Chemical liquid resistant protective film

Abstract

Provided is a composition for forming a protective film, which is capable of forming a protective film having excellent resistance to a wet etching solution for semiconductors, has a high etching rate during dry etching, and can be effectively used as a composition for forming a resist underlayer film. A composition for forming a protective film for a wet etching solution for semiconductors, which contains (A) a compound or polymer having an epoxy structure represented by formula (I), (B) a compound having a thiol structure, and (C) a solvent. (In formula (I), * represents a bonding site. And n represents 1 or 2. X represents an ether bond, an ester bond, or an amide bond when n = 1, and X represents a nitrogen atom or an amide bond when n = 2. )

Description

Technical Field

[0001] This invention relates to a composition for forming a protective film, particularly resistant to wet etchants for semiconductors, and preferably to acidic or alkaline aqueous solutions of hydrogen peroxide, in the photolithography process of semiconductor manufacturing. Furthermore, it relates to methods for manufacturing the protective film formed from the above composition and a substrate with a resist pattern applied to the protective film, as well as methods for manufacturing semiconductor devices. Background Technology

[0002] In semiconductor manufacturing, photolithography is a well-known process that involves placing a photoresist underlayer between a substrate and a photoresist film formed thereon to form a photoresist pattern of the desired shape.

[0003] Patent Document 1 discloses an antireflective coating composition comprising a polymer having a glycidyl group and a polymer having an aromatic group substituted with a hydroxyl group, for use with an externally applied photoresist, and a method for forming a photoresist underlayer film therefrom and for exposure, development, and patterning.

[0004] Patent Document 2 discloses a method for forming a photoresist relief image by coating a composition containing a resin containing epoxy reactive groups such as hydroxyl groups and a crosslinked resin containing epoxy groups onto a substrate and forming a photoresist layer thereon.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2017-107185

[0008] Patent Document 2: Japanese Patent Application Publication No. 2017-187764 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] When a protective film is formed on a semiconductor substrate using a protective film forming composition, and the protective film is used as an etching mask for processing the substrate by wet etching, the protective film is required to have good shielding function against the wet etching solution for semiconductors (i.e., the shielded portion can protect the substrate).

[0011] Previously, to demonstrate resistance to wet etching chemicals, the crosslinking of protective films utilized the reaction of epoxy groups and hydroxyl groups. However, considering its reactivity, the hydroxyl groups required direct bonding to the aromatic ring structure. Furthermore, compositions with typical aromatic ring structures generally exhibit slow etching rates during dry etching due to their high carbon content, making it difficult to achieve high etching rates (ER).

[0012] Therefore, the object of the present invention is to provide a composition for forming a protective film that is capable of forming a protective film with excellent resistance to wet etchants for semiconductors and has a fast etching rate during dry etching and can achieve a high etch rate (ER), and the composition can also be effectively used as a composition for forming a resist underlayer film.

[0013] Methods for solving problems

[0014] In order to solve the above-mentioned problems, the inventors conducted in-depth research and discovered the following composition, which is a crosslinking system of epoxy groups that does not depend solely on the aromatic ring structure by using thiol groups to replace hydroxyl groups. This composition can form a protective film that has high resistance to wet etching solutions, fast etching speed during dry etching, and high etching rate (ER), thus completing the present invention.

[0015] That is, the present invention includes the following solutions.

[0016] [1] A composition for forming a protective film for a wet etching solution for semiconductors, comprising:

[0017] (A) Compounds or polymers having the epoxy structure shown in formula (I) below,

[0018] (B) Compounds with a thiol structure, and

[0019] (C) Solvent.

[0020]

[0021] (In formula (I), * indicates a bonding site. n represents 1 or 2. When n=1, X represents an ether bond, ester bond, or amide bond; when n=2, X represents a nitrogen atom or an amide bond.)

[0022] [2] The protective film forming composition according to [1] further comprises (D) a curing agent.

[0023] [3] The protective film forming composition according to [1] or [2] further comprises (E) a compound or polymer having phenolic hydroxyl groups.

[0024] [4] According to the protective film forming composition of [1], the above-mentioned (A) compound is a compound containing a portion of the structure shown in the following formula (III).

[0025]

[0026] (In formula (III), Ar represents a benzene ring, naphthalene ring, or anthracene ring. n represents 1 or 2. When n=1, X represents an ether bond, ester bond, or amide bond; when n=2, X represents a nitrogen atom or an amide bond.)

[0027] [5] According to the protective film forming composition of [1], the polymer (A) is a polymer containing a phenolic varnish structure having a unit structure shown in the following formula (1-1).

[0028]

[0029] (In formula (1-1), Ar represents a benzene ring, naphthalene ring, or anthracene ring, R 1 The group represents a hydroxyl group, a mercapto group that can be protected by a methyl group, an amino group that can be protected by a methyl group, a halogroup, 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; L 1 Indicates a single bond or an alkylene group with 1 to 10 carbon atoms, n2 represents 1 or 2, E represents a group with an epoxy group or a group with an oxetyl group, and when n2=1, T 1 This refers to an alkylene group with 1 to 10 carbon atoms that can be interrupted by ether, ester, or amide bonds. When n2=2, T 1 This refers to a trivalent hydrocarbon group with 1 to 10 carbon atoms that can be interrupted by a nitrogen atom or an amide bond.

[0030] [6] According to the protective film forming composition of [1], the compound having a thiol structure in (B) above is a polyfunctional thiol compound represented by the following formula (10-1).

[0031]

[0032] (In equation (10-1), R) 7 Indicates a single bond or a straight-chain or branched alkylene group with 1-6 carbon atoms; X represents a single bond or ester bond; A represents an organogroup or heteroatom with 2-12 carbon atoms; r 1 (Represents integers from 2 to 6.)

[0033] [7] In the protective film forming composition according to [2], the curing agent (D) is an alkali.

[0034] [8] In the protective film forming composition according to [7], the base is an imidazole compound.

[0035] [9] According to the protective film forming composition of [8], the above-mentioned base is represented by the following formula (B1).

[0036]

[0037] (In formula (B1), R) 1R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a substituted aryl group, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of a substituted triazine ring, a cyano group, a hydroxyl group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group. 2 R represents an alkylene group having 1 to 4 carbon atoms. 3 R represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group that can be substituted. 4 R represents a hydrogen atom, a formyl group, an alkyl group with 1 to 4 substituted carbon atoms, or an alkoxyalkyl group with 4 or fewer substituted carbon atoms. 5 (This represents a hydrogen atom, a formyl group, an alkyl group with 1 to 4 substituted carbon atoms, or an alkoxyalkyl group with 4 or fewer substituted carbon atoms; n represents 0 or 1.)

[0038]

[10] According to the protective film forming composition of [3], the above (E) compound or polymer having phenolic hydroxyl groups has two or more phenolic hydroxyl groups.

[0039]

[11] According to the protective film forming composition of [3], the above (E) compound or polymer having phenolic hydroxyl groups is a polymer containing the unit structure shown in the following formula (3-1).

[0040]

[0041] (where T is in the formula) 4 R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms that can be substituted by a halogroup. 4 This indicates a halogenated 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 with an alkyl group with 1 to 3 carbon atoms, or alkyl group with 1 to 10 carbon atoms that can be substituted with a hydroxyl group or a halogenated 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.

[0042]

[12] A protective film for a wet etching solution for semiconductors, characterized in that it is a sintered product of a coating film formed by any one of the protective film forming compositions described in any one of [1] to

[11] .

[0043]

[13] A composition for forming a resist underlayer film, comprising:

[0044] (A) Compounds or polymers having the epoxy structure shown in formula (I) below,

[0045] (B) Compounds with a thiol structure, and

[0046] (C) Solvent.

[0047]

[0048] (In formula (I), * indicates a bonding site. n represents 1 or 2. When n=1, X represents an ether bond, ester bond, or amide bond; when n=2, X represents a nitrogen atom or an amide bond.)

[0049]

[14] A method for manufacturing a substrate with a protective film, characterized in that it includes a step of coating a protective film forming composition as described in any one of [1] to

[11] onto a semiconductor substrate and firing it to form a protective film, the manufacturing method being used to manufacture a semiconductor.

[0050]

[15] A method for manufacturing a substrate with a resist pattern, characterized in that it comprises a step of coating a protective film forming composition of any one of [1] to

[11] or a resist underlayer forming composition of

[13] onto a semiconductor substrate and firing it to form a protective film as a resist underlayer; and a step of forming a resist film on the protective film and then exposing and developing it to form a resist pattern, wherein the manufacturing method is used to manufacture a semiconductor.

[0051]

[16] A method for manufacturing a semiconductor device includes the following steps: forming a protective film on a semiconductor substrate on which an inorganic film can be formed using a protective film forming composition as described in any one of [1] to

[11] , forming a resist pattern on the protective film, using the resist pattern as a mask to dry etch the protective film to expose the inorganic film or the surface of the semiconductor substrate, using the dry-etched protective film as a mask to wet etch the inorganic film or the semiconductor substrate with a semiconductor wet etching solution and then washing it.

[0052]

[17] A method for manufacturing a semiconductor device includes the following steps: forming a photoresist underlayer film on a semiconductor substrate on which an inorganic film can be formed using the photoresist underlayer film forming composition described in

[13] ; forming a photoresist pattern on the photoresist underlayer film; using the photoresist pattern as a mask to dry etch the photoresist underlayer film to expose the surface of the inorganic film or the semiconductor substrate; and using the dry-etched photoresist underlayer film as a mask to etch the inorganic film or the semiconductor substrate.

[0053] The effects of the invention

[0054] According to the present invention, a composition for forming a protective film that is capable of forming a protective film with excellent resistance to wet etchants for semiconductors and has a fast etching rate during dry etching and can achieve a high etch rate (ER) can be provided. This composition can also be effectively used as a composition for forming a resist underlayer film. Detailed Implementation

[0055] The present invention will now be described in detail. Furthermore, the following description of the constituent elements is for illustrative purposes only and the invention is not limited to these descriptions.

[0056] (A composition for forming a protective film with a wet etching solution for semiconductors)

[0057] The protective film forming composition for wet etching solutions for semiconductors of the present invention comprises:

[0058] (A) Compounds or polymers having the epoxy structure shown in formula (I) below,

[0059] (B) Compounds with a thiol structure, and

[0060] (C) Solvent.

[0061]

[0062] (In formula (I), * indicates a bonding site. n represents 1 or 2. When n=1, X represents an ether bond, ester bond, or amide bond; when n=2, X represents a nitrogen atom or an amide bond.)

[0063] The protective film forming composition of the present invention may further include (D) a curing agent.

[0064] Furthermore, the protective film forming composition of the present invention may also contain (E) a compound or polymer having phenolic hydroxyl groups.

[0065] Furthermore, the protective film forming composition of the present invention may also include (F) a compound having a hydroxyl group and at least one selected from hydroxyl and carbonyl groups.

[0066] The inventors have discovered that a protective film forming composition comprising (A) a compound or polymer having an epoxy structure as shown in formula (I) above, (B) a compound having a thiol structure, and (C) a solvent, more preferably further comprising (D) a curing agent, and / or (E) a compound or polymer having phenolic hydroxyl groups, and / or (F) a compound having hydroxyl groups, and at least one of hydroxyl and carbonyl groups, can form a protective film that has high resistance to wet etching solutions, fast etching speed during dry etching, and can achieve high etching rate (ER), thus completing the present invention.

[0067] It is speculated that by using a thiol-containing compound (B) to crosslink with a compound or polymer (A) having an epoxy structure, the thiol-containing compound can be well maintained in the cured film. Furthermore, by ensuring that the thiol-containing compound (B) does not contain an aromatic ring structure, a high etching rate (ER) can be achieved. Moreover, by adjusting the amount of thiol-containing compound (B) added, the etching rate can also be expected to be adjusted.

[0068] <(A) compound or polymer>

[0069] The compound or polymer (A) used in this invention has the epoxy structure shown in the above formula (I).

[0070] As a more preferred embodiment of the compound or polymer (A), examples include the polymer shown in the first embodiment below, or the compound shown in the second embodiment.

[0071] <<Option 1>>

[0072] Examples of polymers that can be used as (A) in this invention include the following polymers.

[0073] Examples of such polymers (hereinafter also referred to as the polymer in Scheme 1) include polymers containing phenolic varnish structures having unit structures as shown in Formula (1-1) below, acrylic polymers having unit structures as shown in Formula (1-3) below, etc.

[0074] As a polymer in the first scheme, for example, a polymer containing a phenolic varnish structure is represented by the following formula (1-1):

[0075]

[0076] (In formula (1-1), Ar represents a benzene ring, naphthalene ring, or anthracene ring, R 1 The group represents a hydroxyl group, a mercapto group that can be protected by a methyl group, an amino group that can be protected by a methyl group, a halogroup, 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; L 1 Indicates a single bond or an alkylene group with 1 to 10 carbon atoms, n2 represents 1 or 2, E represents a group with an epoxy group or a group with an oxetyl group, and when n2=1, T 1 This refers to an alkylene group with 1 to 10 carbon atoms that can be interrupted by ether, ester, or amide bonds. When n2=2, T 1 This refers to a trivalent hydrocarbon group with 1 to 10 carbon atoms that can be interrupted by a nitrogen atom or an amide bond.

[0077] Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-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-n-propyl 1-Ethyl-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-n-propyl 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-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, 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.

[0078] Examples of alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, isobutylene, secondary butylene, tert-butylene, cyclobutylene, 1-methyl-cyclopropylene, 2-methyl-cyclopropylene, n-pentylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n-butylene, 1,1-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene, cyclopentylene, 1-methyl-cyclobutylene, 2-methyl-cyclopropylene, etc. Butylene, 3-methyl-cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl-cyclopropylene, 2-ethyl-cyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 2,2-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 1-ethyl-n-butylene 2-Ethyl-n-butylene, 1,1,2-trimethyl-n-propylene, 1,2,2-trimethyl-n-propylene, 1-ethyl-1-methyl-n-propylene, 1-ethyl-2-methyl-n-propylene, cyclohexylene, 1-methyl-cyclopentane, 2-methyl-cyclopentane, 3-methyl-cyclopentane, 1-ethyl-cyclobutylene, 2-ethyl-cyclobutylene, 3-ethyl-cyclobutylene, 1,2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4- -Dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropylene, 2-n-propyl-cyclopropylene, 1-isopropyl-cyclopropylene, 2-isopropyl-cyclopropylene, 1,2,2-trimethyl-cyclopropylene, 1,2,3-trimethyl-cyclopropylene, 2,2,3-trimethyl-cyclopropylene, 1-ethyl-2-methyl-cyclopropylene, 2-ethyl-1-methyl-cyclopropylene, 2-ethyl-2-methyl-cyclopropylene, 2-ethyl-3-methyl-cyclopropylene, n-heptylene, n-octylene, n-nonylene, or n-decylene.

[0079] R 1 An example of an alkyl group having 1 to 10 carbon atoms that is substituted or interrupted by a heteroatom is an alkoxy group having 1 to 10 carbon atoms.

[0080] Examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-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.

[0081] The unit structure shown in formula (1-1) can be one type or a combination of two or more types. For example, it can be a copolymer with multiple unit structures having Ar of the same type. Copolymers with multiple unit structures having different types of Ar, such as Ar having a benzene ring unit structure and Ar having a naphthalene ring unit structure, are also not excluded from the scope of this application.

[0082] The aforementioned phrase "can be interrupted" refers to the following: in the case of alkylene groups with 2 to 10 carbon atoms, it means that any carbon-carbon atom in the alkylene group is interrupted by a heteroatom (i.e., an ether bond in the case of oxygen, and a thioether bond in the case of sulfur), an ester bond, or an amide bond. In the case of 1 carbon atom (i.e., methylene), it means that either side of the carbon atom of the methylene group has a heteroatom (i.e., an ether bond in the case of oxygen, and a thioether bond in the case of sulfur), an ester bond, or an amide bond.

[0083] T 1 This refers to a hydrocarbon group (including alkylene and trivalent hydrocarbon groups) with 1 to 10 carbon atoms that can be interrupted by an ether bond, ester bond, nitrogen atom, or amide bond, but preferably a combination of an ether bond and a methylene group (i.e., "-T" in formula (1-1)). 1 -(E)n2” is the case of glycidyl ether group, the combination of ester bond and methylene group, or the combination of amide bond and methylene group.

[0084] The so-called 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 halogenated groups).

[0085] L 1It represents a single bond or an alkylene group having 1 to 10 carbon atoms, but is preferably represented by the following formula (1-2):

[0086]

[0087] (In equation (1-2), R) 2 R 3 The following groups independently represent hydrogen atoms, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and cyclobutyl, R. 2 R 3 They can bond together to form rings with 3 to 6 carbon atoms. R is preferred. 2 R 3 All are hydrogen atoms (i.e., -(CR) 2 R 3 )- is methylene).

[0088] A halogenated group refers to a halogen (F, Cl, Br, I) that has been substituted with hydrogen.

[0089] In formula (1-1), E is more preferably a group having an epoxy group.

[0090] The polymer with a phenolic varnish structure in Scheme 1 is not particularly limited, for example, as long as it satisfies the unit structure of formula (1-1). It can be a substance manufactured by a method known to the public. Commercially available products can also 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 (…). (e.g., manufactured in Japan).

[0091] The weight-average molecular weight of the polymer with a phenolic varnish structure in Scheme 1 is 100 or more, and is 500 to 200,000, 600 to 50,000, or 700 to 10,000.

[0092] As a polymer with a phenolic varnish structure in the first scheme, a substance having the following unit structure can be cited.

[0093]

[0094] Me represents methyl, and Et represents ethyl.

[0095] As the polymer in the first scheme, for example, an acrylic polymer is represented by the following formula (1-3):

[0096]

[0097] (In equation (1-3), R) 100Indicates a hydrogen atom or a methyl group, n2 represents 1 or 2, E represents a group with an epoxy group or a group with an oxetyl group, and when n2=1, T 2 This refers to an alkylene group with 1 to 10 carbon atoms that can be interrupted by an ether bond, ester bond, or amide bond. When n2=2, T 2 This refers to a trivalent hydrocarbon group with 1 to 10 carbon atoms that can be interrupted by a nitrogen atom or an amide bond.

[0098] The weight-average molecular weight of the acrylic polymer in Scheme 1 is 100~20,000, 300~10,000, or 500~5,000.

[0099] <<Option 2>>

[0100] Examples of compounds (A) used in this invention include the following compounds.

[0101] This compound (hereinafter also referred to as the compound in Scheme 2) is a compound that does not have repeating structural units.

[0102] The compound comprises a terminal group (A1), a polyvalent group (A2), and a linker group (A3), wherein,

[0103] The terminal group (A1) bonds only to the linker group (A3).

[0104] The multivalent group (A2) bonds only to the linker group (A3).

[0105] The linker (A3) can be bonded to a terminal group (A1) on one side and a multivalent group (A2) on the other side, or it can be arbitrarily chosen to be bonded to another linker (A3).

[0106] The terminal group (A1) is any of the structures in formula (I) below.

[0107]

[0108] (In formula (I), * indicates the bonding site with the linker (A3). n represents 1 or 2. When n=1, X represents an ether bond, ester bond, or amide bond; when n=2, X represents a nitrogen atom or an amide bond.)

[0109] Multivalent base (A2) is selected from

[0110] -O-、

[0111] Aliphatic hydrocarbon groups,

[0112] Combinations of aromatic hydrocarbon groups with fewer than 10 carbon atoms and aliphatic hydrocarbon groups, and

[0113] Combination of aromatic hydrocarbon groups with 10 or more carbon atoms and -O-

[0114] The 2-4 valent groups in the middle,

[0115] The linker group (A3) represents an aromatic hydrocarbon group.

[0116] The term "not having repeating structural units" excludes polymers such as polyolefins, polyesters, polyamides, and poly(meth)acrylates that have repeating structural units. Preferably, compound (A) has a weight-average molecular weight of 300 or more and 1,500 or less.

[0117] The “bonding” between terminal groups (A1), multivalent groups (A2), and linker groups (A3) refers to chemical bonding, usually covalent bonding, but it does not preclude it from being an ionic bond.

[0118] The multivalent base (A2) is a 2- to 4-valent base.

[0119] Therefore, the aliphatic hydrocarbon group in the definition of polyvalent group (A2) is a 2- to 4-valent aliphatic hydrocarbon group.

[0120] As non-limiting examples, if divalent aliphatic hydrocarbon groups are exemplified, examples include methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, isobutylene, secondary butylene, tert-butylene, cyclobutylene, 1-methyl-cyclopropylene, 2-methyl-cyclopropylene, n-pentylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n-butylene, 1,1-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene, cyclopentylene, 1-methyl-cyclobutylene, 2 1-Methyl-cyclobutylene, 3-methyl-cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl-cyclopropylene, 2-ethyl-cyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 2,2-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 1-ethyl-n-butylene Butyl, 2-ethyl-n-butylene, 1,1,2-trimethyl-n-propylene, 1,2,2-trimethyl-n-propylene, 1-ethyl-1-methyl-n-propylene, 1-ethyl-2-methyl-n-propylene, cyclohexylene, 1-methyl-cyclopentane, 2-methyl-cyclopentane, 3-methyl-cyclopentane, 1-ethyl-cyclobutylene, 2-ethyl-cyclobutylene, 3-ethyl-cyclobutylene, 1,2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4- Dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropylene, 2-n-propyl-cyclopropylene, 1-isopropyl-cyclopropylene, 2-isopropyl-cyclopropylene, 1,2,2-trimethyl-cyclopropylene, 1,2,3-trimethyl-cyclopropylene, 2,2,3-trimethyl-cyclopropylene, 1-ethyl-2-methyl-cyclopropylene, 2-ethyl-1-methyl-cyclopropylene, 2-ethyl-2-methyl-cyclopropylene, 2-ethyl-3-methyl-cyclopropylene, n-heptene, n-octene, n-nonene, or n-decene alkylene.

[0121] By removing hydrogen from any position in these groups, they become bonded, thus deriving trivalent and tetravalent groups.

[0122] Aromatic hydrocarbon groups with fewer than 10 carbon atoms as defined by the polyvalent group (A2) include benzene, toluene, xylene, mesitylene, cumene, styrene, and indene.

[0123] Aliphatic hydrocarbon groups capable of combining with aromatic hydrocarbon groups having fewer than 10 carbon atoms, besides the aforementioned alkylene groups, include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-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, and 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, 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-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, decyl and other alkyl groups.

[0124] The definition of a polyvalent group (A2) is that any of the aromatic hydrocarbon groups or aliphatic hydrocarbon groups with fewer than 10 carbon atoms can bond with a linker group (A3).

[0125] As an aromatic hydrocarbon group with 10 or more carbon atoms in the definition of a polyvalent group (A2), examples include naphthalene, etc. Anthracene, phenanthrene, tetraphenylene, 9,10-benzophenanthrene, pyrene wait.

[0126] The aromatic hydrocarbon group with 10 or more carbon atoms in the definition of polyvalent group (A2) is preferably bonded to the linker group (A3) via -O-.

[0127] As an aromatic hydrocarbon group in the definition of linking group (A3), examples can be aromatic hydrocarbon groups with fewer than 10 carbon atoms and aromatic hydrocarbon groups with more than 10 carbon atoms.

[0128] The preferred compound (A) has two or more linking groups (A3).

[0129] The compound in the second scheme is preferably represented by, for example, the following formula (II).

[0130]

[0131] (In formula (II),)

[0132] Z 1 and Z 2 Each of the following expressions can be expressed independently: (I)

[0133]

[0134] (In formula (I), * indicates that it is related to Y) 1 Or Y 2 The bonding site. n represents 1 or 2. When n=1, X represents an ether bond, ester bond, or amide bond; when n=2, X represents a nitrogen atom or an amide bond.

[0135] Y 1 and Y 2 Each can independently represent an aromatic hydrocarbon group.

[0136] X 1 and X 2 Each represents -Y independently 1 -Z 1 or -Y 2 -Z 2 ,

[0137] n1 and n2 each independently represent integers from 0 to 4, but either of them is greater than or equal to 1.

[0138] (X 1 In m1, m1 represents either 0 or 1.

[0139] (X 2 In m2, m2 is defined as either 0 or 1.

[0140] Q represents a (n1+n2) valence group selected from -O-, aliphatic hydrocarbon groups, combinations of aromatic hydrocarbon groups with fewer than 10 carbon atoms and aliphatic hydrocarbon groups, and combinations of aromatic hydrocarbon groups with more than 10 carbon atoms and -O-.

[0141] Q is preferably a 2- to 4-valent base.

[0142] In equation (II), Z 1and Z 2 Q is equivalent to the terminal base (A1) mentioned above, Q is equivalent to the multivalent base (A2) mentioned above, and Y... 1 and Y 2 Equivalent to the aforementioned connecting base (A3), and their descriptions, examples, etc. are as described above.

[0143] The compound in the second scheme preferably contains, for example, a partial structure as shown in formula (III) below.

[0144]

[0145] (In formula (III), Ar represents a benzene ring, naphthalene ring, or anthracene ring. n represents 1 or 2. When n=1, X represents an ether bond, ester bond, or amide bond; when n=2, X represents a nitrogen atom or an amide bond.)

[0146] Examples of compounds that can be cited as compounds in Scheme 2 include the following.

[0147]

[0148]

[0149]

[0150] <(B) Compounds with thiol structures>

[0151] The component (B) used in this invention is a compound having a thiol structure.

[0152] Examples of compounds having a thiol structure that are involved in this invention include, for instance, the polyfunctional thiol compounds represented by the following formula (10-1).

[0153]

[0154] (In equation (10-1), R) 7 Indicates a single bond or a straight-chain or branched alkylene group with 1-6 carbon atoms; X represents a single bond or ester bond; A represents an organogroup or heteroatom with 2-12 carbon atoms; r 1 (Represents integers from 2 to 6.)

[0155] A may contain at least one heteroatom or may not contain any heteroatoms.

[0156] Examples of heteroatoms in A include oxygen atoms and nitrogen atoms.

[0157] Examples of polyfunctional thiols represented by formula (10-1) include, for example, 1,2-ethanedithiol, 1,3-propanedithiol, bis(2-mercaptoethyl) ether, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), and pentaerythritol tris(3-mercaptopropyl) ether.

[0158] As a polyfunctional thiol compound represented by the following formula (10-1), commercially available products can be used, for example, MT (registered trademark) PE1 MT NR1, MT BD1, TPMB, TEMB (all manufactured by Showa Denko Co., Ltd.), and TMMP, TEMPIC, PEMP, EGMP-4, DPMP, TMMP II-20P, PEMP II-20P, PEPT (all manufactured by SC Organic Chemicals Co., Ltd.).

[0159] Examples of polyfunctional thiols as shown in formula (10-1) are the following compounds.

[0160]

[0161] The content of (B) the compound having a thiol structure in the protective film forming composition of the present invention is, for example, typically 1% by mass, preferably 5% by mass, relative to the total solid content of the protective film forming composition, with respect to the lower limit of its content; and typically 70% by mass, preferably 50% by mass, and more preferably 30% by mass, relative to the total solid content of the protective film forming composition, with respect to the upper limit of its content.

[0162] <(C) Solvent>

[0163] The protective film forming composition of the present invention can be prepared by dissolving the above-mentioned components in a solvent, preferably an organic solvent, and used in a homogeneous solution state. Furthermore, in the present invention, the solvent (C) is different from the compound shown in (F) described later.

[0164] As the organic solvent for the protective film forming composition of the present invention, any organic solvent capable of dissolving the above-mentioned (A) compound or polymer, the above-mentioned (B) compound having a thiol structure, or other arbitrarily selected solid components can be used without particular limitation. In particular, since the protective film forming composition of the present invention is used in a uniform solution state, it is recommended to use it in conjunction with organic solvents generally used in photolithography processes, taking into account its coating performance.

[0165] Examples of organic solvents include, for example, 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, 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, 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.

[0166] Preferred solvents include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0167] The solid content of the protective film forming composition of the present invention is typically 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content is the percentage of all components in the protective film forming composition after removing the solvent. The proportion of the above-mentioned (A) compound or polymer in the solid content is preferably 1 to 100% by mass, more preferably 1 to 99.9% by mass, even more preferably 50 to 99.9% by mass, even more preferably 50 to 95% by mass, and particularly preferably 50 to 90% by mass.

[0168] <(D) Curing Agent>

[0169] The component (D) used in this invention is a curing agent.

[0170] As a curing agent, there are no particular limitations as long as it can undergo a cross-linking reaction with the epoxy groups of component (A). Examples include alkalis, heat-generating acid agents, phenolic curing agents, amide curing agents, amine curing agents, imidazoles, acid anhydride curing agents, organophosphorus compounds, thiol curing agents, tertiary amines, etc. Salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine coordination compounds, isocyanate-based curing agents, end-capped isocyanate-based curing agents, etc.

[0171] Additionally, for example, 2-phenylimidazole is a base and also an imidazole. Thus, in this invention, there are sometimes multiple specific examples belonging to the sub-concept of the curing agents exemplified above.

[0172] <<Alkali>>

[0173] Examples of bases include imidazole compounds, piperidine compounds, amide compounds, amine compounds, diazabicycloundecene (DBU) compounds, and diazabicyclononene (DBN) compounds. Imidazole compounds, urea compounds, etc. Among them, from the point of view of storage stability, imidazole compounds are preferred.

[0174] The base used in this invention may also include a salt that forms with an acid.

[0175] For example, the following explanation uses imidazole compounds as an example.

[0176] Examples of bases used as components (B) in this invention include, for example, (i) imidazole compounds represented by formula (B1), (ii) salts of imidazole compounds represented by formula (B1) and acids, or (iii) quaternary salts containing cations represented by formula (B2).

[0177]

[0178] (In formula (B1), R) 1 R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a substituted aryl group, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of a substituted triazine ring, a cyano group, a hydroxyl group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group. 2 R represents an alkylene group having 1 to 4 carbon atoms. 3 R represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group that can be substituted. 4 R represents a hydrogen atom, a formyl group, an alkyl group with 1 to 4 substituted carbon atoms, or an alkoxyalkyl group with 4 or fewer substituted carbon atoms. 5 (This represents a hydrogen atom, a formyl group, an alkyl group with 1 to 4 substituted carbon atoms, or an alkoxyalkyl group with 4 or fewer substituted carbon atoms; n represents 0 or 1.)

[0179] Examples of substituents that can be substituted include aryl groups and triazine rings, such as amino or hydroxyl groups.

[0180] Alkyl groups can be either straight-chain or branched.

[0181] Examples of aryl groups include phenyl, naphthyl, biphenyl, anthracene, etc.

[0182] R 4 or R 5 In this context, the substituents referred to as substituted alkyl groups or substituted alkoxyalkyl groups include hydroxyl or cyano groups.

[0183]

[0184] (In formula (B2), R) 1 R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a substituted aryl group, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of a substituted triazine ring, a cyano group, a hydroxyl group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group. 2 R represents an alkylene group having 1 to 4 carbon atoms. 3 R represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group that can be substituted. 4 R represents a hydrogen atom, a formyl group, an alkyl group with 1 to 4 substituted carbon atoms, or an alkoxyalkyl group with 4 or fewer substituted carbon atoms. 5 R represents a hydrogen atom, a formyl group, an alkyl group with 1 to 4 substituted carbon atoms, or an alkoxyalkyl group with 4 or fewer substituted carbon atoms. 6 R represents an alkylene group having 1 to 4 carbon atoms. 7 (This indicates an alkyl group with 1 to 4 carbon atoms, or an aryl group that can be substituted; m represents 0 or 1, and n represents 0 or 1.)

[0185] In equation (B2), R 1 ~R 5 The explanation is the same as in equation (B1). Furthermore, in equation (B2), R... 7 The substituents mentioned in the aryl group that can be substituted include amino or hydroxyl groups. As R 7 Specific examples of aryl groups can be given as the same examples mentioned above.

[0186] In this invention, the base of component (B) forms a salt with the counter anion as described above. The counter anion is not particularly limited, and examples include imide anions, halide ions, carboxylate ions, sulfate ions, sulfonate ions, thiocyanate ions, aluminate ions, borate ions, phosphate ions, phosphonate ions, amide anions, antimony ions, and methyl anions. More specifically, (CF3SO2)2N can be cited as an example. - (CF3SO2)(FSO2)N -(FSO2)2N - (CF3CF2SO2)2N - (CN)2N - OH - Cl - ,Br - I - NO3 - CH3COO - CF3COO - CF3CF2CF2COO - CF3SO3 - CF3CF2SO3 - CF3CF2CF2CF2SO3 - SbF6 - AlCl4 - SCN - PF6 - BF4 - [CF3OCF2CF2BF3] - ]、[(C p F 2p+1 )BF3] - (p represents an integer 1, 2, 3 or 4) etc.

[0187] Examples of anions include those shown below.

[0188]

[0189]

[0190] (where R is in the formula) 40 This refers to alkyl groups with 1 to 10 carbon atoms.

[0191] The bases used in this invention are specifically represented below, taking imidazole compounds as an example, but are not limited to these.

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203] <<Heat-generating acid agents>>

[0204] Examples of heat-generating acid agents include, for instance, pyridine. p-Toluenesulfonate, pyridine Trifluoromethanesulfonate, pyridine p-Phenol sulfonate, K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689 (all manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

[0205] <<Phenolic Curing Agents>>

[0206] Examples of phenolic curing agents include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenolic varnish, bisphenol A phenolic varnish, o-cresol phenolic varnish, m-cresol phenolic varnish, p-cresol phenolic varnish, xylenol phenolic varnish, poly(p-hydroxystyrene), hydroquinone, resorcinol, and catechol. tert-butylcatechol, tert-butylhydroquinone, phloroglucinol, pyroglucinol, tert-butylpyroglucinol, allylated pyroglucinol, polyallylated pyroglucinol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated derivatives of the above dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenolic varnish, allylated pyroglucinol, etc.

[0207] <<Amine-based curing agents>>

[0208] Examples of amine-based curing agents include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines.

[0209] Examples of aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, trimethyl-1,6-hexanediamine, diethylenetriamine, iminodipropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, and tetra(hydroxyethyl)ethylenediamine.

[0210] Examples of polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, and polyoxypropylene triamine.

[0211] Examples of alicyclic amines include isophorone diamine, menthane diamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, and norbornene diamine.

[0212] Examples of aromatic amines include, for example, tetrachloro-p-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, m-aminophenol, m-aminobenzylamine, benzyl dimethylamine, 2-dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, α,α'-bis(4-aminophenyl)-p-diisopropylbenzene, etc.

[0213] <<Imidazole>>

[0214] Examples of imidazoles include, for example, 2-phenylimidazolium, 2-ethyl-4(5)-methylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyano-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, and 1-cyanoethyl-2-phenylimidazolium. Trimethicone salts, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolium isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, and adducts of epoxy resins with the above-mentioned imidazoles, etc.

[0215] <<Anhydride-based curing agents>>

[0216] Examples of anhydride-based curing agents include anhydrides and modified anhydrides.

[0217] Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelic anhydride, polysedimentic anhydride, poly(ethyl octadecanoic acid) anhydride, poly(phenyl hexadecanoic acid) anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl nadic anhydride. Anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol dipreptyltricarboxylate dianhydride, chlorobrittle anhydride, nadic anhydride, methylnadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthous succinic anhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthous succinic anhydride, etc.

[0218] Examples of modified acid anhydrides include substances obtained by modifying the aforementioned acid anhydrides with glycols. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Furthermore, copolymers of two or more of these glycols and / or polyether glycols can also be used. In addition, in modified acid anhydrides, it is preferable to modify them with 0.4 mol or less of a glycol relative to 1 mol of the acid anhydride.

[0219] <<Organophosphines>>

[0220] Examples of organophosphorus compounds include, for example, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine.

[0221] << Salt >>

[0222] As Salts, for example, tetraphenyl Tetraphenylborate, tetraphenyl ·Ethyltriphenylborate, tetrabutyl Tetrabutylborate, etc.

[0223] <<Tetraphenylboron salt>>

[0224] Examples of tetraphenylboron salts include 2-ethyl-4-methylimidazolium tetraphenylboronate and N-methylmorpholine tetraphenylboronate.

[0225] As for the content of (D) curing agent in the protective film forming composition of the present invention, for example, the lower limit of its content is generally 0.0001 mass relative to the total solid components of the protective film forming composition, preferably 0.01 mass, more preferably 0.1 mass, and the upper limit of its content is generally 50 mass relative to the total solid components of the protective film forming composition, preferably 40 mass, more preferably 30 mass.

[0226] <(E) Compounds or polymers having phenolic hydroxyl groups>

[0227] The protective film forming composition of the present invention may further comprise (E) a compound or polymer having phenolic hydroxyl groups.

[0228] (E) There is no particular limitation on compounds or polymers having phenolic hydroxyl groups, as long as they do not impair the effects of the invention. Of course, the compounds or polymers having phenolic hydroxyl groups in (E) are different from the compounds or polymers in (A) above.

[0229] (E) There are no particular limitations on the weight-average molecular weight of compounds or polymers having phenolic hydroxyl groups (hereinafter also referred to as (E) compounds or polymers), for example, 300 to 50,000.

[0230] (E) The compound or polymer preferably has two or more phenolic hydroxyl groups.

[0231] As a more preferred embodiment of the (E) compound or polymer, examples include the compounds or polymers shown in embodiments 3 to 5 below.

[0232] <<Option 3>>

[0233] Examples of compounds or polymers (E) used in this invention include those shown in Formula 2-1.

[0234]

[0235] (where R is in the formula) 2 Each can independently represent a halogenated 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 halogenated group. A 1 With A 2 Each is independently an alkylene group having 1 to 10 carbon atoms, a divalent organogroup derived from a bicyclic compound, a biphenylene group, or a -C(T) group. 2 (T) 3 The divalent organogroups or combinations thereof shown in the figure are T. 2T represents a halogenated 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 halogenated group. 3 This represents a hydrogen atom or a monovalent group as shown in (Formula 2-1-a).

[0236]

[0237] In (Equation 2-1-a), * indicates that it is related to T. 3 The sites where the carbon atoms are bonded. R 2 R in (Equation 2-1) 2 They have the same meaning. '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.

[0238] Preferably, m1, n3~n5 and r2 are 0, and m2 is 1.

[0239] The halogen groups, alkoxy groups, and alkyl groups involved in (Formula 2-1) are explained as described above.

[0240] Examples of bicyclic compounds include dicyclopentadiene, substituted dicyclopentadiene, tetracyclic [4.4.0.12,5.17,10]dodecane-3,8-diene, or substituted tetracyclic [4.4.0.12,5.17,10]dodecane-3,8-diene. Substitution refers to the independent substitution of one or more hydrogen atoms in a bicyclic compound by a halogroup, nitro group, amino group, or hydroxyl group, or by an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 40 carbon atoms that can be substituted by these groups. A divalent organogroup derived from a bicyclic compound refers to a group with two bonds derived by removing any two hydrogen atoms from the bicyclic compound.

[0241] 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.

[0242] As specific examples of the compounds shown in (Formula 2-1), the following compounds can be cited.

[0243]

[0244] As (E) compounds or polymers, they can be the compounds shown below.

[0245]

[0246] <<Option 4>>

[0247] Examples of compounds or polymers used in this invention include, for instance, the compound shown in (Formula 2-2).

[0248]

[0249] (where R is in the formula) 3 The group can be represented by a halogenated 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 halogenated group. Q 1 This indicates a single bond, oxygen atom, sulfur atom, sulfonyl group, carbonyl group, imino group, aryl group with 6 to 40 carbon atoms, or alkyl group with 1 to 10 carbon atoms that can be substituted by a halogroup. 'a' represents an integer from 1 to 6. 'n6' represents an integer from 0 to 2. 'r3' represents an integer from 0 to 3.

[0250] The alkoxy, alkyl, and halogroups in (Formula 2-2) are explained as described above.

[0251] Examples of arylene groups with 6 to 40 carbon atoms include phenylene, o-methylphenylene, m-methylphenylene, p-methylphenylene, o-chlorophenylene, m-chlorophenylene, p-chlorophenylene, o-fluorophenylene, p-fluorophenylene, o-methoxyphenylene, p-methoxyphenylene, p-nitrophenylene, p-cyanophenylene, α-naphthylene, β-naphthylene, o-biphenylene, m-biphenylene, p-biphenylene, 1-anthraylene, 2-anthraylene, 9-anthraylene, 1-phenanthylene, 2-phenanthylene, 3-phenanthylene, 4-phenanthylene, and 9-phenanthylene.

[0252] Examples of alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, isobutylene, secondary butylene, tert-butylene, cyclobutylene, 1-methyl-cyclopropylene, 2-methyl-cyclopropylene, n-pentylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n-butylene, 1,1-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene, cyclopentylene, 1-methyl-cyclobutylene, 2-methyl-cyclopropylene, etc. Butylene, 3-methyl-cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl-cyclopropylene, 2-ethyl-cyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 2,2-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 1-ethyl-n-butylene 2-Ethyl-n-butylene, 1,1,2-trimethyl-n-propylene, 1,2,2-trimethyl-n-propylene, 1-ethyl-1-methyl-n-propylene, 1-ethyl-2-methyl-n-propylene, cyclohexylene, 1-methyl-cyclopentane, 2-methyl-cyclopentane, 3-methyl-cyclopentane, 1-ethyl-cyclobutylene, 2-ethyl-cyclobutylene, 3-ethyl-cyclobutylene, 1,2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4- -Dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropylene, 2-n-propyl-cyclopropylene, 1-isopropyl-cyclopropylene, 2-isopropyl-cyclopropylene, 1,2,2-trimethyl-cyclopropylene, 1,2,3-trimethyl-cyclopropylene, 2,2,3-trimethyl-cyclopropylene, 1-ethyl-2-methyl-cyclopropylene, 2-ethyl-1-methyl-cyclopropylene, 2-ethyl-2-methyl-cyclopropylene, 2-ethyl-3-methyl-cyclopropylene, n-heptylene, n-octylene, n-nonylene, or n-decylene.

[0253] As specific examples of the compounds shown in (Formula 2-2), the following compounds can be cited.

[0254]

[0255] (E) The compound can be the compound shown in formula (4-1) below.

[0256]

[0257] (where R is in the formula) 5This indicates a halogenated 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 with an alkyl group with 1 to 3 carbon atoms, or alkyl group with 1 to 10 carbon atoms that can be substituted with a hydroxyl group or a halogenated group. In the formula, n8 represents an integer of 4, 5, 6, or 8.

[0258] The terms above are explained as described above.

[0259] The following are specific examples of compounds represented by formula (4-1).

[0260]

[0261] (E) The compound can be the compound shown in formula (5-1) and formula (5-1-a).

[0262]

[0263] (In the formula, n9 and n10 represent integers 0 or 1 respectively, R) 6 The groups represented are halogenated, carboxylated, nitro, cyano, methylenedioxy, acetoxy, methylthio, alkoxy with 1 to 9 carbon atoms, amino groups that can be substituted with alkyl groups with 1 to 3 carbon atoms, or alkyl groups with 1 to 10 carbon atoms that can be substituted with hydroxyl or halogenated groups. 'a' represents an integer from 1 to 6. 'n11' represents the integer 1 or 2. 'r5' represents the integer 0 to 3. '*' indicates the site of bonding with the structure shown in formula (5-1) or the site of bonding with the structure shown in formula (5-1-a).

[0264] The terms mentioned above are explained as described above.

[0265] The following are specific examples of compounds represented by formulas (5-1) and (5-1-a).

[0266]

[0267] (E) The compound can be one of the compounds shown below.

[0268]

[0269]

[0270] <<Option 5>>

[0271] As for the (E) compound or polymer used in this invention, there are no particular limitations as long as the polymer does not impair the effect of the invention. For example, the (E) polymer preferably has a structure with at least three repeating units.

[0272] (E) There are no particular limitations on the weight-average molecular weight of the polymer, but for example, it is 1,000 to 50,000.

[0273] (E) The polymer preferably contains the unit structure shown in Formula 3-1 below.

[0274]

[0275] (where T is in the formula) 4 R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms that can be substituted by a halogroup. 4 This indicates a halogenated 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 with an alkyl group with 1 to 3 carbon atoms, or alkyl group with 1 to 10 carbon atoms that can be substituted with a hydroxyl group or a halogenated 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.

[0276] The halogenated groups, alkyl groups, and alkoxy groups are explained as described above.

[0277] The polymer shown in (Formula 3-1) can be a polymer containing one unit structure shown in (Formula 3-1) or a copolymer containing two or more unit structures shown in (Formula 3-1).

[0278] As a specific example of the polymer (E) shown in (Formula 3-1), a polymer containing the unit structure described below can be cited.

[0279]

[0280] (In the above formula, m and n in the repeating unit structure represent the molar ratio of copolymerization.)

[0281] <(F)Component>

[0282] The protective film forming composition of the present invention may further comprise (F) a compound having a hydroxyl group and at least one selected from hydroxyl and carbonyl groups (hereinafter sometimes referred to as "the compound shown in (F)" or "compound (F)").

[0283] Examples of the number of carbon atoms in a compound (F) include 2 to 20.

[0284] As compound (F), the preferred compounds are those shown in formula (20-1), formula (20-2), and formula (20-3).

[0285]

[0286] (In equation (20-1), R) 1 ~R 4Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms.

[0287] In formula (20-2), X represents -O- or -NR- (R represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms that may have a hydroxyl group, an aryl group with 6 to 12 carbon atoms that may have a substituent, or an aralkyl group with 7 to 13 carbon atoms that may have a substituent). n represents an integer from 1 to 3. When n is 2 or 3, X can be the same or different.

[0288] In equation (20-3), R 11 R indicates an alkyl group having 1 to 4 carbon atoms. 12 (This refers to alkyl groups with 1 to 6 carbon atoms.)

[0289] R in equation (20-1) 1 ~R 4 The alkyl and hydroxyalkyl groups can be straight-chain, branched, or cyclic, but are preferably straight-chain.

[0290] Equation (20-1) preferably R 1 ~R 3 R represents a hydrogen atom. 4 It refers to an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms.

[0291] Examples of aromatic rings in aryl groups with 6 to 12 carbon atoms that can have substituents include benzene rings and naphthalene rings.

[0292] Examples of aromatic rings in aralkyl groups having 7 to 13 carbon atoms that can have substituents include, for example, benzene rings and naphthalene rings.

[0293] Examples of substituents that can be aryl groups with 6 to 12 carbon atoms or aralkyl groups with 7 to 13 carbon atoms include, for example, alkyl groups with 1 to 6 carbon atoms and alkoxy groups with 1 to 6 carbon atoms.

[0294] R in -NR- of formula (20-2) is preferably an alkyl group having 1 to 6 carbon atoms and a aryl group having 6 to 12 carbon atoms and a substituent. The alkyl group having 1 to 6 carbon atoms and a hydroxyl group is preferably a hydroxyalkyl group, more preferably a 2-hydroxyethyl group.

[0295] In equation (20-2), when X is -O-, n is preferably 2.

[0296] In equation (20-2), when X is -NR-, n is preferably 1.

[0297] Examples of compounds (F) include the following compounds.

[0298]

[0299]

[0300] The content of compound (F) in the protective film forming composition of the present invention is not particularly limited, but the lower limit of its content is preferably 0.5% by mass, more preferably 1% by mass, and particularly preferably 5% by mass relative to compound (A) or polymer, and the upper limit of its content is preferably 50% by mass, more preferably 30% by mass, and particularly preferably 20% by mass relative to compound (A) or polymer.

[0301] The content of compound (F) in the protective film forming composition of the present invention is not particularly limited, but the lower limit of its content relative to solvent (C) is preferably 0.0001 mass, more preferably 0.005 mass, particularly preferably 0.001 mass, and the upper limit of its content relative to solvent (C) is preferably 50 mass, more preferably 30 mass, particularly preferably 20 mass.

[0302] (Composition for forming the lower layer film of the resist)

[0303] The composition for forming a resist underlayer film of the present invention comprises:

[0304] (A) Compounds or polymers having the epoxy structure shown in formula (I) above,

[0305] (B) Compounds with a thiol structure, and

[0306] (C) Solvent.

[0307] The protective film forming composition of the present invention not only exhibits excellent resistance to wet etching solutions for semiconductors, but can also be effectively used as a composition for forming a resist underlayer film.

[0308] The explanation of the terminology used in the resist lower film forming composition of the present invention is the same as that in the explanation of the protective film forming composition described above.

[0309] (Manufacturing methods for protective films, resist underlayers, substrates with resist patterns, and semiconductor devices, etc.)

[0310] The following describes a method for manufacturing a substrate with a resist pattern using the protective film forming composition (resist underlayer film forming composition) of the present invention, and a method for manufacturing a semiconductor device.

[0311] The protective film of the present invention is a fired product of a coated film formed by the protective film forming composition of the present invention.

[0312] The resist underlayer film of the present invention is a sintered product of the coating film of the resist underlayer film forming composition of the present invention.

[0313] The method for manufacturing a substrate with a protective film according to the present invention includes the steps of coating a semiconductor substrate with the protective film forming composition of the present invention and firing it to form a protective film. The method for manufacturing a substrate with a protective film is used in the manufacture of semiconductors.

[0314] The method for manufacturing a substrate with a resist pattern according to the present invention includes a step of coating a protective film forming composition of the present invention or a resist underlayer forming composition of the present invention onto a semiconductor substrate and firing it to form a protective film as a resist underlayer; and a step of forming a resist film on the protective film, followed by exposure and development to form a resist pattern. The method for manufacturing a substrate with a resist pattern is used in the manufacture of semiconductors.

[0315] One embodiment of the semiconductor device manufacturing method of the present invention includes the following steps: forming a protective film on a semiconductor substrate on which an inorganic film can be formed using the protective film forming composition of the present invention; forming a resist pattern on the protective film; using the resist pattern as a mask to dry etch the protective film to expose the inorganic film or the surface of the semiconductor substrate; using the dry-etched protective film as a mask to wet etch the inorganic film or the semiconductor substrate using a semiconductor wet etching solution and then washing it.

[0316] One embodiment of the semiconductor device manufacturing method of the present invention includes the following steps: forming a photoresist underlayer film on a semiconductor substrate on which an inorganic film can be formed using the photoresist underlayer film forming composition of the present invention; forming a photoresist pattern on the photoresist underlayer film; using the photoresist pattern as a mask to dry etch the photoresist underlayer film to expose the inorganic film or the surface of the semiconductor substrate; and using the dry-etched photoresist underlayer film as a mask to etch the inorganic film or the semiconductor substrate.

[0317] The substrate with resist pattern of the present invention can be manufactured by coating the above-mentioned protective film forming composition (resist underlayer film forming composition) onto a semiconductor substrate and then firing it.

[0318] Examples of semiconductor substrates coated with the protective film forming composition (resist underlayer film forming composition) of the present invention include, for example, silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0319] When using a semiconductor substrate with an inorganic film formed on its surface, this inorganic film is formed by, for example, ALD (Atomic Layer Deposition), CVD (Chemical Vapor Deposition), reactive sputtering, ion plating, vacuum evaporation, and spin coating (SOG). Examples of such inorganic films include, for instance, polycrystalline silicon 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 also be a substrate with varying elevations, such as vias (holes) and trenches (grooves). For example, a via is approximately circular when viewed from above, with a diameter of, for example, 2 nm to 20 nm and a depth of, for example, a groove (a recess in the substrate) with a width of 2 nm to 20 nm and a depth of 50 nm to 500 nm. The protective film forming composition (resist underlayer film forming composition) of the present invention contains compounds with small weight-average molecular weight and average particle size, thus allowing the composition to be embedded without defects such as pores (voids) in substrates with varying elevations as described above. The absence of defects such as pores is an important characteristic for subsequent processes in semiconductor manufacturing (wet etching / dry etching of semiconductor substrates, resist patterning).

[0320] On such a semiconductor substrate, the protective film forming composition (resist underlayer film forming composition) of the present invention is coated using a suitable coating method such as a spin coater or a coating machine. Then, the protective film (resist underlayer film) is formed by baking using a heating means such as a hot plate. Baking conditions are 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 above range, cross-linking may become insufficient, making it difficult to obtain the resistance of the formed protective film (resist underlayer film) to resist solvents or alkaline hydrogen peroxide aqueous solutions. On the other hand, when the baking temperature is higher than the above range, the protective film (resist underlayer film) may sometimes decompose due to heat.

[0321] A resist film is formed on the protective film as described above, followed by exposure and development to form a resist pattern.

[0322] Exposure is performed using a mask (photomask) to form a prescribed pattern, employing, for example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (ultraviolet light), or EB (electron ray). Development is performed using an alkaline developer, appropriately selected from a development temperature of 5°C to 50°C and a development time of 10 seconds to 300 seconds. As an alkaline developer, aqueous solutions of bases such as inorganic bases (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia), primary amines (e.g., ethylamine, n-propylamine), secondary amines (e.g., diethylamine, di-n-butylamine), tertiary amines (e.g., triethylamine, methyldiethylamine), alkanolamines (e.g., dimethylethanolamine, triethanolamine), quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide), cyclic amines (e.g., pyrrole, piperidine), etc., can also be used. Furthermore, an appropriate amount of surfactants such as isopropanol or nonionic surfactants can be added to the aforementioned alkaline aqueous solutions. Among these, quaternary ammonium salts are preferred developers, with tetramethylammonium hydroxide and choline being more preferred. Furthermore, surfactants or similar substances can be added to these developers. Alternatively, organic solvents such as butyl acetate can be used instead of alkaline developers to develop the portions of the photoresist where the alkaline dissolution rate has not been improved.

[0323] Next, using the formed resist pattern as a mask, the protective film (underlying resist film) is dry-etched. At this time, if the aforementioned inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed; if the aforementioned inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed.

[0324] Furthermore, by using the dry-etched protective film (resist underlayer film) (where the resist pattern remains on the protective film / resist underlayer film, the resist pattern is also used) as a mask, wet etching is performed using a semiconductor wet etchant to form the desired pattern.

[0325] As a wet etching solution for semiconductors, general chemical solutions used for etching semiconductor wafers can be used, such as acidic or alkaline substances.

[0326] Examples of substances that exhibit acidity include, for example, 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.

[0327] Examples of substances exhibiting alkalinity include alkaline hydrogen peroxide solution, which is produced by mixing organic amines such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, and triethanolamine with hydrogen peroxide water to achieve an alkaline pH. SC-1 (ammonia-hydrogen peroxide solution) is a specific example. Furthermore, substances that achieve an alkaline pH, such as urea, can be mixed with hydrogen peroxide water, and heating can induce the thermal decomposition of urea to produce ammonia, ultimately resulting in an alkaline solution that can also be used as a chemical solution for wet etching.

[0328] Among them, acidic hydrogen peroxide water or alkaline hydrogen peroxide water is preferred.

[0329] These chemical solutions may also contain additives such as surfactants.

[0330] The desired operating temperature for the semiconductor wet etching solution 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.

[0331] Example

[0332] The present invention and its effects will be further described in detail below through examples, but the present invention is not limited to these examples.

[0333] The weight-average molecular weights of the compounds synthesized in the following examples of this specification were determined using gel permeation chromatography (hereinafter referred to as GPC). The determination was performed using... The GPC apparatus manufactured by (Company Name) and the measurement conditions are as follows.

[0334] GPC column

[0335] Column temperature: 40℃

[0336] Solvent: Tetrahydrofuran (THF)

[0337] Flow rate: 1.0 ml / minute

[0338] Standard sample: polystyrene ( (manufactured by) (Company)

[0339] <Explanation of Terms>

[0340] PGME: Propylene Glycol Monomethyl Ether

[0341] PGMEA: Propylene glycol monomethyl ether acetate

[0342] <Example 1>

[0343] 2.88 g of epoxy phenolic varnish resin EOCN-104S (produced by Nippon Kayaku Co., Ltd., equivalent to formula (a-1) below) (weight average molecular weight 3100), 0.72 g of VP-2500 (produced by Nippon Soda Co., Ltd., equivalent to formula (e-1) below, weight average molecular weight 3687), 0.043 g of 1B2PZ (produced by Shikoku Kasei Kogyo Co., Ltd., equivalent to formula (d-1) below), 0.29 g of 1,2-hexanediol (produced by Tokyo Kasei Kogyo Co., Ltd., equivalent to formula (f-1) below), 0.58 g of TMMP (produced by SC Organic Chemicals Co., Ltd., equivalent to formula (b-1) below), 28.65 g of PGMEA, and 66.85 g of PGME were mixed to prepare a solution with a solid content of 4.0% by mass. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0344]

[0345]

[0346]

[0347]

[0348]

[0349] <Example 2>

[0350] 2.88 g of epoxy phenolic varnish resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight 3100), 0.72 g of VP-2500 (manufactured by Nippon Soda Co., Ltd., weight average molecular weight 3687), 0.043 g of 1B2PZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 0.29 g of 1,2-hexanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.58 g of TEMPIC (manufactured by SC Organic Chemicals Co., Ltd., equivalent to formula (b-2) below), 28.65 g of PGMEA, and 66.85 g of PGME were mixed to prepare a solution with a solid content of 4.0% by mass. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0351]

[0352] <Example 3>

[0353] The following components were used: 2.88g of epoxy phenolic varnish resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., with a weight average molecular weight of 3100), 0.72g of VP-2500 (manufactured by Nippon Soda Co., Ltd., with a weight average molecular weight of 3687), 0.043g of 1B2PZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.), and 0.29g of 1,2-hexanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.). MT (Registered Trademark) TPMB Co., Ltd. The product, equivalent to 0.58 g of the following formula (b-3)), 28.65 g of PGMEA, and 66.85 g of PGME, was mixed to prepare a solution with a solid content of 4.0% by mass. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0354]

[0355] <Example 4>

[0356] The following components were used: 2.88g of epoxy phenolic varnish resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., with a weight average molecular weight of 3100), 0.72g of VP-2500 (manufactured by Nippon Soda Co., Ltd., with a weight average molecular weight of 3687), 0.043g of 1B2PZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.), and 0.29g of 1,2-hexanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.). MT (Registered Trademark) NR1 (Co., Ltd.) The product, equivalent to 0.58 g of the following formula (b-4)), 28.65 g of PGMEA, and 66.85 g of PGME, was mixed to prepare a solution with a solid content of 4.0% by mass. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0357]

[0358] <Comparative Example 1>

[0359] 3.30 g of epoxy phenolic varnish resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight 3100), 0.82 g of VP-2500 (manufactured by Nippon Soda Co., Ltd., weight average molecular weight 3687), 0.049 g of 1B2PZ (manufactured by Shikoku Kasei Corporation), 0.33 g of 1,2-hexanediol (manufactured by Tokyo Kasei Corporation), 28.65 g of PGMEA, and 66.85 g of PGME were mixed to prepare a solution with a solid content of 4.0% by mass. This solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0360] <Comparative Example 2>

[0361] The following components were used: 2.88g of epoxy phenolic varnish resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., with a weight average molecular weight of 3100), 0.72g of VP-2500 (manufactured by Nippon Soda Co., Ltd., with a weight average molecular weight of 3687), 0.043g of 1B2PZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.), and 0.29g of 1,2-hexanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.). Mw-390 (strain) The product, equivalent to 0.58 g of the following formula (b2-1), 28.65 g of PGMEA, and 66.85 g of PGME were mixed to prepare a solution with a solid content of 4.0% by mass. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0362]

[0363] <Comparative Example 3>

[0364] The following components were used: 2.55g of epoxy phenolic varnish resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., with a weight average molecular weight of 3100), 0.64g of VP-2500 (manufactured by Nippon Soda Co., Ltd., with a weight average molecular weight of 3687), 0.038g of 1B2PZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.), and 0.25g of 1,2-hexanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.). Mw-390 (strain) 1.02 g of the product, 28.65 g of PGMEA, and 66.85 g of PGME were mixed to prepare a solution with a solid content of 4.0% by mass. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0365] (Tolerance test to alkaline hydrogen peroxide aqueous solution)

[0366] The protective film forming compositions prepared in Examples 1-4 and the protective film forming compositions prepared in Comparative Examples 1-3 were each coated onto a silicon substrate on which a titanium nitride film was formed. The substrates were then fired at 250°C. The resulting coatings were immersed in an alkaline hydrogen peroxide aqueous solution with the compositions shown in Table 1 below at the temperatures shown in the table for 3 minutes, followed by washing with water. The state of the coatings after drying was visually observed. The results are shown in Table 2 below. "×" indicates a state where the film has peeled off, while "○" indicates a state where the film has not peeled off.

[0367]

[0368] (Determination of dry etching rate)

[0369] The following etching machine and etching gas were used to determine the dry etching rate.

[0370] Lam2300 ( (Manufactured): H2 / N2

[0371] The film forming speed was determined by comparing the film thickness reduction before and after dry etching, using protective film forming compositions prepared in Examples 1-4 and Comparative Examples 1-3 respectively, applied to a silicon substrate and fired at 250°C. The results are shown in Table 2. In Table 2, the film thickness reduction of Comparative Example 1 is set to 1, and the film thickness reduction of Examples 1-4 and Comparative Examples 2-3 is expressed as a ratio.

[0372] (Tolerance test to organic solvents)

[0373] A coating film prepared by coating a silicon substrate with the protective film forming compositions prepared in Examples 1-4 and the protective film forming compositions prepared in Comparative Examples 1-3, respectively, and firing at 250°C, was immersed in a substance obtained by mixing PGME and PGMEA, which are used as solvents for photoresist solutions, in a 7:3 ratio. The film thickness before and after immersion was compared to confirm that the film was insoluble in the solvent. Regarding the measurement results, cases where the film thickness reduction was less than 1% and the film was insoluble were marked as "○", and cases where the film thickness reduction was more than 1% and the film was soluble were marked as "×". The results are shown in Table 2.

[0374]

[0375] Generally, lower carbon content increases the likelihood of achieving higher etching rates (ER), but in Comparative Examples 2 and 3, the ER showed almost no change. This can be attributed to... Mw390 showed almost no reaction with EOCN-104S and VP-2500, leaving no residue in the cured film.

[0376] On the other hand, in Examples 1 to 4, which contain compounds with thiol structures, the etching rate (ER) increased by 4 to 7% by adding 20% ​​by mass relative to the amount of EOCN-104S. This can be attributed to the reaction of the compounds with thiol structures with the epoxy groups in the compounds or polymers described above (A), leaving residues in the film.

[0377] Therefore, Examples 1 to 4, which contain compounds with thiol structures, have higher etching rates (ER) compared to Comparative Examples 1 to 3.

[0378] According to the results in Table 2 above, the coatings made using the protective film forming compositions prepared in Examples 1 to 4 have high resistance to alkaline hydrogen peroxide aqueous solution, and can improve the etching rate (ER) compared with Comparative Examples 1 to 3.

[0379] Industrial availability

[0380] The protective film forming composition of the present invention exhibits excellent resistance to wet etching solutions during substrate processing, thus providing a protective film with minimal damage during substrate processing. Furthermore, the protective film forming composition of the present invention has a fast etching rate during dry etching, enabling the provision of a protective film with a high etch rate (ER). In addition, the resist underlayer film forming composition of the present invention exhibits excellent resistance to wet etching solutions during substrate processing and also excels in achieving a high etch rate (ER).

Claims

1. A composition for forming a protective film with a wet etching solution for semiconductors, comprising: (A) Compounds or polymers having the epoxy structure shown in formula (I) below, (B) Compounds with a thiol structure, and (C) Solvent, In formula (I), * represents the bonding site; n represents 1 or 2; when n=1, X represents an ether bond, ester bond, or amide bond, and when n=2, X represents a nitrogen atom or amide bond.

2. The protective film forming composition according to claim 1, further comprising (D) a curing agent.

3. The protective film forming composition according to claim 1 or 2, further comprising (E) a compound or polymer having phenolic hydroxyl groups.

4. The composition for forming a protective film according to claim 1, wherein compound (A) is a compound comprising a portion of the structure shown in formula (III) below. In formula (III), Ar represents a benzene ring, naphthalene ring, or anthracene ring; n represents 1 or 2; when n=1, X represents an ether bond, ester bond, or amide bond, and when n=2, X represents a nitrogen atom or amide bond.

5. The composition for forming a protective film according to claim 1, wherein the polymer (A) is a polymer containing a phenolic varnish structure having a unit structure shown in formula (1-1). In formula (1-1), Ar represents a benzene ring, naphthalene ring, or anthracene ring, and R... 1 The group represents a hydroxyl group, a mercapto group that can be protected by a methyl group, an amino group that can be protected by a methyl group, a halogroup, 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; L 1 Indicates a single bond or an alkylene group with 1 to 10 carbon atoms, n2 represents 1 or 2, E represents a group with an epoxy group or a group with an oxetyl group, and when n2=1, T 1 This refers to an alkylene group with 1 to 10 carbon atoms that can be interrupted by ether, ester, or amide bonds. When n2=2, T 1 It represents a trivalent hydrocarbon group with 1 to 10 carbon atoms that can be interrupted by a nitrogen atom or an amide bond.

6. The composition for forming a protective film according to claim 1, wherein the compound having a thiol structure (B) is a polyfunctional thiol compound represented by the following formula (10-1), In equation (10-1), R 7 Indicates a single bond or a straight-chain or branched alkylene group with 1-6 carbon atoms; X represents a single bond or ester bond; A represents an organogroup or heteroatom with 2-12 carbon atoms; r 1 It represents integers from 2 to 6.

7. The composition for forming a protective film according to claim 2, wherein the curing agent (D) is an alkali.

8. The composition for forming a protective film according to claim 7, wherein the base is an imidazole compound.

9. The composition for forming a protective film according to claim 8, wherein the alkali is represented by the following formula (B1), In equation (B1), R 1 R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a substituted aryl group, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of a substituted triazine ring, a cyano group, a hydroxyl group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group. 2 R represents an alkylene group having 1 to 4 carbon atoms. 3 R represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group that can be substituted. 4 R represents a hydrogen atom, a formyl group, an alkyl group with 1 to 4 substituted carbon atoms, or an alkoxyalkyl group with 4 or fewer substituted carbon atoms. 5 The group represents a hydrogen atom, a formyl group, an alkyl group with 1 to 4 substituted carbon atoms, or an alkoxyalkyl group with 4 or fewer substituted carbon atoms, where n represents 0 or 1.

10. The protective film forming composition according to claim 3, wherein the (E) compound or polymer having phenolic hydroxyl groups has two or more phenolic hydroxyl groups.

11. The composition for forming a protective film according to claim 3, wherein the (E) compound or polymer having phenolic hydroxyl groups is a polymer comprising the unit structure shown in formula (3-1) below. In the formula, T 4 R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms that can be substituted by a halogroup. 4 The following groups are represented: halogenated, carboxylated, nitro, cyano, methylenedioxy, acetoxy, methylthio, alkoxy with 1 to 9 carbon atoms, amino group that can be substituted by alkyl group with 1 to 3 carbon atoms, or alkyl group with 1 to 10 carbon atoms that can be substituted by hydroxyl or halogenated groups; r4 represents an integer from 0 to 3; n7 represents an integer from 0 to 2; a represents an integer from 1 to 6.

12. A protective film for wet etching solutions used in semiconductors, characterized in that, It is a fired product of a coated film formed by the composition for forming a protective film according to any one of claims 1 to 11.

13. A composition for forming a resist underlayer film, comprising: (A) Compounds or polymers having the epoxy structure shown in formula (I) below, (B) Compounds with a thiol structure, and (C) Solvent, In formula (I), * represents the bonding site; n represents 1 or 2; when n=1, X represents an ether bond, ester bond, or amide bond, and when n=2, X represents a nitrogen atom or amide bond.

14. A method for manufacturing a substrate with a protective film, characterized in that, It includes the step of coating a protective film forming composition according to any one of claims 1 to 11 onto a semiconductor substrate and firing it to form a protective film, the manufacturing method being used to manufacture a semiconductor.

15. A method for manufacturing a substrate with a resist pattern, characterized in that, It includes the process of coating the protective film forming composition of any one of claims 1 to 11 or the resist underlayer film forming composition of claim 13 onto a semiconductor substrate and firing it to form a protective film as a resist underlayer film; The manufacturing method involves forming a resist film on the protective film, followed by exposure and development to form a resist pattern, and is used to manufacture semiconductors.

16. A method for manufacturing a semiconductor device, comprising the steps of: forming a protective film on a semiconductor substrate on which an inorganic film can be formed using a protective film forming composition according to any one of claims 1 to 11; forming a resist pattern on the protective film; dry etching the protective film using the resist pattern as a mask to expose the inorganic film or the surface of the semiconductor substrate; using the dry-etched protective film as a mask, wet etching the inorganic film or the semiconductor substrate using a semiconductor wet etching solution and then washing it.

17. A method for manufacturing a semiconductor device, comprising the steps of: forming a photoresist underlayer film on a semiconductor substrate on which an inorganic film can be formed using the photoresist underlayer film forming composition of claim 13; forming a photoresist pattern on the photoresist underlayer film; dry etching the photoresist underlayer film using the photoresist pattern as a mask to expose the inorganic film or the surface of the semiconductor substrate; and etching the inorganic film or the semiconductor substrate using the dry-etched photoresist underlayer film as a mask.

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