Composition for resist underlayer film formation

Abstract

The present application provides a composition for forming an antireflective underlayer film, which comprises a polymer (A) having a partial structure represented by the following formula (A), a polymer (B) having a polymerizable multiple bond, and a solvent (C). (In the formula (A), R 11 represents a (n+2)-valent group having at least either one of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. R 12 represents a hydrogen atom, or represents an alkyl group having 1 to 13 carbon atoms which can be substituted. n represents 1 or 2. When n is 2, two R 12 may be the same or different. R represents a bonding position.

Description

Technical Field

[0001] This invention relates to compositions for forming a photoresist underlayer, photoresist underlayers, laminates, methods for manufacturing semiconductor devices, and methods for patterning. Background Technology

[0002] For a long time, microfabrication has been carried out in the manufacturing of semiconductor devices using photolithography with photoresist compositions. This microfabrication process involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with active light such as ultraviolet light through a mask pattern depicting a device pattern, and developing the image. The resulting photoresist pattern is then used as a protective film to etch the substrate, thereby forming micro-uneven surfaces on the substrate surface corresponding to the photoresist pattern. In recent years, with the increasing integration of semiconductor devices, in addition to the previously used i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), the practical application of EUV light (wavelength 13.5nm) or EB (electron beam) in cutting-edge microfabrication has been studied for the active light used. Consequently, poor photoresist pattern formation due to the influence of the semiconductor substrate has become a major problem. Therefore, to solve this problem, methods for setting a photoresist underlayer film between the photoresist and the semiconductor substrate are being widely researched.

[0003] As a composition for forming a resist underlayer film, a composition for forming a resist underlayer film has been proposed comprising a compound (A) of formula (1) (in formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring or a heterocyclic ring) dissolved in a solvent, a compound (B) having two functional groups reactive to epoxy groups, and a compound (C) having one functional group reactive to epoxy groups (see Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2022 / 075339 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] The characteristics required for the lower layer of the resist film include, for example, not mixing with the resist film formed on the upper layer (insoluble in resist solvent) and being able to improve the adhesion of the resist pattern to form a fine resist pattern.

[0009] The present invention was made in view of the above circumstances, and its object is to provide a composition for forming a resist underlayer film capable of forming fine resist patterns, and a method for manufacturing a resist underlayer film, a stack, a semiconductor device, and a patterning method using the composition for forming a resist underlayer film.

[0010] Problem-solving methods

[0011] The inventors conducted in-depth research to solve the above problems and found that the above problems could be solved, thus completing the present invention with the following key points.

[0012] That is, the present invention includes the following solutions.

[0013] [1] A composition for forming a resist underlayer film, comprising a polymer (A) having a partial structure represented by the following formula (A), a polymer (B) having polymerizable multiple bonds, and a solvent (C).

[0014] In formula (A), R 11 R represents an (n+2) valence group having at least one of aromatic hydrocarbon rings and aliphatic hydrocarbon rings. 12 This represents a hydrogen atom, or an alkyl group that can be substituted with at least one group selected from alkoxy groups having 1 to 13 carbon atoms, alkylcarbonyloxy groups having 2 to 13 carbon atoms, alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylthio groups having 1 to 13 carbon atoms, nitro groups, alkylsulfonyloxy groups having 1 to 13 carbon atoms, and alkoxysulfonyl groups having 1 to 13 carbon atoms, and has 1 to 13 carbon atoms. n represents 1 or 2. When n is 2, the two R groups... 12 They can be the same or different. Indicates the bonding location.

[0015] [2] According to the composition for forming a resist underlayer film as described in [1], the polymer (B) is a polymer (B-1) having a structural unit represented by the following formula (B-1) or a polymer (B-2) having a structural unit represented by the following formula (B-2).

[0016] In equation (B-1), R 1 This indicates an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. L 1 Indicates a single bond or a linking group. L 2 This indicates a monovalent group having the aforementioned polymerizable multiple bonds.

[0017]

[0018] In equation (B-2), A 11 A12 A 13 A 14 A 15 and A 16 Each can independently represent a hydrogen atom, a methyl group, or an ethyl group, Q. 21 R represents a divalent organic group. 21 This indicates a divalent group having the polymerizable multiple bonds described above.

[0019] [3] According to the composition for forming a resist underlayer film as described in [2], the L in the structural unit represented by formula (B-1) 1 -L 2 It has a structure represented by the following formulas (1a), (1b) or (1c).

[0020]

[0021] In equations (1a) to (1c), R 2 It refers to an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. a and b represents the bonding position. a represents the main chain side of polymer (B-1). b represents the end of the side chain of polymer (B-1).

[0022] [4] The composition for forming a resist underlayer film according to any one of [1] to [3], wherein the polymer (A) has a structural unit represented by the following formula (A-11).

[0023]

[0024] In formula (A-11), A 1 A 2 A 3 A 4 A 5 and A 6 Each of these can independently represent a hydrogen atom, a methyl group, or an ethyl group; Q represents a divalent organic group. R 11 R represents an (n+2) valence organic group having at least one of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. 12 This represents a hydrogen atom, or an alkyl group that can be substituted with at least one group selected from alkoxy groups having 1 to 13 carbon atoms, alkylcarbonyloxy groups having 2 to 13 carbon atoms, alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylthio groups having 1 to 13 carbon atoms, nitro groups, alkylsulfonyloxy groups having 1 to 13 carbon atoms, and alkoxysulfonyl groups having 1 to 13 carbon atoms, and has 1 to 13 carbon atoms. n represents 1 or 2. When n is 2, the two R groups... 12 They can be the same or different.

[0025] [5] According to the composition for forming a resist underlayer film as described in [4], Q in the formula (A-11) represents any one of the following formulas (A-21) and (A-22).

[0026]

[0027] In equation (A-21), X 1 This represents the divalent group shown in formula (A-21-1), formula (A-21-2), or formula (A-21-3). 1 and Z 2 Each can independently represent a single bond or a divalent group as shown in the following formula (A-21-4). Indicates the bonding location.

[0028] In equation (A-22), Q 1 This indicates a divalent group having an aromatic or aliphatic hydrocarbon ring. n1 and n2 each independently represent 0 or 1. Indicates the bonding location.

[0029]

[0030] In equations (A-21-1) to (A-21-3), R 1 ~R 5 Each of the following groups independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkenyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkynyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from alkyl groups having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. R 1 and R 2 They can also bond with each other to form rings with 3 to 6 carbon atoms. R 3 and R 4 They can also bond with each other to form rings with 3 to 6 carbon atoms. Indicates the bonding location. 1 indicates the bonding position with a carbon atom. 2 indicates the bonding position with the nitrogen atom.

[0031]

[0032] In equation (A-21-4), m1 is an integer from 1 to 4, and m2 is 0 or 1. 3 indicates the bonding position with the nitrogen atom. 4 indicates the bonding position with a carbon atom.

[0033] [6] According to the composition for forming a resist underlayer film as described in [5], Q in formula (A-22) 1 It represents any one of the following formulas (A-22-1) to (A-22-4).

[0034]

[0035] In equations (A-22-1) to (A-22-4), R 31 ~R 36 Each of these can be independently represented as a halogen atom, a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkoxy group with 2 to 6 carbon atoms, an alkenyloxy group with 2 to 6 carbon atoms, an alkynyloxy group with 2 to 6 carbon atoms, an acyl group with 2 to 6 carbon atoms, an aryloxy group with 6 to 12 carbon atoms, an arylcarbonyl group with 7 to 13 carbon atoms, or an aralkyl group with 7 to 13 carbon atoms. Indicates the bonding location.

[0036] In equation (A-22-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. R 31 When there are two or more R, there are two or more R 31 They can be the same or different.

[0037] In equation (A-22-2), Z 1 This indicates a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms. n12 and n13 each independently represent integers from 0 to 4. R 32 When there are two or more R, there are two or more R 32 They can be the same or different. R 33 When there are two or more R, there are two or more R 33 They can be the same or different.

[0038] In formula (A-22-3), Y 1 and Y 2 Each can independently represent a single bond or an alkylene group with 1 to 6 carbon atoms. n14 represents an integer from 0 to 4. R 34 When there are two or more R, there are two or more R 34 They can be the same or different.

[0039] In formula (A-22-4), Z 2 This indicates a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms. n15 and n16 each independently represent integers from 0 to 4. R 35 When there are two or more R, there are two or more R35 They can be the same or different. R 36 When there are two or more R, there are two or more R 36 They can be the same or different.

[0040] [7] The composition for forming a resist underlayer film according to any one of [1] to [6], wherein the mass ratio of the polymer (A) to the polymer (B) (polymer (A): polymer (B)) is 20:80 to 80:20.

[0041] [8] The composition for forming a resist underlayer film according to any one of [1] to [7], wherein the solvent (C) comprises at least one monocarboxylic acid ester selected from alkylene glycol monoalkyl ethers and alkylene glycol monoalkyl ethers.

[0042] [9] The composition for forming a resist underlayer film according to any one of [1] to [8], wherein it further comprises a crosslinking agent (D).

[0043]

[10] In the composition for forming a resist underlayer film according to [9], the crosslinking agent (D) is at least one selected from amino plastic crosslinking agents and phenolic plastic crosslinking agents.

[0044]

[11] The composition for forming a resist underlayer film according to any one of [1] to

[10] , wherein it further comprises a curing catalyst (E).

[0045]

[12] The composition for forming a resist underlayer film according to any one of [1] to

[11] is used for EUV lithography.

[0046]

[13] The composition for forming a resist underlayer film according to any one of [1] to

[12] is used to form a metal-containing resist underlayer film.

[0047]

[14] A resist underlayer film, which is a cured product of the resist underlayer film forming composition described in any one of [1] to

[13] .

[0048]

[15] A stack comprising a semiconductor substrate and the resist underlayer film described in

[14] .

[0049]

[16] A method for manufacturing a semiconductor device, comprising:

[0050] The process of forming a photoresist underlayer film on a semiconductor substrate using any one of [1] to

[13] 's photoresist underlayer film forming composition; and

[0051] The process of forming a resist film on the lower resist film.

[0052]

[17] A pattern forming method, comprising

[0053] The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition according to any one of [1] to

[13] ; The process of forming a resist film on the lower resist film; The process of irradiating the resist film with light or an electron beam, followed by developing the resist film to obtain a resist pattern; and The process of using the resist pattern as a mask to etch the underlying resist film.

[0054] Invention Effects

[0055] According to the present invention, a composition for forming a photoresist underlayer film capable of forming fine photoresist patterns can be provided, as well as a method for manufacturing a photoresist underlayer film, a stack, a semiconductor device, and a patterning method using the composition for forming a photoresist underlayer film. Detailed Implementation

[0056] (Composition for forming the lower layer of the resist film)

[0057] The composition for forming a resist underlayer film of the present invention comprises a polymer (A), a polymer (B), and a solvent (C).

[0058] The composition for forming the lower layer film of the resist may include a crosslinking agent (D), a curing catalyst (E), etc.

[0059] Polymer (A) has a partial structure represented by the following formula (A).

[0060] Polymer (B) has polymerizable multiple bonds.

[0061] By including polymer (A) and polymer (B) in the composition for forming the resist underlayer film, fine resist patterns can be formed on the resist underlayer film formed by the composition for forming the resist underlayer film.

[0062] While the exact cause is uncertain, the inventors believe that the partial structure represented by formula (A) in polymer (A) and the polymerizable multiple bonds in polymer (B) improve the adhesion of the resist pattern to the underlying resist film. Furthermore, the inventors believe that this improved adhesion results in even finer resist patterns not easily collapsing, thereby enabling the formation of micro-fine resist patterns.

[0063] <Polymer (A)>

[0064] Polymer (A) has a partial structure represented by the following formula (A).

[0065]

[0066] In formula (A), R 11 R represents an (n+2) valence group having at least one of aromatic hydrocarbon rings and aliphatic hydrocarbon rings. 12 This represents a hydrogen atom, or an alkyl group that can be substituted with at least one group selected from alkoxy groups having 1 to 13 carbon atoms, alkylcarbonyloxy groups having 2 to 13 carbon atoms, alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylthio groups having 1 to 13 carbon atoms, nitro groups, alkylsulfonyloxy groups having 1 to 13 carbon atoms, and alkoxysulfonyl groups having 1 to 13 carbon atoms, and has 1 to 13 carbon atoms. n represents 1 or 2. When n is 2, the two R groups... 12 They can be the same or different. Indicates the bonding location.

[0067] The preferred bonding position in formula (A) is a bond with a carbon atom.

[0068] Polymer (A) preferably has structural units represented by the following formula (A-11). It should be noted that, for example, a portion of the structure represented by formula (A) is a part of the structural unit represented by the following formula (A-11).

[0069]

[0070] In formula (A-11), A 1 A 2 A 3 A 4 A 5 and A 6 Each of these can independently represent a hydrogen atom, a methyl group, or an ethyl group; Q represents a divalent organic group. R 11 R represents an (n+2) valence organic group having at least one of aromatic hydrocarbon rings and aliphatic hydrocarbon rings. 12 This represents a hydrogen atom, or an alkyl group that can be substituted with at least one group selected from alkoxy groups having 1 to 13 carbon atoms, alkylcarbonyloxy groups having 2 to 13 carbon atoms, alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylthio groups having 1 to 13 carbon atoms, nitro groups, alkylsulfonyloxy groups having 1 to 13 carbon atoms, and alkoxysulfonyl groups having 1 to 13 carbon atoms, and has 1 to 13 carbon atoms. n represents 1 or 2. When n is 2, the two R groups... 12 They can be the same or different.

[0071] < <R 11 >>

[0072] In equations (A) and (A-11), R 11 It represents an (n+2) valence organic group having at least one of aromatic hydrocarbon rings and aliphatic hydrocarbon rings.

[0073] There is no particular limitation on the number of carbon atoms in the (n+2) valence organic group, but the number of carbon atoms is preferably 4 to 30, more preferably 4 to 20, and particularly preferably 4 to 15.

[0074] Examples of aromatic hydrocarbon rings that are the (n+2) valence organic groups include, for example, benzene rings, naphthalene rings, and anthracene rings. Examples of aliphatic hydrocarbon rings include, for example, cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0075] Aliphatic hydrocarbon rings can have polycyclic structures.

[0076] Aliphatic hydrocarbon rings may or may not have unsaturated bonds.

[0077] Aliphatic hydrocarbon rings can be aliphatic hydrocarbon rings that form bridging polycyclic structures. Bridging polycyclic structures can have heteroatoms as constituent atoms. Examples of heteroatoms include oxygen atoms and nitrogen atoms. Examples of bridging polycyclic structures include norbornene rings.

[0078] As R 11 Examples of trivalent organic groups include the following. These trivalent organic groups can be substituted by alkyl, alkylcarbonyl, hydroxyl, alkoxy, alkoxycarbonyl, halogen atom, nitro, or combinations of two or more of these. In the following formulas, Indicates the bonding location.

[0079]

[0080] As a trivalent organic group, a trivalent organic group represented by the following formula is preferred.

[0081]

[0082] In the formula, q represents an integer from 0 to 3, and R 2 This indicates an alkyl group with 1 to 6 carbon atoms, or an alkoxy group with ~6 carbon atoms. Where q represents 2 or 3, R... 2 They can be the same or different. Indicates the bonding location.

[0083] As R 11 For example, the following tetravalent organic groups can be listed.

[0084]

[0085] In equations (x-1) to (x-11), R 1 ~R 4Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, a monovalent organic group with 1 to 6 carbon atoms and a fluorine atom, or a phenyl group. R 5 and R 6 Each can be used independently to represent a hydrogen atom or a methyl group. Indicates the bonding location.

[0086]

[0087] In formulas (X3-1) and (X3-2), x and y independently represent single bonds, ether bonds, carbonyl groups, ester bonds, alkyl dienes with 1 to 5 carbon atoms, 1,4-phenylene groups, sulfonyl groups, or amide groups, and j and k are integers of 0 or 1. Indicates the bonding location.

[0088] Indicates the bonding location.

[0089] The tetravalent organic group represented by formula (X3-1) or (X3-2) can be any of the structures shown in formulas (X3-3) to (X3-19) below.

[0090] Indicates the bonding location.

[0091] < <R 12 >>

[0092] In equations (A) and (A-11), R 12 It refers to a hydrogen atom or an alkyl group having 1 to 13 substituted carbon atoms.

[0093] The alkyl group having 1 to 13 carbon atoms may be substituted with at least one group selected from alkoxy group having 1 to 13 carbon atoms, alkyl carbonyloxy group having 2 to 13 carbon atoms, alkoxy carbonyl group having 2 to 13 carbon atoms, alkyl thio group having 1 to 13 carbon atoms, nitro group, alkyl sulfonyloxy group having 1 to 13 carbon atoms, and alkoxy sulfonyl group having 1 to 13 carbon atoms.

[0094] The alkyl group having 1 to 13 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

[0095] As an alkoxy group having 1 to 13 carbon atoms, an alkoxy group having 1 to 8 carbon atoms is preferred, and an alkoxy group having 1 to 6 carbon atoms is more preferred.

[0096] As an alkyl carbonyl group having 2 to 13 carbon atoms, an alkyl carbonyl group having 2 to 8 carbon atoms is preferred, and an alkyl carbonyl group having 2 to 6 carbon atoms is more preferred.

[0097] As an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms is preferred, and an alkoxycarbonyl group having 2 to 6 carbon atoms is more preferred.

[0098] The alkylthio group having 1 to 13 carbon atoms is preferably an alkylthio group having 1 to 8 carbon atoms, and more preferably an alkylthio group having 1 to 6 carbon atoms.

[0099] As an alkylsulfonyloxy group having 1 to 13 carbon atoms, an alkylsulfonyloxy group having 1 to 8 carbon atoms is preferred, and an alkylsulfonyloxy group having 1 to 6 carbon atoms is more preferred.

[0100] The alkoxysulfonyl group having 1 to 13 carbon atoms is preferably an alkoxysulfonyl group having 1 to 8 carbon atoms, and more preferably an alkoxysulfonyl group having 1 to 6 carbon atoms.

[0101] In this specification, the term "alkyl" is not limited to a straight chain; it can be a branched chain or a cyclic chain. Examples of straight-chain or branched-chain alkyl groups include, for example, methyl, ethyl, isopropyl, tert-butyl, and n-hexyl. Examples of cyclic alkyl groups (cycloalkyl groups) include, for example, cyclobutyl, cyclopentyl, and cyclohexyl.

[0102] In this specification, examples of alkoxy groups include, for example, methoxy, ethoxy, n-pentoxy, isopropoxy, etc.

[0103] In this specification, examples of alkyl carbonyloxy groups include, for example, methyl carbonyloxy and ethyl carbonyloxy.

[0104] In this specification, examples of alkoxycarbonyl groups include, for example, methoxycarbonyl, ethoxycarbonyl, and isopropoxycarbonyl.

[0105] In this specification, examples of alkylthio groups include, for example, methylthio, ethylthio, n-pentylthio, isopropylthio.

[0106] In this specification, examples of alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, etc.

[0107] In this specification, as an alkynyl group, there are groups in which the double bonds of the alkenyl groups listed above are replaced with triple bonds.

[0108] In this specification, fluorine, chlorine, bromine, and iodine atoms can be listed as halogen atoms.

[0109] As R 12 From the perspective of achieving the desired effects of the present invention, alkyl groups having 1 to 13 carbon atoms or alkyl groups having 1 to 13 carbon atoms substituted with alkoxy groups having 1 to 13 carbon atoms are preferred.

[0110] When n is 2, two R values ​​are preferred. 12 same.

[0111] < <q>>

[0112] In formula (A-11), Q represents a divalent organic group. There are no particular limitations on the divalent organic group, but a divalent organic group having a heteroatom is preferred, and a divalent organic group having a nitrogen atom and an oxygen atom is more preferred. Examples of heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms.

[0113] There is no particular limitation on the number of carbon atoms in the divalent organic group, but it is preferred to have 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.

[0114] As for Q, it is preferred to be represented by any one of the following formulas (A-21) and (A-22) from the perspective of obtaining the desired effect of the present invention.

[0115]

[0116] In equation (A-21), X 1 This represents the divalent group shown in formula (A-21-1), formula (A-21-2), or formula (A-21-3). 1 and Z 2 Each can independently represent a single bond or a divalent group as shown in the following formula (A-21-4). Indicates the bonding location.

[0117] In equation (A-22), Q 1 This indicates a divalent group having an aromatic or aliphatic hydrocarbon ring. n1 and n2 each independently represent 0 or 1. Indicates the bonding location.

[0118]

[0119] In equations (A-21-1) to (A-21-3), R 1 ~R 5 Each of the following groups independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkenyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkynyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from alkyl groups having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. R 1 and R 2 They can also bond with each other to form rings with 3 to 6 carbon atoms. R 3 and R 4 They can also bond with each other to form rings with 3 to 6 carbon atoms. Indicates the bonding location. 1 indicates the bonding position with a carbon atom. 2 indicates the bonding position with the nitrogen atom.

[0120]

[0121] In equation (A-21-4), m1 is an integer from 1 to 4, and m2 is 0 or 1. 3 indicates the bonding position with the nitrogen atom. 4 indicates the bonding position with a carbon atom.

[0122] Q in equation (A-22) 1 It is preferably represented by any one of the following formulas (A-22-1) to (A-22-4).

[0123]

[0124] In equations (A-22-1) to (A-22-4), R 31 ~R 36 Each of these can be independently represented as a halogen atom, a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkoxy group with 2 to 6 carbon atoms, an alkenyloxy group with 2 to 6 carbon atoms, an alkynyloxy group with 2 to 6 carbon atoms, an acyl group with 2 to 6 carbon atoms, an aryloxy group with 6 to 12 carbon atoms, an arylcarbonyl group with 7 to 13 carbon atoms, or an aralkyl group with 7 to 13 carbon atoms. Indicates the bonding location.

[0125] In equation (A-22-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. R 31 When there are two or more R, there are two or more R 31 They can be the same or different.

[0126] In equation (A-22-2), Z 1 This indicates a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms. n12 and n13 each independently represent integers from 0 to 4. R 32 When there are two or more R, there are two or more R 32 They can be the same or different. R 33 When there are two or more R, there are two or more R 33 They can be the same or different.

[0127] In formula (A-22-3), Y 1 and Y 2 Each can independently represent a single bond or an alkylene group with 1 to 6 carbon atoms. n14 represents an integer from 0 to 4. R 34 When there are two or more R, there are two or more R 34 They can be the same or different.

[0128] In formula (A-22-4), Z 2 This indicates a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms. n15 and n16 each independently represent integers from 0 to 4. R 35 When there are two or more R, there are two or more R 35 They can be the same or different. R 36 When there are two or more R, there are two or more R 36 They can be the same or different.

[0129] As Q in equation (A-11), for example, the following structures can be listed.

[0130] Indicates the bonding location.

[0131] When polymer (A) has a structural unit represented by formula (A-11), there is no particular limitation on the mass ratio of the structural unit represented by formula (A-11) in polymer (A), but it is preferably 50% to 100% by mass, more preferably 75% to 100% by mass, and particularly preferably 90% to 100% by mass.

[0132] There are no particular limitations on the method for manufacturing polymer (A). For example, a method can be given by reacting at least one of the tetracarboxylic dianhydride represented by formula (A1) and the tricarboxylic dianhydride represented by formula (A2), the diepoxide represented by formula (2A), and the compound represented by formula (C). In this case, polymer (A) having the structural unit represented by formula (A-11) can be obtained.

[0133] For example, at least one of the tetracarboxylic dianhydride represented by formula (A1) and the tricarboxylic dianhydride represented by formula (A2) and the diepoxide represented by formula (2A) are dissolved in an organic solvent containing a large excess of the compound represented by formula (C). Then, polymerization is carried out in the presence of a catalyst that activates the epoxy groups, thereby obtaining polymer (A).

[0134] It should be noted that in R 12 In the case of hydrogen atoms, compounds represented by formula (C) are not used; other inert organic solvents are used instead.

[0135] Alternatively, in the above reaction, tetracarboxylic acid or tricarboxylic acid can be used instead of tetracarboxylic dianhydride represented by formula (A1) and tricarboxylic anhydride represented by formula (A2).

[0136] Catalysts for activating epoxy groups include, for example, quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. The amount of catalyst used can be selected from 0.1% to 10% by mass relative to the total mass of the polymer feedstock used in the reaction. The optimal conditions for the polymerization reaction can be selected, for example, from 80 to 160°C and 2 to 50 hours.

[0137]

[0138] In equations (A1) and (A2), R 11 R in equation (A-11) 11 They have the same meaning.

[0139]

[0140] In equation (2A), A 1 A 2 A 3 A 4 A 5 A 6 Q and A in equation (A-11) are respectively 1 A 2 A 3 A 4 A 5 A 6 It has the same meaning as Q.

[0141]

[0142] In equation (C), R 12 R in equation (A-11) 12 They have the same meaning.

[0143] The following compounds can be listed as examples of compounds represented by formula (C).

[0144]

[0145] There is no particular limitation on the molecular weight of polymer (A).

[0146] The lower limit of the weight-average molecular weight of polymer (A) is, for example, 500, 1,000, 2,000 or 3,000.

[0147] The upper limit of the weight-average molecular weight of polymer (A) is, for example, 100,000, 75,000 or 50,000.

[0148] The content of polymer (A) in the composition for forming the lower layer of the resist film is not particularly limited, but from the viewpoint of obtaining the effect of the present invention, it is preferably 20% to 50% by mass, more preferably 25% to 45% by mass, relative to the film composition.

[0149] It should be noted that, in this invention, the membrane constituents refer to components other than the solvent contained in the composition.

[0150] <Polymer (B)>

[0151] Polymer (B) has polymerizable multiple bonds.

[0152] The polymerizable multiple bond is, for example, one or more polymerizable multiple bonds selected from carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds.

[0153] The polymer (B) may have polymerizable multiple bonds in the main chain or in the side chain.

[0154] Polymer (B) is a different polymer from polymer (A).

[0155] Polymer (B) is an organic polymer.

[0156] Polymer (B) can be a homopolymer or a copolymer.

[0157] Polymer (B) has, for example, (meth)acryloyl, vinyl aryl (e.g., styrene), ethyleneoxy, allyl, etc., as polymerizable multiple bonds in its side chain.

[0158] Polymer (B) has, for example, vinyl (-CH=CH-) groups on the main chain or side chain as polymerizable multiple bonds as described above.

[0159] As for polymer (B), from the viewpoint of obtaining the effects of the present invention, polymer (B-1) having the structural unit represented by the following formula (B-1) is preferred.

[0160] As for polymer (B), from the viewpoint of obtaining the effects of the present invention, polymer (B-2) having the structural unit represented by the following formula (B-2) is preferred.

[0161] <<Polymer (B-1)>>

[0162] Polymer (B-1) is, for example, a polymer formed by polymerizing polymerizable unsaturated bonds of a compound containing groups having polymerizable unsaturated bonds. Polymer (B-1) can be a homopolymer or a copolymer.

[0163] Examples of groups that have polymerizable unsaturated bonds include (meth)acryloyl, vinyl aryl (e.g., styryl), ethoxy, allyl, etc.

[0164] For example, in polymer (B-1), polymerizable multiple bonds are bonded to the main chain of polymer (B-1) through linking groups having structures obtained by reacting epoxy groups with nucleophilic functional groups.

[0165] As a nucleophilic functional group, it can be selected from one or more of the following groups: carboxyl, hydroxyl, amino, and thiol. The hydroxyl group may or may not be a phenolic hydroxyl group.

[0166] When the epoxy group reacts with the carboxyl group, the reaction proceeds as follows to form the following structure (S1).

[0167]

[0168] In the formula, Indicates the bonding location.

[0169] Alternatively, for example, in polymer (B-1), polymerizable multiple bonds are bonded to the main chain of polymer (B-1) via linking groups having structures obtained by reacting isocyanate groups with nucleophilic functional groups. In this case, nucleophilic functional groups can be, for example, one or more selected from hydroxyl, amino, and thiol groups. The hydroxyl group may or may not be a phenolic hydroxyl group.

[0170] The polymer (B-1) has a structural unit represented by the following formula (B-1).

[0171]

[0172] In equation (B-1), R 1 This indicates an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. L 1 Indicates a single bond or a linking group. L 2 This indicates a monovalent group that has the aforementioned polymerizable multiple bonds.

[0173] 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-methylcyclopropyl, 2-methylcyclopropyl, n-pentyl, 1-methyln-butyl, 2-methyln-butyl, 3-methyln-butyl, 1,1-dimethyln-propyl, 1,2-dimethyln-propyl, 2,2-dimethyln-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methyln-butyl... Cyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 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-butyl Methyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl The following compounds are used: 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl, n-heptyl, cycloheptyl, norbornyl, n-octyl, cyclooctyl, n-nonyl, isobornyl, tricyclononyl, n-decyl, adamantyl, tricyclodecyl, etc. Among these, methyl is preferred.

[0174] In L 1 In the case of a linking group, there is no particular limitation on the number of carbon atoms in the linking group; for example, 1 to 10 can be cited.

[0175] L 1 When the linking group is used, examples of linking groups include those with a structure obtained by reacting an epoxy group with a nucleophilic functional group, and those with a structure obtained by reacting an isocyanate group with a nucleophilic functional group.

[0176] As L 1 For example, the following linking groups (L1-1) to (L1-11) can be listed.

[0177]

[0178] In the formula, 1 represents R in equation (B-1) 1 The bonding positions of the carbon atoms bonded on the top. 2 represents L in equation (B-1) 2 The bonding location of the bond.

[0179] L 2 It is a monovalent group with polymerizable multiple bonds. The monovalent group can be the polymerizable multiple bond itself.

[0180] There is no particular restriction on the number of carbon atoms in the monovalent group; for example, it can be 1 to 20 or 1 to 10.

[0181] L 2 For example, the following monovalent groups (L2-1) to (L2-81) can be listed.

[0182]

[0183] In the formula, Indicates the bonding location.

[0184] The following combinations can be cited as examples of the combination of linking groups (L1-1) to (L1-9) and monovalent groups (L2-1) to (L2-7).

[0185] • Combination of (L1-1) and (L2-1)

[0186] Combinations of (L1-1) and (L2-2)

[0187] • Combination of (L1-1) and (L2-7)

[0188] • Combination of (L1-2) and (L2-3)

[0189] • Combination of (L1-2) and (L2-4)

[0190] • Combination of (L1-2) and (L2-7)

[0191] • Combination of (L1-3) and (L2-3)

[0192] • Combination of (L1-3) and (L2-4)

[0193] • Combination of (L1-4) and (L2-7)

[0194] • Combination of (L1-5) and (L2-1)

[0195] • Combination of (L1-5) and (L2-2)

[0196] • Combination of (L1-6) and (L2-1)

[0197] • Combination of (L1-6) and (L2-2)

[0198] • Combination of (L1-7) and (L2-5)

[0199] • Combination of (L1-7) and (L2-6)

[0200] • Combination of (L1-8) and (L2-7)

[0201] • Combination of (L1-9) and (L2-7)

[0202] It should be noted that the combination of (L1-1) and (L2-1) has the same meaning as the combination of (L1-2) and (L2-3). The combination of (L1-1) and (L2-2) has the same meaning as the combination of (L1-2) and (L2-4).

[0203] In addition, L in the structural unit represented by equation (B-1) 1 -L 2 Preferably, the structure has the following formula (1a), (1b) or (1c).

[0204]

[0205] In equations (1a) to (1c), R 2 It refers to an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. a and b represents the bonding position. a represents the main chain side of polymer (B-1). b represents the end of the side chain of polymer (B-1).

[0206] It should be noted that, b can also be the bonding position with a hydrogen atom.

[0207] As structural units represented by equation (B-1), the following structural units can be listed for example.

[0208]

[0209] As an example of a polymer (B-1) having a structural unit represented by formula (B-1), it can be obtained by reacting a glycidyl methacrylate polymer with a compound (C1) having polymerizable multiple bonds and a carboxyl group, as described below. The glycidyl methacrylate polymer can be a homopolymer or a copolymer. Examples of copolymers include copolymers of glycidyl methacrylate and 2-hydroxyethyl methacrylate, and copolymers of glycidyl methacrylate and 2-hydroxypropyl methacrylate.

[0210]

[0211] In the formula, R 1 and L 2 respectively with R in equation (B-1) 1 and L 2 They have the same meaning.

[0212] The reaction can be carried out, for example, in the presence of a catalyst such as tetrabutylphosphonium bromide.

[0213] Examples of compounds having polymerizable multiple bonds and carboxyl groups (C1) include, for example, acrylic acid, methacrylic acid, 4-vinylbenzoic acid, sorbic acid, tetrahydric acid, maleic acid, 1-cyclohexene-1-carboxylic acid, 2-benzylacrylic acid, trans-cinnamic acid, trans-4-methoxycinnamic acid, α-phenylcinnamic acid, monomethyl fumarate, α-cyanocinonic acid, 4-nitrocinnamic acid, 3-nitrocinnamic acid, etc.

[0214] As another example of a polymer (B-1) having a structural unit represented by formula (B-1), it can be obtained, for example, by reacting a hydroxyl-containing (meth)acrylate polymer with a compound (C2) having polymerizable multiple bonds and isocyanate groups, as described below. The hydroxyl-containing (meth)acrylate polymer can be a homopolymer or a copolymer.

[0215]

[0216] In the formula, R 1 and L 2 respectively with R in equation (B-1) 1 and L 2 They have the same meaning. R 11 R represents a divalent organic group. 12 It represents a single bond or a divalent organic group.

[0217] R 11 For example, alkylene groups having 1 to 4 carbon atoms.

[0218] R 12 For example, it can be a single bond or an alkylene group with 1 to 4 carbon atoms.

[0219] As another example of a polymer (B-1) having a structural unit represented by formula (B-1), it can be obtained by reacting a styrene-based polymer having hydroxyl or amino groups with a compound (C2) having polymerizable multiple bonds and isocyanate groups, as described below. The styrene-based polymer having hydroxyl or amino groups can be a homopolymer or a copolymer.

[0220]

[0221] In the formula, R 1 and L 2 respectively with R in equation (B-1) 1 and L 2 They have the same meaning. R 12 It represents a single bond or a divalent organic group.

[0222] R 12 For example, it can be a single bond or an alkylene group with 1 to 4 carbon atoms.

[0223] As compounds having polymerizable multiple bonds and isocyanate groups (C2), the following compounds can be listed as examples.

[0224]

[0225] The polymer (B-1) may have structural units other than those represented by formula (B-1). Examples of such structural units include those represented by formula (B-12), formula (B-13), and formula (B-14).

[0226]

[0227] In equation (B-12), R 2 L represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. 3 It represents a monovalent group with 1 to 20 carbon atoms.

[0228] In equation (B-13), R 2 Indicates an alkyl group with 1 to 10 hydrogen atoms, Ar indicates a benzene ring or a naphthalene ring, L 4 This indicates a hydroxyl, cyano, nitro, or amino group (-NH2). L 5 This represents a halogen atom, an alkyl group with 1 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms. m1 represents an integer from 0 to 3. m2 represents an integer from 0 to 5. The sum of m1 and m2 is 0 to 5. When m1 is 2 or 3, multiple L... 4 They can be the same or different. When m2 is 2~5, multiple L 5 They can be the same or different.

[0229] In equation (B-14), R 2 L represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. 6 It represents a monovalent organic group selected from alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 40 carbon atoms, wherein at least one hydrogen atom of the alkyl group and the aryl group can be replaced by a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

[0230] As L in equation (B-12) 3 The monovalent group having 1 to 20 carbon atoms, for example, represents a monovalent organic group selected from alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 40 carbon atoms, wherein at least one hydrogen atom of the aforementioned alkyl and aryl groups can be replaced by a hydroxyl group. Furthermore, for the aforementioned alkyl groups, an oxygen atom can be inserted between carbon atoms.

[0231] Additionally, as L 3 Monovalent groups with 1 to 20 carbon atoms, for example, can be represented by the group represented by the following formula (2-1).

[0232]

[0233] In equation (2-1), L 3a It indicates an alkyl group with 1 to 6 carbon atoms that can be substituted, or an aromatic hydrocarbon group that can be substituted.

[0234] As L 3a Aromatic hydrocarbon groups, such as phenyl and naphthyl, can be listed.

[0235] As L 3a Substituents in alkyl groups having 1 to 6 carbon atoms can be substituted, such as halogen atoms and hydroxyl groups. There can be one or more substituents. When there are multiple substituents, they can be the same or different.

[0236] As L 3a Substituents in substituted aromatic hydrocarbon groups can include, for example, halogen atoms, hydroxyl groups, and alkyl groups with 1 to 3 carbon atoms that can be replaced by halogen atoms. There can be one or more substituents. When there are multiple substituents, they can be the same or different.

[0237] R 2 The alkyl groups representing 1 to 10 carbon atoms, and L 3 and L 6 Specific examples of alkyl groups having 1 to 10 carbon atoms are as described above.

[0238] As L 5 Halogen atoms in the atom can be exemplified by fluorine, chlorine, bromine, iodine, etc.

[0239] As L 5 Alkyl groups having 1 to 6 carbon atoms can be exemplified by, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, etc.

[0240] As L 5 Alkoxy groups with 1 to 6 carbon atoms can be exemplified by methoxy, ethoxy, propoxy, butoxy, etc.

[0241] m1 represents an integer from 0 to 3, which can be 0, 1, 2, or 3.

[0242] m2 represents an integer from 0 to 5, which can be 0, 1, 2, 3, 4, or 5.

[0243] As L 3 and L 6 Aryl groups with 6 to 40 carbon atoms can be listed as 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, etc.

[0244] As L 6 Alkoxy groups with 1 to 6 carbon atoms can be exemplified by methoxy, ethoxy, propoxy, butoxy, etc.

[0245] Examples of compounds that can be used as monomers for the derivation formula (B-12) include the following.

[0246]

[0247] Examples of compounds that can be used as monomers for the derivation formula (B-13) include the following.

[0248]

[0249] Me represents methyl.

[0250] Examples of compounds that can be used as monomers for the derivation formula (B-14) include the following.

[0251]

[0252] There is no particular limitation on the proportion of the structural unit represented by formula (B-1) in polymer (B-1). The molar ratio of the structural unit represented by formula (B-1) relative to all structural units of polymer (B-1) can be, for example, 20 mol% to 100 mol%, 40 mol% to 100 mol%, or 60 mol% to 100 mol%.

[0253] There is no particular limitation on the proportion of the total (S) of the structural units represented by formula (B-12), formula (B-13) and formula (B-14) in polymer (B-1). The molar ratio of the total (S) relative to all structural units of polymer (B-1) can be, for example, 0 mol% to 80 mol%, or more than 0 mol% and less than 60 mol%.

[0254] Polymer (B-1) may contain structural units other than those represented by formula (B-1), structural unit sites represented by formula (B-12), structural units represented by formula (B-13), and structural units other than those represented by formula (B-14). In this case, the molar percentage of other structural units in all structural units of polymer (B-1) is, for example, greater than 0 mol% and less than 20 mol%.

[0255] <<Polymer (B-2)>>

[0256] The polymer (B-2) has the structural unit represented by the following formula (B-2).

[0257]

[0258] In equation (B-2), A 11 A 12 A 13 A 14 A 15 and A 16 Each can independently represent a hydrogen atom, a methyl group, or an ethyl group, Q. 21 R represents a divalent organic group. 21 This indicates a divalent group having the aforementioned polymerizable multiple bonds.

[0259] As Q 21 Specific examples and preferred examples can be given by citing specific examples and preferred examples of Q in formula (A-11).

[0260] As R 21 The polymerizable multiple bonds it possesses are preferably carbon-carbon double bonds.

[0261] As R 21 The number of carbon atoms, for example, can be 2 to 10.

[0262] R 21 It may or may not have heteroatoms.

[0263] R 21 It can also be a divalent hydrocarbon group.

[0264] As R 21 For example, the following structures can be listed.

[0265] Indicates the bonding location.

[0266] The mass ratio of the structural unit represented by formula (B-2) in polymer (B-2) is not particularly limited, but is preferably 50% to 100% by mass, more preferably 75% to 100% by mass, and particularly preferably 90% to 100% by mass.

[0267] There are no particular limitations on the method of manufacturing polymer (B-2), and examples include reacting a dicarboxylic acid represented by formula (1B) with a diepoxide represented by formula (2B).

[0268] Catalysts for activating epoxy groups include, for example, quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. The amount of catalyst used can be selected from 0.1% to 10% by mass relative to the total mass of the polymer feedstock used in the reaction. The optimal conditions for the polymerization reaction can be selected from, for example, a range of 80–160°C and 2–50 hours.

[0269]

[0270] In equation (1B), R 21 R in equation (B-2) 21 They have the same meaning.

[0271]

[0272] In equation (2B), A 11 A 12 A 13 A 14 A 15 A 16 and Q 21 Compare with A in equation (B-2) respectively 11 A 12 A 13 A 14 A 15 A 16 and Q 21 They have the same meaning.

[0273] There are no particular restrictions on the molecular weight of polymer (B).

[0274] The lower limit of the weight-average molecular weight of polymer (B) is, for example, 500, 1,000, 2,000 or 3,000.

[0275] The upper limit of the weight-average molecular weight of polymer (B) is, for example, 100,000, 50,000 or 30,000.

[0276] The content of polymer (B) in the composition for forming the lower layer of the resist film is not particularly limited, but from the viewpoint of obtaining the effect of the present invention, it is preferably 20% to 50% by mass, more preferably 25% to 45% by mass, relative to the film composition.

[0277] There are no particular limitations on the mass ratio of polymer (A) to polymer (B) (polymer (A): polymer (B)), but from the viewpoint of obtaining the desired effect of the present invention, it is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and particularly preferably 40:60 to 60:40.

[0278] The total content of polymer (A) and polymer (B) in the composition for forming the lower layer of the resist film is not particularly limited. However, from the viewpoint of obtaining the effects of the present invention, it is preferably 40% to 100% by mass, more preferably 50% to 95% by mass, and particularly preferably 60% to 90% by mass, relative to the film composition.

[0279] <Solvent (C)>

[0280] As a solvent (C), there are no particular restrictions; it can be water or an organic solvent.

[0281] Examples of organic solvents include monoalkylene glycol ethers and monocarboxylic acid esters of monoalkylene glycol ethers.

[0282] Examples of alkylene groups that are monoalkylene glycol ethers include those with 2 to 4 carbon atoms.

[0283] Examples of alkyl groups that can be used as monoalkylene glycol ethers include alkyl groups having 1 to 4 carbon atoms.

[0284] Examples of alkylene glycol monoalkyl ethers with 3 to 8 carbon atoms are given.

[0285] Examples of alkylene glycol monoalkyl ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0286] Examples of alkylene derivatives that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkylene derivatives having 2 to 4 carbon atoms.

[0287] Examples of alkyl groups that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkyl groups having 1 to 4 carbon atoms.

[0288] Monocarboxylic acids that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers include saturated monocarboxylic acids with 2 to 4 carbon atoms.

[0289] Examples of saturated monocarboxylic acids with 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid.

[0290] Examples of monocarboxylic acid esters that are monoalkylene glycol monoalkyl ethers include, for example, 5 to 10 carbon atoms.

[0291] Examples of monocarboxylic acid esters that are monoalkylene glycol monoalkyl ethers include, for example, methyl cellolytic acetate, ethyl cellolytic acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.

[0292] Other organic solvents that can be listed include, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.

[0293] Among these solvents (C), monoalkylene glycol monoalkyl ethers and monocarboxylic acid esters of monoalkylene glycol monoalkyl ethers are preferred.

[0294] These solvents (C) can be used alone or in combination of two or more.

[0295] There is no particular limitation on the mass ratio of organic solvent in solvent (C), but it is preferably 50% to 100% by mass.

[0296] The content of solvent (C) in the composition for forming the lower layer of the resist film is not particularly limited, but is preferably 50% to 99.99% by mass, more preferably 75% to 99.95% by mass, and particularly preferably 90% to 99.9% by mass.

[0297] <Crosslinking agent (D)>

[0298] There are no particular restrictions on its use as a crosslinking agent (D).

[0299] The crosslinking agent (D) has a different structure from polymers (A) and (B).

[0300] As a crosslinking agent (D), amino plastic crosslinking agents and phenolic plastic crosslinking agents are preferred.

[0301] Amino plastic crosslinking agents are addition condensation products of amino compounds such as melamine and guanidine with formaldehyde.

[0302] Phenolic plastic crosslinking agents refer to the addition condensation products of compounds with phenolic hydroxyl groups and formaldehyde.

[0303] Examples of crosslinking agents (D) include compounds having two or more of the following structures.

[0304]

[0305] In the structure, R 101 It represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. Indicates the bonding location.

[0306] Bonding positions, such as bonds to nitrogen atoms or carbon atoms that form aromatic hydrocarbon rings.

[0307] As R 101 Preferably, it contains hydrogen atoms, methyl, ethyl or groups represented by the following structures.

[0308]

[0309] In the structure, R 102 It represents a hydrogen atom, a methyl group, or an ethyl group. Indicates the bonding location.

[0310] As a crosslinking agent (D), melamine compounds, guanidine compounds, glycourea compounds, urea compounds, and compounds with phenolic hydroxyl groups are preferred. They can be used alone or in combination of two or more.

[0311] Examples of melamine compounds include, for example, hexahydroxymethyl melamine, hexamethoxymethyl melamine, compounds obtained by methoxymethylation of 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine, or mixtures thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, compounds obtained by acyloxymethylation of 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine, or mixtures thereof.

[0312] Examples of guanidine compounds include, for example, tetrahydroxymethylguanidine, tetramethoxymethylguanidine, compounds or mixtures thereof obtained by methoxymethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylguanidine, tetramethoxyethylguanidine, tetraacyloxyguanidine, compounds or mixtures thereof obtained by acyloxymethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylguanidine, etc.

[0313] Examples of glycourea compounds include, for example, tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds or mixtures thereof obtained by methoxymethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycourea, compounds or mixtures thereof obtained by acylmethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycourea, etc.

[0314] Alternatively, as a glycourea compound, it can be, for example, a glycourea derivative represented by the following formula (1E).

[0315]

[0316] In formula (1E), each of the four R1s independently represents a methyl or ethyl group, and each of the R2 and R3 independently represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a phenyl group.

[0317] Examples of compounds represented by formula (1E-1) to (1E-6) below can be cited as glycourea derivatives represented by the above formula (1E).

[0318]

[0319] The glycourea derivative represented by formula (1E) is obtained, for example, by reacting the glycourea derivative represented by formula (2E) below with at least one compound represented by formula (3d) below.

[0320]

[0321] In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.

[0322]

[0323] In equation (3d), R 1 It indicates methyl or ethyl.

[0324] Examples of compounds represented by formula (2E) as glycourea derivatives can be listed, such as those represented by formulas (2E-1) to (2E-4). Furthermore, examples of compounds represented by formula (3d) as compounds can be listed, such as those represented by formulas (3d-1) and (3d-2).

[0325]

[0326] Examples of urea compounds include tetrahydroxymethylurea, tetramethoxymethylurea, compounds or mixtures thereof obtained by methoxymethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylurea, and tetramethoxyethylurea.

[0327] Examples of compounds having phenolic hydroxyl groups include those represented by formulas (G-1) or (G-2) below.

[0328]

[0329] In equations (G-1) and (G-2), Q 1 This indicates a single bond or an organic group with an m1 valence.

[0330] R 1 and R 4 They respectively represent alkyl groups having 2 to 10 carbon atoms, or alkyl groups having 2 to 10 carbon atoms and having an alkoxy group having 1 to 10 carbon atoms.

[0331] R 2 and R 5 These represent hydrogen atoms or methyl groups, respectively.

[0332] R 3 and R 6 They represent alkyl groups with 1 to 10 carbon atoms, or aryl groups with 6 to 40 carbon atoms, respectively.

[0333] n1 is an integer of 1 ≤ n1 ≤ 3, n2 is an integer of 2 ≤ n2 ≤ 5, n3 is an integer of 0 ≤ n3 ≤ 3, n4 is an integer of 0 ≤ n4 ≤ 3, and 3 ≤ (n1 + n2 + n3 + n4) ≤ 6.

[0334] n5 is an integer of 1 ≤ n5 ≤ 3, n6 is an integer of 1 ≤ n6 ≤ 4, n7 is an integer of 0 ≤ n7 ≤ 3, n8 is an integer of 0 ≤ n8 ≤ 3, and 2 ≤ (n5 + n6 + n7 + n8) ≤ 5.

[0335] m1 represents an integer from 2 to 10.

[0336] In addition, compounds having phenolic hydroxyl groups can be listed as, for example, compounds represented by the following formula (G-3) or formula (G-4).

[0337] The compound represented by formula (G-1) or formula (G-2) can be obtained by reacting the compound represented by formula (G-3) or formula (G-4) with a hydroxyl-containing ether compound or an alcohol having 2 to 10 carbon atoms.

[0338]

[0339] In equations (G-3) and (G-4), Q 2 This indicates a single bond or an m2 valence organic group.

[0340] R 8 R 9 R 11 and R 12 These represent hydrogen atoms or methyl groups, respectively.

[0341] R 7 and R 10 They represent alkyl groups with 1 to 10 carbon atoms, or aryl groups with 6 to 40 carbon atoms, respectively.

[0342] n9 is an integer where 1 ≤ n9 ≤ 3, n 10 It is 2≤n 10 Integers ≤ 5, n 11 It is 0≤n 11 Integers ≤ 3, n 12 It is 0≤n 12 Integers ≤ 3, and 3 ≤ (n-9+n) 10 +n 11 +n 12 ≤6.

[0343] n 13 It is 1≤n 13 Integers ≤ 3, n 14 It is 1≤n 14 Integers ≤ 4, n 15 It is 0≤n 15 Integers ≤ 3, n 16 It is 0≤n 16 Integers ≤ 3, and 2 ≤ (n 13 +n 14 +n 15 +n 16 ≤5.

[0344] m2 represents an integer from 2 to 10.

[0345] As Q 2 The m2 valence organic groups in the text can be exemplified by, for example, m2 valence organic groups with 1 to 4 carbon atoms.

[0346] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0347]

[0348] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds.

[0349]

[0350] The above-mentioned compounds can be obtained as products manufactured by Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. For example, Asahi Organic Materials Co., Ltd.'s trade name TMOM-BP can be cited as an example of such a product.

[0351] Among them, glycourea compounds are preferred, specifically, tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds or mixtures thereof obtained by methoxymethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycourea, compounds or mixtures thereof obtained by acylmethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycourea, and more preferably tetramethoxymethylglycourea.

[0352] The molecular weight of the crosslinking agent (D) is not particularly limited, but is preferably 500 or less.

[0353] The content of crosslinking agent (D) in the composition for forming the lower layer of the resist film is not particularly limited, and is, for example, 1% to 70% by mass relative to the total of polymer (A) and polymer (B), preferably 5% to 60% by mass.

[0354] <Cure Catalyst (E)>

[0355] The curing catalyst (E) included as an optional component in the composition for forming the lower layer film of the resist can be either a thermal acid-generating agent or a photo-acid-generating agent, with a thermal acid-generating agent being preferred.

[0356] Examples of heat-generating acid agents include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium p-toluenesulfonate), pyridinium phenolsulfonate, pyridinium p-hydroxybenzenesulfonate (pyridinium p-phenolsulfonate salt), pyridinium trifluoromethanesulfonate, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, N-methylmorpholine-5-sulfosalicylic acid, and other sulfonic acid and carboxylic acid compounds.

[0357] Examples of photoacid-generating agents include onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0358] Examples of ononium salt compounds include, for example, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0359] Examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0360] Examples of disulfonyl diazonium compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyl diazonium.

[0361] The curing catalyst (E) can be used alone, or two or more can be used in combination.

[0362] When using a curing catalyst (E), the content of the curing catalyst (E) relative to the crosslinking agent (D) is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass.

[0363] <Other Ingredients>

[0364] In the composition for forming the lower layer of the resist film, a surfactant may be added to prevent pinholes, streaks, etc., and to further improve the coating properties against surface unevenness.

[0365] Examples of surfactants include linear or branched alkylbenzene sulfonic acids (e.g., dodecylbenzene sulfonic acid), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene oil-based ether, etc.; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; dehydrated sorbitol monolaurate, dehydrated sorbitol monopalmitate, dehydrated sorbitol monostearate, dehydrated sorbitol monooleate, dehydrated sorbitol trioleate, dehydrated sorbitol tristearate, etc.; and polyoxyethylene dehydrated sorbitol monolaurate, polyoxyethylene dehydrated sorbitol monopalmitate, polyoxyethylene dehydrated sorbitol monostearate, etc. Nonionic surfactants such as sorbitol trioleate, polyoxyethylene dehydrated sorbitol tristearate, and other polyoxyethylene dehydrated sorbitol fatty acid esters; Eptop EF301, EF303, EF352 (manufactured by Tokem Prodact, trade name); Megafack F171, F173, R-30 (manufactured by DIC Co., Ltd., trade name); Florad Fluorinated surfactants such as FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), Asahigard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd., trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0366] The amount of these surfactants is typically 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solids of the composition for forming the lower layer of the resist film.

[0367] These surfactants can be added individually or in combination of two or more.

[0368] The composition for forming the lower layer of the resist film may include a polymerization inhibitor (free radical scavenger) as needed. Examples of polymerization inhibitors include 2,6-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-tert-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, 4-methoxy-1-naphthol, etc.

[0369] There is no particular limitation on the content of the polymerization inhibitor in the composition for forming the lower layer film of the resist, but it is preferably less than 1% by mass relative to the solids.

[0370] The solids contained in the resist lower film forming composition of the present invention, that is, the components other than the solvent mentioned above, are, for example, 0.01% to 10% by mass.

[0371] The composition for forming the resist underlayer is suitable for use in EUV lithography.

[0372] The composition for forming a resist underlayer film is suitable for forming an underlayer film containing a metal resist.

[0373] (Underlying film of the resist)

[0374] The resist underlayer film of the present invention is a cured product of the above-mentioned resist underlayer film forming composition.

[0375] The photoresist underlayer film can be manufactured, for example, by coating the above-described photoresist underlayer film forming composition onto a semiconductor substrate and then firing it.

[0376] Examples of semiconductor substrates that can be used to form a composition for coating a resist underlayer include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0377] When using a semiconductor substrate with an inorganic film formed on its surface, the inorganic film can be formed, for example, by ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum evaporation, or spin coating (spin-coated glass: SOG). Examples of such inorganic films include polycrystalline silicon films, silicon oxide films, silicon nitride films, BPSG (borophosphosilicate glass) films, titanium nitride films, titanium oxynitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0378] On such a semiconductor substrate, the composition for forming the resist underlayer film of the present invention is coated using a suitable coating method such as a spin coater or a coating machine. Then, it is baked using a heating means such as a heating plate, thereby forming the resist underlayer film. The 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.

[0379] Examples of thicknesses for the underlying layer of the photoresist film include 0.001 μm (1 nm) ~ 10 μm, 0.002 μm (2 nm) ~ 1 μm, 0.005 μm (5 nm) ~ 0.5 μm (500 nm), 0.001 μm (1 nm) ~ 0.05 μm (50 nm), 0.002 μm (2 nm) ~ 0.05 μm (50 nm), 0.003 μm (3 nm) ~ 0.05 μm (50 nm), 0.004 μm (4 nm) ~ 0.05 μm (50 nm), and 0.005 μm. m (5nm) ~ 0.05μm (50nm), 0.003μm (3nm) ~ 0.03μm (30nm), 0.003μm (3nm) ~ 0.02μm (20nm), 0.005μm (5nm) ~ 0.02μm (20n) m), 0.003μm (3nm) ~ 0.01μm (10nm), 0.005μm (5nm) ~ 0.01μm (10nm), 0.003μm (3nm) ~ 0.006μm (6nm), or 0.005μm (5nm).

[0380] The method for determining the thickness of the resist underlayer film in this specification is as follows.

[0381] • Measuring device name: Elliptic polarization film thickness measuring device RE-3100 (SCREEN Co., Ltd.)

[0382] • SWE (Single Wavelength Ellipsometry) Mode

[0383] • 8-point arithmetic mean (e.g., measuring 8 points at 1cm intervals in the X direction of the wafer).

[0384] (Laminated body)

[0385] The stack of the present invention comprises a semiconductor substrate and a photoresist underlayer film of the present invention.

[0386] Examples of semiconductor substrates include the semiconductor substrates described above.

[0387] The photoresist underlayer is, for example, disposed on a semiconductor substrate.

[0388] (Semiconductor device manufacturing methods and patterning methods)

[0389] The method for manufacturing the semiconductor device of the present invention includes at least the following steps.

[0390] • The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition of the present invention; and

[0391] • The process of forming a resist film on the resist underlayer film.

[0392] The pattern forming method of the present invention includes at least the following steps.

[0393] • A process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition of the present invention; • The process of forming a resist film on the underlying resist film; • The process of irradiating a photoresist film with light or an electron beam, followed by developing the photoresist film to obtain a photoresist pattern; and • The process of using a resist pattern as a mask to etch the underlying resist film.

[0394] Typically, a resist film is formed on the lower layer of the resist film.

[0395] The thickness of the resist film is, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, or 1,000 nm or less. The lower limits are 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, and 10 nm.

[0396] As a photoresist film formed on a resist underlayer by known methods (e.g., coating and firing of the photoresist composition), there are no particular limitations as long as it responds to the light or electron beam (EB) used in the irradiation. Both negative and positive photoresists can be used.

[0397] It should be noted that, in this specification, the resist that responds to EB is also referred to as a photoresist.

[0398] As photoresists, there are positive photoresists containing phenolic varnish resin and 1,2-naphthoquinone diazonium sulfonate; chemically amplified photoresists containing binders and photoacid generators that increase the rate of alkali dissolution through acid decomposition; low-molecular-weight compounds that increase the rate of alkali dissolution through acid decomposition; chemically amplified photoresists containing alkali-soluble binders and photoacid generators; and photoresists containing metal elements, etc. Examples include JSR Corporation's product V146G, Shiplay Corporation's product APEX-E, Sumitomo Chemical Co., Ltd.'s product PAR710, and Shin-Etsu Chemical Industry Co., Ltd.'s products AR2772 and SEPR430, etc. In addition, examples of fluorine-containing polymeric photoresists described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000) can be cited.

[0399] Alternatively, you can use WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, and WO2019 / 172054. WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Patent Application No. 2018-180525, WO2018 / 190088, Japanese Patent Application Publication No. 2018-070596, Japanese Patent Application Publication No. 2018-028090, Japanese Patent Application Publication No. 2016-153409, Japan Special opening 2016-130240, Japanese special opening 2016-108325, Japanese special opening 2016-047920, Japanese special opening 2016-035570 , Japan’s special opening 2016-035567, Japan’s special opening 2016-035565, Japan’s special opening 2019-101417, Japan’s special opening 2019-1173 73. Japan Special Opening 2019-052294, Japanese Special Opening 2019-008280, Japanese Special Opening 2019-008279, Japanese Special Opening 2019-003176, Japanese Special Opening 2019-003175, Japanese Special Opening 2018-197853, Japanese Special Opening 2019-191298, Japanese Special Opening 201 9-061217, Japan’s special opening 2018-045152, Japan’s special opening 2018-022039, Japan’s special opening 2016-090441, Japan’s special opening 2015-10878, Japan’s special opening 2012-168279, Japan’s special opening 2012-022261, Japan’s special opening 2012-022258, Japan’s special opening The so-called resist compositions, radiation-sensitive resin compositions, and high-resolution patterning compositions based on organometallic solutions described in Japanese Patent Application Publication Nos. 2011-043749, 2010-181857, 2010-128369, WO2018 / 031896, 2019-113855, WO2017 / 156388, WO2017 / 066319, 2018-41099, WO2016 / 065120, WO2015 / 026482, 2016-29498, and 2011-253185 are metal-containing resist compositions, but are not limited to these.

[0400] Examples of resist compositions include the following.

[0401] An active light-sensitive or radiation-sensitive resin composition comprising resin A and a compound represented by the following general formula (121), wherein resin A comprises repeating units having acid-degradable groups having polar groups removed by acid action.

[0402]

[0403] In general formula (121), m represents an integer from 1 to 6.

[0404] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0405] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0406] L2 indicates an alkylene group or a single bond that may have substituents.

[0407] W1 represents a cyclic organic group that may have substituents.

[0408] M ＋ It represents a cation.

[0409] A composition for forming a metal film in extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to the 3rd to 7th periods of Groups 3 to 15 of the periodic table.

[0410] A radiation-sensitive resin composition comprising a polymer and an acid-generating agent, said polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) containing an acid-dissociating group.

[0411]

[0412] In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an aromatic hydrocarbon with 6 to 20 carbon atoms. 1 It is a hydroxyl, thioalkyl, or monovalent organic group with 1 to 20 carbon atoms. n is an integer from 0 to 11. When n is 2 or more, multiple R... 1 Same or different. R 2 It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), R 3 It is a monovalent group containing 1 to 20 carbon atoms of the aforementioned acid-dissociable groups. Z is a single bond, an oxygen atom, or a sulfur atom. R 4 It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0413] An anti-corrosion composition comprising a resin (A1) and an acid-generating agent, wherein the resin (A1) comprises structural units having a cyclic carbonate structure, structural units represented by the following formula, and structural units having acid-indestabilizing groups.

[0414]

[0415] In the formula, R 2 X represents an alkyl group, hydrogen atom, or halogen atom with 1 to 6 carbon atoms that can have halogen atoms. 1 For single bond, -CO-O- or -CO-NR 4 - , Indicates the bonding position with -Ar, R 4 Ar represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms and having one or more groups selected from hydroxyl and carboxyl groups.

[0416] Examples of resist films include the following films.

[0417] A photoresist film comprising a base resin comprising repeating units represented by formula (a1) and / or repeating units represented by formula (a2) below, and repeating units of acid bonded to the polymer backbone by exposure.

[0418]

[0419] In equations (a1) and (a2), R A Each can be independently a hydrogen atom or a methyl group. R 1 and R 2 Each is an independent tertiary alkyl group having 4 to 6 carbon atoms. R 3 Each atom can be independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. X 1 It is a single bond, a phenylene or naphthylene group, or a linking group containing at least one selected from ester bonds, lactone rings, phenylene, and naphthylene groups, and having 1 to 12 carbon atoms. X 2 It can be a single bond, ester bond, or amide bond.

[0420] Examples of materials that can be used as corrosion-resistant materials include the following.

[0421] A corrosion-resistant material comprising a polymer having repeating units represented by formula (b1) or formula (b2).

[0422]

[0423] In equations (b1) and (b2), R A It can be a hydrogen atom or a methyl group. X 1 It is a single bond or an ester group. X 2 It is a linear, branched, or cyclic alkylene group with 1 to 12 carbon atoms or an aryl group with 6 to 10 carbon atoms. A portion of the methylene group constituting the alkylene group may be substituted with an ether group, an ester group, or a group containing an lactone ring. Additionally, X 2 At least one hydrogen atom is replaced by a bromine atom. X 3 It is a single bond, an ether group, an ester group, or a straight-chain, branched-chain, or cyclic alkylene group having 1 to 12 carbon atoms, wherein a portion of the methylene group constituting the alkylene group may be substituted with an ether group or an ester group. Rf 1 ~Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Additionally, Rf 1 and Rf 2 They can also combine to form carbonyl groups. 1 ~R 5 Each group is independently a linear, branched, or cyclic alkyl group with 1 to 12 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, an alkynyl group with 2 to 12 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aralkyl group with 7 to 12 carbon atoms, or an aryloxyalkyl group with 7 to 12 carbon atoms. Some or all of the hydrogen atoms in these groups may be substituted with hydroxyl, carboxyl, halogen, oxo, cyano, amide, nitro, sulfonyl, sulfonyl, or sulfonium-containing salt groups. A portion of the methylene group constituting these groups may optionally be substituted with an ether, ester, carbonyl, carbonate, or sulfonate group. Additionally, R... 1 and R 2 They can also form rings together with the sulfur atoms they are bonded to.

[0424] A corrosion-resistant material comprising a base resin, said base resin comprising a polymer containing repeating units represented by the following formula (a).

[0425]

[0426] In equation (a), R A It can be a hydrogen atom or a methyl group. R 1 It is a hydrogen atom or an acid-labile group. R 2 It is a straight-chain, branched-chain, or cyclic alkyl group with 1 to 6 carbon atoms, or a halogen atom other than bromine. X 1 It is a single bond or phenylene, or a straight-chain, branched-chain, or cyclic alkylene with 1 to 12 carbon atoms that may contain an ester group or lactone ring. X 2 It can be -O-, -O-CH2-, or -NH-. m is an integer from 1 to 4. u is an integer from 0 to 3. However, m+u is an integer from 1 to 4.

[0427] A photoresist composition that generates acid upon exposure and whose solubility in a developer changes under the influence of the acid. It contains a substrate component (A) whose solubility in the developer changes under the action of acid, and a fluorinated additive component (F) that exhibits decomposition properties in alkaline developers. The fluorinated additive component (F) contains a fluoropolymer component (F1), which has a structural unit (f1) containing a base-dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).

[0428]

[0429] In equation (f2-r-1), Rf 21 Each can be independently a hydrogen atom, alkyl group, alkoxy group, hydroxy group, hydroxyalkyl group, or cyano group. n” is an integer from 0 to 2. This indicates the bonding location.

[0430] The above structural unit (f1) includes structural units represented by the following general formula (f1-1) or structural units represented by the following general formula (f1-2).

[0431]

[0432] In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms. X is a divalent linking group without an acid-dissociating site. A aryl X is a divalent aromatic cyclic group that can have substituents. 01 It is a single bond or a divalent linker. R 2 Each is an organic group that independently contains a fluorine atom.

[0433] As a corrosion resist composition, it can be a metal-containing corrosion resist.

[0434] Metal-containing photoresists are also known as metal oxide photoresists (MOR), with tin oxide photoresists being a prime example.

[0435] As a metal oxide resist material, for example, a coating composition comprising a network of metal hydroxyl oxides having organic ligands through metal carbon bonds and / or metal carboxylate bonds, as described in Japanese Patent Application Publication No. 2019-113855, can be cited.

[0436] An example of a metal-containing resist is the use of a peroxo ligand as a radiation-sensitive stabilizing ligand. Details of peroxide-based metal hydroxides are described in, for example, the patent document described in paragraph (0011) of Japanese Patent Publication No. 2019-532489. As such patent documents, for example, US Patent No. 9,176,377B2, US Patent Application Publication No. 2013 / 0224652A1, US Patent No. 9,310,684B2, US Patent Application Publication No. 2016 / 0116839A1, and US Patent Application Publication No. 15 / 291738 can be cited.

[0437] A coating that includes a metal hydroxide network having an organic ligand through a metal-carbon bond and / or a metal carboxylate bond.

[0438] A composition based on inorganic hydroxide.

[0439] A coating solution that includes an organic solvent, a first organometallic composition, and a hydrolyzable metal compound. The first organometallic composition is represented by the formula R z SnO （2-（z／2）-（x／2）） (OH) x (where 0 < z ≤ 2 and 0 < (z + x) ≤ 4), the formula R’ n SnX 4-n (where n = 1 or 2), or a mixture thereof, where R and R’ are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof; the hydrolyzable metal compound is represented by the formula MX’ v (where M is a metal selected from Groups 2 to 16 of the Periodic Table of the Elements, v is a number from 2 to 6, and X’ is a ligand having a hydrolyzable M-X bond or a combination thereof).

[0440] A coating solution that includes an organic solvent and a first organometallic compound represented by the formula RSnO （3／2-x／2） (OH) x (where 0 < x < 3). The solution contains from about 0.0025 M to about 1.5 M of tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, and the alkyl or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom.

[0441] An aqueous precursor solution for inorganic pattern formation that includes a mixture of water, a metal lower oxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand containing a peroxide group.

[0442] Other examples of metal-containing corrosion inhibitors include the compositions described in Japanese Patent Application Publication No. 2011-253185, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, Japanese Patent Application Publication No. 2020-122959, Japanese Patent Application Publication No. 2020-122960, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367 and WO2021 / 016229.

[0443] All of these contents are incorporated into this specification as if they were explicitly stated.

[0444] There are no particular limitations on the method for forming a metal resist film from a metal resist, and a method of coating a coating type resist material (a composition for forming a metal resist film) as a metal resist and then firing it can be cited.

[0445] Alternatively, the metal resist film can also be formed by vapor deposition. As a method for forming a metal resist film based on vapor deposition, the method described in Japanese Patent Application Publication No. 2017-116923 can be cited as an example. The contents of Japanese Patent Application Publication No. 2017-116923 are incorporated herein by reference in their entirety. It should be noted that in Japanese Patent Application Publication No. 2017-116923, the metal resist film of the present invention is referred to as a metal oxide film.

[0446] Irradiation with light or electron beams is performed, for example, by using a mask (photomask) to form a prescribed pattern. Examples include i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam). The resist underlayer film formation composition of the present invention is preferably used for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation applications, and more preferably for EUV (extreme ultraviolet) exposure applications.

[0447] There are no particular restrictions on the irradiation energy of the electron beam and the amount of light exposure.

[0448] After exposure to light or electron beams and before development, baking (PEB: Post Exposure Bake) can be performed.

[0449] There are no particular limitations on the baking temperature, but it is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C.

[0450] There are no particular restrictions on the baking time, but it is preferred to be 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0451] For developing, for example, alkaline developing solutions or organic solvents are used.

[0452] Examples of developing temperatures include 5°C to 50°C.

[0453] For example, development time can range from 10 seconds to 300 seconds.

[0454] As an alkaline developer, aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alkanolamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and piperidine can be used. Furthermore, appropriate amounts of alcohols such as isopropanol and nonionic surfactants can be added to the above-mentioned alkaline aqueous solutions. Among these, aqueous solutions of quaternary ammonium salts are preferred, and aqueous solutions of tetramethylammonium hydroxide and choline are more preferred. Furthermore, surfactants can be added to these developers. Organic solvents such as butyl acetate can also be used instead of alkaline developers for development, to develop the portion of the photoresist where the alkali dissolution rate is not improved.

[0455] Organic solvents can be used as developers for metal resists, and development is performed by applying the developer (solvent) after light or electron beam irradiation. Thus, for example, when using a negative metal resist film, the unexposed portions of the metal resist film are removed, forming a pattern of the metal resist film.

[0456] Examples of organic solvents that can be used as developers include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate. Butyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Examples include esters, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. Furthermore, surfactants may be added to these developing solutions.

[0457] Next, the formed resist pattern is used as a mask to etch the underlying resist film. Etching can be dry etching or wet etching, but dry etching is preferred.

[0458] When the aforementioned inorganic film is formed on the surface of the semiconductor substrate being used, the surface of the inorganic film is exposed; when the aforementioned inorganic film is not formed on the surface of the semiconductor substrate being used, the surface of the semiconductor substrate is exposed. Then, by processing the semiconductor substrate using a known method (such as dry etching), a semiconductor device can be manufactured.

[0459] Example

[0460] The following examples illustrate the content of the present invention in detail, but the present invention is not limited to these examples.

[0461] The weight-average molecular weights of the polymers shown in Examples 1-9 below are based on gel permeation chromatography (hereinafter referred to as GPC). A GPC apparatus manufactured by Higashi Sou Co., Ltd. was used in the determination, and the determination conditions are as follows.

[0462] GPC pillars: Shodex KF803L, Shodex KF802, Shodex KF801 (registered trademark) (Showa Denko Co., Ltd.)

[0463] Column temperature: 40℃

[0464] Solvent: N,N-dimethylformamide (DMF)

[0465] Flow rate: 0.6 ml / min

[0466] Standard sample: Polystyrene (manufactured by Higashi Sou Corporation)

[0467] <Synthesis example 1>

[0468] 8.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 5.45 g of diethylbarbituric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.48 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) were added to 56.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out under reflux heating for 10 hours to obtain a solution containing polymer 1. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. When GPC analysis was performed, the weight-average molecular weight of the polymer in the obtained solution, converted to standard polystyrene, was 10,000. The polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (1b).

[0469]

[0470] <Synthesis example 2>

[0471] 7.00 g of Denacol Ex711 (manufactured by Nagasekemex Co., Ltd.), 5.61 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.31 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) were added to 51.70 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 100°C for 24 hours to obtain a solution containing polymer 2. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. When GPC analysis was performed, the weight-average molecular weight of the polymer in the obtained solution, converted to standard polystyrene, was 12,000. The polymer obtained in this synthesis example has the structural units represented by the following formulas (1c) and (1d).

[0472]

[0473] <Synthesis Example 3>

[0474] 7.00 g of Denacol Ex201 (manufactured by Nagasekex Co., Ltd.), 6.86 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.20 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 32.81 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 130°C for 24 hours to obtain a solution containing polymer 3. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. When GPC analysis was performed, the weight-average molecular weight of the polymer in the obtained solution, converted to standard polystyrene, was 19,000. The polymer obtained in this synthesis example has the structural units represented by the following formulas (1e) and (1d).

[0475]

[0476] <Synthesis example 4>

[0477] 7.00 g of Denacol Ex711 (manufactured by Nagasekemex Co., Ltd.), 4.97 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.31 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) were added to 49.11 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 100°C for 24 hours to obtain a solution containing polymer 4. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. When GPC analysis was performed, the weight-average molecular weight of the polymer in the obtained solution, converted to standard polystyrene, was 16,000. The polymer obtained in this synthetic example has the structural units represented by the following formulas (1c) and (1f).

[0478]

[0479] <Synthesis example 5>

[0480] 7.00 g of Denacol Ex201 (manufactured by Nagasekex Co., Ltd.), 6.17 g of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.76 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 55.71 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 100°C for 24 hours to obtain a solution containing polymer 5. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. When GPC analysis was performed, the weight-average molecular weight of the polymer in the obtained solution, converted to standard polystyrene, was 31,000. The polymer obtained in this synthetic example has the structural units represented by the following formulas (1e) and (1f).

[0481]

[0482] <Synthesis Example 6>

[0483] 20.00 g of polyglycidyl methacrylate (manufactured by Maruzen Petrochemical Co., Ltd.), 4.88 g of sorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 16.77 g of propylene glycol monomethyl ether and 2.58 g of propylene glycol monomethyl ether acetate in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 100°C for 24 hours to obtain a solution containing polymer 6. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate. GPC analysis showed that the polymer in the obtained solution had a weight-average molecular weight of 25,000 converted to standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formula (1 g).

[0484]

[0485] <Synthesis Example 7>

[0486] 20.00 g of polyglycidyl methacrylate (manufactured by Maruzen Petrochemical Co., Ltd.), 3.75 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 15.07 g of propylene glycol monomethyl ether and 0.88 g of propylene glycol monomethyl ether acetate in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 100°C for 24 hours to obtain a solution containing polymer 7. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate. GPC analysis showed that the polymer in the obtained solution had a weight-average molecular weight of 21,000 converted to standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formula (1h).

[0487]

[0488] <Synthesis example 8>

[0489] 20.00 g of polyglycidyl methacrylate (manufactured by Maruzen Petrochemical Co., Ltd.), 3.28 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 14.36 g of propylene glycol monomethyl ether and 0.17 g of propylene glycol monomethyl ether acetate in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 100°C for 24 hours to obtain a solution containing polymer 8. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate. When GPC analysis was performed, the weight-average molecular weight of the polymer in the obtained solution, converted to standard polystyrene, was 21,000. The polymer obtained in this synthesis example has the structural unit represented by the following formula (1i).

[0490]

[0491] <Synthesis Example 9>

[0492] 20.00 g of polyglycidyl methacrylate (manufactured by Maruzen Petrochemical Co., Ltd.), 3.66 g of tetracarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 14.93 g of propylene glycol monomethyl ether and 0.74 g of propylene glycol monomethyl ether acetate in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 100°C for 24 hours to obtain a solution containing polymer 9. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate. When GPC analysis was performed, the weight-average molecular weight of the polymer in the obtained solution, converted to standard polystyrene, was 21,000. The polymer obtained in this synthesis example has the structural unit represented by the following formula (1j).

[0493]

[0494] [Preparation of the composition for forming the lower layer of the resist]

[0495] (Example and Comparative Examples)

[0496] The polymers, crosslinking agents, curing catalysts and solvents obtained in the above synthesis examples 1 to 9 were mixed in the proportions shown in Table 1 and filtered with a fluoropolymer filter with a pore size of 0.1 μm to prepare the resist underlayer film forming compositions of Examples 1 to 7 and Comparative Examples 1 to 3, respectively.

[0497] The abbreviations in Table 1 are as follows.

[0498] PL-LI: Tetramethoxymethylglyoxal

[0499] PGME-PL: Imidazolo[4,5-d]imidazol-2,5(1H,3H)dione, tetrahydro-1,3,4,6-tetra[(2-methoxy-1-methylethoxy)methyl]- (structural formula below)

[0500] Py-PSA: Pyridinium p-hydroxybenzenesulfonic acid

[0501] PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0502] PGME: Propylene Glycol Monomethyl Ether

[0503] [Dissolution test in photoresist solvent]

[0504] The photoresist underlayer film formation compositions of Examples 1-7 and Comparative Examples 1-3 were respectively coated onto silicon wafers serving as semiconductor substrates using a spin coater. The silicon wafers were placed on a hot plate and baked at 205°C for 1 minute to form photoresist underlayer films (film thickness 5 nm). These photoresist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 70 / 30 (volume ratio) as the solvent used as the photoresist. Film thickness variations of less than 1 Å were considered "good", and film thickness variations of 5 Å or more were considered "poor". The results are shown in Table 2.

[0505]

[0506] [Resist Pattern Formation Experiment Based on Electron Beam Drawing Apparatus]

[0507] The photoresist underlayer film formation compositions of Examples 1-7 and Comparative Examples 1-3 were respectively coated onto silicon wafers using a spin coater. The silicon wafers were baked on a hot plate at 205°C for 60 seconds to obtain a photoresist underlayer film with a thickness of 5 nm. An EUV positive photoresist solution was spin-coated onto this photoresist underlayer film, and heated at 130°C for 60 seconds to form an EUV photoresist film. This photoresist film was then irradiated with an electron beam patterning apparatus (ELS-G130) under specified conditions. After irradiation, it was baked at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and then developed by spin-dip immersion for 30 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) as the photoresist developer. A photoresist pattern with a line size of 16 nm to 28 nm was formed. The length of the resist pattern was measured using a scanning electron microscope (manufactured by Hitachi Hiteknologis Co., Ltd., CG4100).

[0508] For the photoresist pattern thus obtained, evaluate whether a 22nm line and gap (L / S) can be formed.

[0509] A 22 nm mL / S pattern was confirmed to have formed. Furthermore, the charge amount at which a 22 nm line / 44 nm spacing (line to gap (L / S=1 / 1)) was formed was taken as the optimal irradiation energy, and the irradiation energy at this point (μC / cm²) was determined. 2 (See Table 3.)

[0510] Furthermore, regarding the minimum CD size, the limit CD size without pattern collapse is shown in Table 3. In Examples 1-7, compared with Comparative Examples 1-3, it was confirmed that the minimum CD size was improved.

[0511] < / q>

Claims

1. A composition for forming a resist underlayer film, comprising a polymer (A) having a partial structure represented by the following formula (A), a polymer (B) having polymerizable multiple bonds, and a solvent (C); In formula (A), R 11 Represents an (n+2) valence group having at least one of aromatic hydrocarbon rings and aliphatic hydrocarbon rings; R 12 Represents a hydrogen atom, or an alkyl group that can be substituted by at least one group selected from alkoxy groups having 1 to 13 carbon atoms, alkylcarbonyloxy groups having 2 to 13 carbon atoms, alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylthio groups having 1 to 13 carbon atoms, nitro groups, alkylsulfonyloxy groups having 1 to 13 carbon atoms, and alkoxysulfonyl groups having 1 to 13 carbon atoms, and has 1 to 13 carbon atoms; n represents 1 or 2; when n is 2, the two R groups... 12 They can be the same or different; Indicates the bonding location.

2. The composition for forming a resist underlayer film according to claim 1, wherein the polymer (B) is a polymer (B-1) having a structural unit represented by the following formula (B-1) or a polymer (B-2) having a structural unit represented by the following formula (B-2). In equation (B-1), R 1 Indicates an alkyl group having 1 to 10 hydrogen atoms; L 1 Indicates a single bond or linking group; L 2 This indicates a monovalent group having the aforementioned polymerizable multiple bonds; In equation (B-2), A 11 A 12 A 13 A 14 A 15 and A 16 Each can independently represent a hydrogen atom, a methyl group, or an ethyl group, Q. 21 R represents a divalent organic group; 21 This indicates a divalent group having the polymerizable multiple bonds described above.

3. The composition for forming a resist underlayer film according to claim 2, wherein the L in the structural unit represented by formula (B-1) 1 -L 2 It has a structure represented by the following formulas (1a), (1b) or (1c); In equations (1a) to (1c), R 2 Indicates an alkyl group having 1 to 10 hydrogen atoms or carbon atoms; a and b represents the bonding position. a represents the main chain side of polymer (B-1). b represents the terminal side of the side chain of polymer (B-1).

4. The composition for forming a resist underlayer film according to claim 1, wherein the polymer (A) has a structural unit represented by the following formula (A-11); In formula (A-11), A 1 A 2 A 3 A 4 A 5 and A 6 Each can independently represent a hydrogen atom, methyl group, or ethyl group; Q represents a divalent organic group; R 11 R represents an organic group having at least one of the following: an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; 12 Represents a hydrogen atom, or an alkyl group that can be substituted by at least one group selected from alkoxy groups having 1 to 13 carbon atoms, alkylcarbonyloxy groups having 2 to 13 carbon atoms, alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylthio groups having 1 to 13 carbon atoms, nitro groups, alkylsulfonyloxy groups having 1 to 13 carbon atoms, and alkoxysulfonyl groups having 1 to 13 carbon atoms, and has 1 to 13 carbon atoms; n represents 1 or 2; when n is 2, the two R groups... 12 They can be the same or different.

5. The composition for forming a resist underlayer film according to claim 4, wherein Q in formula (A-11) represents any one of the following formulas (A-21) and (A-22); In equation (A-21), X 1 Z represents the divalent group shown in formula (A-21-1), formula (A-21-2), or formula (A-21-3) below; 1 and Z 2 Each can independently represent a single bond or a divalent group as shown in the following formula (A-21-4); Indicates the bonding location; In equation (A-22), Q 1 This indicates a divalent group having an aromatic or aliphatic hydrocarbon ring; n1 and n2 each independently represent 0 or 1; Indicates the bonding location; In equations (A-21-1) to (A-21-3), R 1 ~R 5 Each of the following groups independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkenyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkynyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from alkyl groups having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms; R 1 and R 2 They can also bond together to form rings with 3 to 6 carbon atoms; R 3 and R 4 They can also bond with each other to form rings with 3 to 6 carbon atoms; Indicates the bonding location; 1 indicates the bonding position with a carbon atom; 2 indicates the bonding position with the nitrogen atom; In equation (A-21-4), m1 is an integer from 1 to 4, and m2 is 0 or 1. 3 indicates the bonding position with the nitrogen atom. 4 indicates the bonding position with a carbon atom.

6. The composition for forming a resist underlayer film according to claim 5, wherein Q in formula (A-22) 1 This represents any one of the following formulas (A-22-1) to (A-22-4); In equations (A-22-1) to (A-22-4), R 31 ~R 36 Each of the following can be independently represented: halogen atom, hydroxyl group, alkyl group with 1 to 6 carbon atoms, alkenyl group with 2 to 6 carbon atoms, alkynyl group with 2 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkenyloxy group with 2 to 6 carbon atoms, alkynyloxy group with 2 to 6 carbon atoms, acyl group with 2 to 6 carbon atoms, aryloxy group with 6 to 12 carbon atoms, arylcarbonyl group with 7 to 13 carbon atoms, or aralkyl group with 7 to 13 carbon atoms; Indicates the bonding location; In equation (A-22-1), n3 represents 0 or 1; when n3 is 0, n11 represents an integer from 0 to 4; when n3 is 1, n11 represents an integer from 0 to 6; R 31 When there are two or more R, there are two or more R 31 They can be the same or different; In equation (A-22-2), Z 1 Indicates a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms; n12 and n13 each independently represent integers from 0 to 4; R 32 When there are two or more R, there are two or more R 32 They can be the same or different; R 33 When there are two or more R, there are two or more R 33 They can be the same or different; In formula (A-22-3), Y 1 and Y 2 Each independently represents a single bond or an alkylene group with 1 to 6 carbon atoms; n14 represents an integer from 0 to 4; R 34 When there are two or more R, there are two or more R 34 They can be the same or different; In formula (A-22-4), Z 2 Indicates a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms; n15 and n16 each independently represent integers from 0 to 4; R 35 When there are two or more R, there are two or more R 35 They can be the same or different; R 36 When there are two or more R, there are two or more R 36 They can be the same or different.

7. The composition for forming a resist underlayer film according to claim 1, wherein the mass ratio of polymer (A) to polymer (B) (polymer (A): polymer (B)) is 20:80 to 80:

20.

8. The composition for forming a resist underlayer film according to claim 1, wherein the solvent (C) comprises at least one selected from monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkylene glycol monoalkyl ethers.

9. The composition for forming a resist underlayer film according to claim 1, further comprising a crosslinking agent (D).

10. The composition for forming a resist underlayer film according to claim 9, wherein the crosslinking agent (D) is at least one selected from amino plastic crosslinking agents and phenolic plastic crosslinking agents.

11. The composition for forming a resist underlayer film according to claim 1, further comprising a curing catalyst (E).

12. The composition for forming a resist underlayer film according to claim 1, used in EUV lithography.

13. The composition for forming a resist underlayer film according to claim 1, used to form a metal-containing resist underlayer film.

14. A resist underlayer film, which is a cured product of the resist underlayer film forming composition according to any one of claims 1 to 13.

15. A stack comprising a semiconductor substrate and a photoresist underlayer as claimed in claim 14.

16. A method for manufacturing a semiconductor device, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition according to any one of claims 1 to 13; and The process of forming a resist film on the lower resist film.

17. A method for forming a pattern, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition according to any one of claims 1 to 13; The process of forming a resist film on the lower resist film; The process of irradiating the resist film with light or an electron beam, followed by developing the resist film to obtain a resist pattern; and The process of using the resist pattern as a mask to etch the underlying resist film.

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