry-etched. At this time, when the aforementioned inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed; when the aforementioned inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed.

[0086] Furthermore, by using the protective film (resistor underlayer film composition) formed after dry etching (when the resistor pattern remains on the protective film / resistor underlayer film, the resistor pattern is also present) as a mask, wet etching is performed using a semiconductor wet etching solution to form the desired pattern.

[0087] As a wet etching solution for semiconductors, it can be used with general solutions for etching semiconductor wafers, such as acidic or alkaline substances.

[0088] Examples of substances that exhibit acidity include hydrogen peroxide, hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, ammonium hydrogen fluoride, buffered hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, or mixtures thereof.

[0089] Substances exhibiting alkalinity can include organic amines such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, and triethanolamine mixed with hydrogen peroxide to produce alkaline hydrogen peroxide solution. A specific example is SC-1 (ammonia-hydrogen peroxide solution). Other substances that can make the pH alkaline include, for instance, mixing urea and hydrogen peroxide solution, and then heating to cause the thermal decomposition of urea to produce ammonia, ultimately making the pH alkaline. Such solutions can also be used as wet etching solutions.

[0090] Of these, acidic hydrogen peroxide water or alkaline hydrogen peroxide water is preferred.

[0091] These solutions may contain additives such as surfactants.

[0092] The desired operating temperature for the wet etching solution used in semiconductors is 25°C to 90°C, and more preferably 40°C to 80°C. The desired wet etching time is 0.5 minutes to 30 minutes, and more preferably 1 minute to 20 minutes. [Example]

[0093] Although the following examples illustrate the contents of the present invention, the present invention is not limited thereto.

[0094] The weight-average molecular weights of the compounds shown in Synthetic Examples 1 to 8 of this specification were determined by gel permeation chromatography (hereinafter referred to as GPC). A GPC apparatus manufactured by Tosoh Corporation was used in the determination, and the determination conditions were as follows.

[0095] GPC tubing: Shodex KF803L, Shodex KF802, Shodex KF801 [Registered Trademark] (Showa Denko Co., Ltd.) Column temperature: 40℃ Solvent: Tetrahydrofuran (THF) Flow rate: 1.0 ml / min Standard sample: Polystyrene (Tosoh Corporation)

[0096] <Terminology Explanation> PGME: Propylene Glycol Monomethyl Ether PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0097] <Example 1> A 4.3% by weight solution of epoxy phenolic varnish resin EOCN-104S (produced by Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) was prepared by mixing 5.92g of TrisP-HAP (produced by Honshu Chemical Industry Co., Ltd., equivalent to formula (a-2)) (6% by weight PGME solution), 3.55g of K-PURE [trademark registered] TAG-2689 (produced by King Industries Co., Ltd.) as a hot acid generator (0.5% by weight PGME solution), 0.18g of R-40-LM (DIC Co., Ltd.) (1% by weight PGMEEA solution), 29.18g of PGMEA, and 5.26g of PGME. This solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2μm to form a protective film.

[0098]

[0099] <Example 2> A 4.5% (w / w) solid solution was prepared by mixing 5.32 g of epoxy phenolic varnish resin EOCN-104S (produced by Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) (30% PGMEA solution, weight average molecular weight 3,100), 10.63 g of TrisP-HAP (produced by Honshu Chemical Industry Co., Ltd., equivalent to formula (a-2)) (6% PGMEA solution), 3.19 g of K-PURE [trademark registered] TAG-2689 (produced by King Industries Co., Ltd.) as a hot acid generator (0.5% PGMEA solution), 0.18 g of R-40-LM (DIC Co., Ltd.) (1% PGMEA solution), 29.55 g of PGMEA, and 1.16 g of PGME. This solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to form a protective film.

[0100]

[0101] <Example 3> A 4.0% by weight solution of epoxy phenolic varnish resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) was prepared, consisting of 2.40 g (30% by weight PGMEA solution, weight average molecular weight 3,100), 0.24 g (30% by weight PGMEA solution) of VP-8000 (a product of Nippon Soda Co., Ltd., equivalent to formula (a-3), weight average molecular weight 10,257), 0.72 g (1% by weight PGMEA solution) of K-PURE [trademark registered] TAG-2689 (a product of King Industries Co., Ltd.) as a hot acid generator, 0.072 g (1% by weight PGMEA solution) of R-40-LM (DIC Co., Ltd.) (1% by weight PGMEA solution), 11.52 g of PGMEA, and 5.05 g of PGME. This solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to form a protective film.

[0102]

[0103] <Example 4> A 4.0% (w / w) solution of epoxy phenolic varnish resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) was prepared, consisting of 2.03 g of EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-3), weight average molecular weight 10,257), 0.61 g of VP-8000 (a product of Nippon Soda Co., Ltd., equivalent to formula (a-3), weight average molecular weight 10,257), 0.61 g of K-PURE [trademark registered] TAG-2689 (a product of King Industries Co., Ltd.) as a hot acid generator, 0.061 g of R-40-LM (a product of DIC Co., Ltd.) (a product of 1% (w / w) PGMEA), 11.53 g of PGMEA, and 5.16 g of PGME. This solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to form a protective film.

[0104]

[0105] <Example 5> A 4.0% (w / w) solid solution was prepared by mixing 3.60 g of epoxy phenolic varnish resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) (30% PGMEA solution, weight average molecular weight 3,100), 2.70 g of TEP-DF (a product of Asahi Organics Co., Ltd., equivalent to formula (a-4)) (4% PGMEA solution), 1.08 g of K-PURE [trademark registered] TAG-2689 (a product of King Industries Co., Ltd.) as a hot acid generator (1% PGMEA solution), 0.11 g of R-40-LM (DIC Co., Ltd.) (1% PGMEA solution), 17.53 g of PGMEA, and 4.98 g of PGME. This solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to form a protective film.

[0106]

[0107] <Example 6> A 4.0% (w / w) solution of epoxy phenolic varnish resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) was prepared, consisting of 3.05 g of EOCN-104S (30% PGMEA solution, weight average molecular weight 3,100), 6.87 g of TEP-DF (4% PGMEA solution, equivalent to formula (a-4)), 0.92 g of K-PURE (trademark registered) TAG-2689 (King Industries Co., Ltd.) as a hot acid generator (1% PGMEA solution), 0.092 g of R-40-LM (DIC Co., Ltd.) (1% PGMEA solution), 17.93 g of PGMEA, and 1.14 g of PGME. This solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to form a protective film.

[0108]

[0109] <Example 7> A 4.0% (w / w) solid solution was prepared by mixing 3.60 g of epoxy phenolic varnish resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) (30% PGMEA solution, weight average molecular weight 3,100), 2.70 g of TEP-TPA (a product of Asahi Organics Co., Ltd., equivalent to formula (a-5)) (4% PGMEA solution), 1.08 g of K-PURE [trademark registered] TAG-2689 (a product of King Industries Co., Ltd.) as a hot acid generating agent (1% PGMEA solution), 0.108 g of R-40-LM (DIC Co., Ltd.) (1% PGMEA solution), 17.53 g of PGMEA, and 4.98 g of PGME. This solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to form a protective film.

[0110]

[0111] <Example 8> A 4.0% (w / w) solution of epoxy phenolic varnish resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) was prepared, consisting of 3.05 g of EOCN-104S (30% PGMEA solution, weight average molecular weight 3,100), 6.87 g of TEP-TPA (4% PGMEA solution, equivalent to formula (a-5)), 0.92 g of K-PURE (trademark registered) TAG-2689 (King Industries Co., Ltd.) as a hot acid generator (1% PGMEA solution), 0.092 g of R-40-LM (DIC Co., Ltd.) (1% PGMEA solution), 17.93 g of PGMEA, and 1.14 g of PGME. This solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to form a protective film.

[0112]

[0113] <Example 9> A 4.0% (w / w) solution of epoxy phenolic varnish resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) was prepared by mixing 2.40g of EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-6), equivalent to formula (a-6), equivalent to formula (a-1)), 0.24g of NM8280G (a product of Asahi Organics Co., Ltd., equivalent to formula (a-6), equivalent to formula (a-6), equivalent to formula (a-6), equivalent to formula (a-1)), 0.72g of K-PURE (trademark registered) TAG-2689 (a product of King Industries Co., Ltd.) as a hot acid generator, 0.072g of R-40-LM (a product of DIC Co., Ltd.) (a product of 1% (w / w) PGMEA), 11.52g of PGMEA, and 5.05g of PGME. This solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2μm to form a protective film.

[0114]

[0115] <Example 10> A 4.0% (w / w) solution of epoxy phenolic varnish resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) was prepared by mixing 2.03g of EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-6), weight average molecular weight 6,819) with 0.60g of NM8280G (a product of Asahi Organics Co., Ltd., equivalent to formula (a-6), weight average molecular weight 6,819), 0.61g of K-PURE [trademark registered] TAG-2689 (a product of King Industries Co., Ltd.) as a hot acid generator with 11.53g of PGMEA and 5.76g of PGMEA. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2μm to form a protective film.

[0116]

[0117] <Comparative Example 1> A mixture of epoxy phenolic varnish resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., equivalent to formula (a-1) 7.46g (30% by mass PGMEA solution, weight average molecular weight 3,100), K-PURE [trademark registered] TAG-2689 (a product of King Industries Co., Ltd.) as a hot acid generating agent 2.68g (0.5% by mass PGMEA solution), 28.21g of PGMEA and 11.65g of PGMEA, as a 4.5% by mass solution of solid components, was prepared by filtering the solution using a polytetrafluoroethylene microfilter with a pore size of 0.2μm to form a protective film.

[0118]

[0119] (Coating formation) By spin-coating the protective film forming composition prepared in Examples 1 to 10 and the film forming composition prepared in Comparative Example 1 onto a silicon substrate on which a titanium nitride film is formed on the surface, and baking at 250°C for 60 seconds, a coating film with a thickness of 100 nm is produced.

[0120] (Tolerance test to alkaline hydrogen peroxide aqueous solution) For the protective film forming compositions prepared in Examples 1 to 10 and for the protective film forming composition prepared in Comparative Example 1, the coatings formed on a silicon substrate with a titanium nitride film formed on the surface were immersed in an alkaline hydrogen peroxide aqueous solution of the composition shown in Table 1 below at the same temperature as shown in the table. The state of the coatings after washing with water and drying was then visually observed. The results are shown in Table 2 below. The values ​​in Table 2 are expressed as the ratio of the time observed when the comparative examples were peeled off at the baseline.

[0121] Based on the results in Table 2 above, the coatings made from the protective film forming compositions prepared in Examples 1 to 10, compared with Comparative Example 1, showed improved resistance to alkaline hydrogen peroxide aqueous solution.

[0122] (Optical parameter testing) The protective film formulations prepared according to Examples 1-10 and Comparative Example 1 described in this specification were coated onto silicon wafers using a spinner. The wafers were then baked at 250°C for 1 minute on a hot plate to form a resist underlayer film (film thickness 50 nm). Furthermore, the n-value (refractive index) and k-value (attenuation coefficient or absorption coefficient) of these films were measured at wavelengths of 193 nm and 248 nm using a spectrophotometer (JAWoollam, VUV-VASE VU-302). The results are shown in Table 3.

[0123] [Industrial Applicability]

[0124] The protective film forming composition of the present invention exhibits excellent resistance and a low dry etching rate when wet etching solutions are applied during substrate processing, thus providing a protective film with minimal damage during substrate processing. The resist underlayer film forming composition of the present invention also exhibits excellent resistance and a low dry etching rate when wet etching solutions are applied during substrate processing.

Claims

1. A protective film forming composition for wet etching solutions for semiconductors, comprising: (A) a polymer having a unit structure represented by the following formula (1-1):

1. (In formula (1-1), Ar represents a benzene ring, a naphthalene ring, or an anthracene ring; R1 represents a hydroxyl group, a methyl-protected mercapto group, a methyl-protected amino group, a halogen group, or an alkyl group with 1 to 10 carbon atoms that can be substituted or interrupted by a heteroatom, or can also be substituted by a hydroxyl group; n1 represents an integer from 0 to 3; L1 represents a single bond or an alkyl group with 1 to 10 carbon atoms; E represents an epoxy group; when T1 is n2=1, it represents a single bond or an alkyl group with 1 to 10 carbon atoms that can be interrupted by an ether bond, ester bond, or amide bond; when T1 is n2=2, it represents a nitrogen atom or an amide bond), (B) compounds having phenolic hydroxyl groups other than catechol. Or a polymer, (C) a hot acid generating agent and (D) a solvent, wherein the aforementioned compound or polymer is a compound or polymer represented by formula (2-1), a compound represented by formula (2-2), a polymer containing a unit structure represented by formula (3-1), or a polymer containing a unit structure represented by any one of formulas (3-1-a) to (3-1-o), wherein the aforementioned compound or polymer has two or more phenolic hydroxyl groups, wherein the weight average molecular weight of the aforementioned polymer (A) is 500 to 200,000, and the weight average molecular weight of the aforementioned polymer (B) is 1,000 to 50,000.

1. (In the formula, R2 and T2 each independently represent a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group; A1 and A2 each independently represent an alkyl group with 1 to 10 carbon atoms, a divalent organic group derived from a ring compound, a divalent organic group represented by a phenyl group or -CT2T3-, or a combination thereof; T3 represents a hydrogen atom or a monovalent group represented by (Formula 2-1-a):) 1. In (Equation 2-1-a), * indicates the bonding site of the carbon atom bonded to T3; a represents an integer from 1 to 6; n3 to n5 each independently represent an integer from 0 to 2; r2 represents an integer from 0 to 3; m1 and m2 each independently represent a number from 0 to 10,000,000.

1. (In the formula, R3 represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, and alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group; Q1 represents a single bond, oxygen atom, sulfur atom, sulfonyluyl group, carbonyl group, imino group, aryl group with 6 to 40 carbon atoms, and aryl group with 1 to 10 carbon atoms that can be substituted by a halogen group; a represents an integer from 1 to 6; n6 represents an integer from 0 to 2; r3 represents an integer from 0 to 3) 1. (In the formula, T4 represents an alkyl group with 1 to 10 carbon atoms that can be substituted by a halogen group; R4 represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, or alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group; r4 represents an integer from 0 to 3; n7 represents an integer from 0 to 2; a represents an integer from 1 to 6) 1. (In the above formula, the repeated units m and n represent the mole ratio of copolymerization).

2. As in claim 1, the protective film forming composition, wherein, In the aforementioned equation (2-1), m1, n3~n5 and r2 are 0, and m2 is 1.

3. A protective film for a wet etching solution for semiconductors, characterized in that it is a sintered product of a coating film composed of a protective film forming composition as claimed in claim 1 or 2.

4. A resistive underlayer film forming composition comprising (A) a polymer having a unit structure represented by the following formula (1-1):

4. (In formula (1-1), Ar represents a benzene ring, a naphthalene ring, or an anthracene ring; R1 represents a hydroxyl group, a methyl-protected mercapto group, a methyl-protected amino group, a halogen group, or an alkyl group with 1 to 10 carbon atoms that can be substituted or interrupted by a heteroatom, or can also be substituted by a hydroxyl group; n1 represents an integer from 0 to 3; L1 represents a single bond or an alkyl group with 1 to 10 carbon atoms; E represents an epoxy group; when T1 is n2=1, it represents a single bond or an alkyl group with 1 to 10 carbon atoms that can be interrupted by an ether bond, ester bond, or amide bond; when T1 is n2=2, it represents a nitrogen atom or an amide bond), (B) compounds having phenolic hydroxyl groups other than catechol. Or a polymer, (C) a hot acid generating agent and (D) a solvent, wherein the aforementioned compound or polymer is a compound or polymer represented by formula (2-1), a compound represented by formula (2-2), a polymer containing a unit structure represented by formula (3-1), or a polymer containing a unit structure represented by any one of formulas (3-1-a) to (3-1-o), wherein the aforementioned compound or polymer has two or more phenolic hydroxyl groups, wherein the weight average molecular weight of the aforementioned polymer (A) is 500 to 200,000, and the weight average molecular weight of the aforementioned polymer (B) is 1,000 to 50,000.

4. (In the formula, R2 and T2 each independently represent a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group; A1 and A2 each independently represent an alkyl group with 1 to 10 carbon atoms, a divalent organic group derived from a ring compound, a divalent organic group represented by a phenyl group or -CT2T3-, or a combination thereof; T3 represents a hydrogen atom or a monovalent group represented by (Formula 2-1-a):) 4. In (Equation 2-1-a), * indicates the bonding site of the carbon atom bonded to T3; a represents an integer from 1 to 6; n3 to n5 each independently represent an integer from 0 to 2; r2 represents an integer from 0 to 3; m1 and m2 each independently represent a number from 0 to 10,000,000.

4. (In the formula, R3 represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, and alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group; Q1 represents a single bond, oxygen atom, sulfur atom, sulfonyluyl group, carbonyl group, imino group, aryl group with 6 to 40 carbon atoms, and aryl group with 1 to 10 carbon atoms that can be substituted by a halogen group; a represents an integer from 1 to 6; n6 represents an integer from 0 to 2; r3 represents an integer from 0 to 3) 4. (In the formula, T4 represents an alkyl group with 1 to 10 carbon atoms that can be substituted by a halogen group; R4 represents a halogen group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group with 1 to 9 carbon atoms, amino group that can be substituted by an alkyl group with 1 to 3 carbon atoms, or alkyl group with 1 to 10 carbon atoms that can be substituted by a hydroxyl group or a halogen group; r4 represents an integer from 0 to 3; n7 represents an integer from 0 to 2; a represents an integer from 1 to 6) 4. (In the above formula, the repeated units m and n represent the mole ratio of copolymerization).

5. A resistive underlayer film, characterized in that it is a sintered product of a coating film composed of a resistive underlayer film forming composition as claimed in claim 4.

6. A method for manufacturing a substrate with a protective film, characterized in that it is used in the manufacture of semiconductors, and includes the step of coating a protective film forming composition as claimed in claim 1 or 2 onto a semiconductor substrate having a stepped surface and firing it to form a protective film.

7. A method for manufacturing a substrate with a resist pattern, characterized by comprising the steps of coating a protective film composition as claimed in claim 1 or 2 or a resist underlayer film forming composition as claimed in claim 4 onto a semiconductor substrate and firing it to form a protective film as a resist underlayer film; forming a resist film on the protective film; and then exposing and developing it to form a resist pattern, and using it in the manufacture of semiconductors.

8. A method for manufacturing a semiconductor device, comprising the steps of forming a composition using a protective film as claimed in claim 1 or 2 on a semiconductor substrate on which an inorganic film can be formed, forming a protective film, forming a resist pattern on the protective film, using the resist pattern as a mask, dry etching the protective film to expose the surface of the inorganic film or the semiconductor substrate, using the dry-etched protective film as a mask, wet etching and cleaning the inorganic film or the semiconductor substrate using a semiconductor wet etching solution.

9. A method for manufacturing a semiconductor device, comprising the steps of forming a composition using a resist underlayer film as claimed in claim 4 on a semiconductor substrate on which an inorganic film can be formed, forming a resist underlayer film, forming a resist pattern on the resist underlayer film, using the resist pattern as a mask, dry etching the resist underlayer film to expose the surface of the inorganic film or the semiconductor substrate, and using the dry-etched resist underlayer film as a mask to etch the inorganic film or the semiconductor substrate.

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