Composition for forming resist underlayer film

Abstract

Provided is a composition for forming a resist underlayer film, the composition comprising: a polymer having a repeating unit represented by formula (1), a repeating unit represented by formula (2), and / or a repeating unit represented by formula (3); and a solvent. (In formula (1), PAG represents a residue of a photoacid generator.)

Description

Composition for forming a resist underlayer film

[0001] The present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a laminate, a method for manufacturing a semiconductor device, and a method for forming a pattern.

[0002] Conventionally, microfabrication using lithography with resist compositions has been performed in the manufacturing of semiconductor devices. This microfabrication method involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with an active light such as ultraviolet light through a mask pattern on which the device pattern is drawn, developing the film, and then etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the photoresist pattern. In recent years, semiconductor devices have become more highly integrated, and in addition to the conventionally used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. Consequently, poor resist pattern formation has become a major problem. Therefore, in order to solve this problem, methods of providing a resist underlayer film between the resist and the semiconductor substrate are being widely investigated.

[0003] As a resist underlayer film forming composition, for example, a resist underlayer film forming composition has been proposed that contains a polymer having a substructure represented by a specific formula and a solvent (see claim 9 of Patent Document 1).

[0004] International Publication No. 2023 / 068075 brochure

[0005] Characteristics required for a resist underlayer film include, for example, no intermixing with the resist film formed on the upper layer (being insoluble in the resist solvent), and capability of forming a fine resist pattern. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming a resist underlayer film capable of forming a resist underlayer film that can form a fine resist pattern, as well as a resist underlayer film, a laminate, a method for producing a semiconductor element, and a pattern forming method using the composition for forming a resist underlayer film.

[0006] In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that the above problems can be solved, and completed the present invention having the following gist.

[0007] That is, the present invention includes the following aspects. [1] A composition for forming a resist underlayer film, comprising a polymer having a repeating unit represented by the following formula (1), and at least one of a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3), and a solvent. (In formula (1), R ａ１ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and L １ represents a single bond or a divalent group, and PAG represents a residue of a photoacid generator. In formula (2), R ａ２ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and X １ represents -O- or -NR ２ - (R ２ represents a hydrogen atom or a monovalent organic group.), and R １ represents a hydrogen atom or a monovalent organic group. When X １ is -NR ２ -, R １ and R ２ may together form a ring structure. In formula (3), R ａ３(wherein represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and Ar represents a monovalent aromatic group which may have substituents.) [2] The resist underlayer film forming composition according to [1], wherein PAG in formula (1) is represented by the following formula (PAG-1) or the following formula (PAG-2). (In formula (PAG-1), Y １ａ － This represents a monovalent group having a monovalent anionic structure, Y １ｃ ＋ Y represents a monovalent aromatic onium cation. In formula (PAG-2), Y ２ｃ ＋ This represents a monovalent group having a monovalent aromatic onium cation structure, Y ２ａ － represents a monovalent anion.) [3] In the above formula (PAG-1), Y １ａ － However, R １０１ SO ３ － or R １０１ CO ２ － (R １０１ represents a divalent organic group having 1 to 40 carbon atoms. ) represents, and in the above formula (PAG-2), Y ２ａ － However, R １０２ SO ３ － or R １０２ CO ２ － (R １０２ A resist underlayer film forming composition as described in [2], where Y represents a monovalent organic group having 1 to 40 carbon atoms. [4] In the formula (PAG-1), Y １ｃ ＋ However, it represents a monovalent aromatic sulfonium cation or a monovalent aromatic iodonium cation, and in the formula (PAG-2), the Y ２ｃ ＋The resist underlayer film forming composition according to [3], wherein the repeating unit represented by formula (1) is a repeating unit represented by the following formula (1-1). (In formula (1-1), R ａ１ Ar represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms that may be substituted with a halogen atom. １ represents a divalent aromatic group which may have substituents, and Y １ｃ ＋ (wherein represents a monovalent aromatic onium cation.) [6] A resist underlayer film forming composition according to any one of [1] to [5], wherein the repeating unit represented by formula (1) is the repeating unit represented by the following formula (1-1-1). (In formula (1-1-1), R ａ１ Y represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. １ｃ ＋(wherein represents a monovalent aromatic onium cation.) [7] A resist underlayer film forming composition according to any one of [1] to [6], wherein the polymer comprises repeating units represented by formula (1) and repeating units represented by formula (2). [8] A resist underlayer film forming composition according to any one of [1] to [7], wherein the Ar in formula (3) does not contain at least one of a phenolic hydroxyl group and a group that gives a phenolic hydroxyl group by the action of an acid. [9] A resist underlayer film forming composition according to any one of [1] to [8], wherein the molar ratio of the repeating unit represented by formula (1) to the total repeating units of the polymer is 0.1 mol% to 60 mol%.

[10] A resist underlayer film forming composition according to any one of [1] to [9], wherein the solvent comprises at least one selected from the group consisting of a carboxylic acid having a hydroxyl group, a linear or cyclic alkyl ketone, a cyclic lactone, an alkylene glycol monoalkyl ether, a monocarboxylic acid ester of an alkylene glycol monoalkyl ether, and an alkoxycarboxylic acid ester of an alkylene glycol monoalkyl ether.

[11] A resist underlayer film forming composition according to any one of [1] to

[10] , further comprising a crosslinking agent.

[12] A resist underlayer film forming composition according to

[11] , wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

[13] A resist underlayer film forming composition according to

[11] or

[12] , wherein the content of the crosslinking agent is 1% by mass to 60% by mass with respect to the polymer.

[14] A resist underlayer film forming composition according to any one of [1] to

[13] , further comprising a curing catalyst.

[15] A resist underlayer film forming composition according to any one of [1] to

[14] , further comprising at least one of a photoacid generator and a photodegradable quencher.

[16] A resist underlayer film forming composition according to any one of [1] to

[15] , further comprising a surfactant.

[17] A resist underlayer film forming composition according to any one of [1] to

[16] , used in EB or EUV lithography.

[18] A resist underlayer film forming composition according to any one of [1] to

[17] , used for forming an underlayer film of a metal-containing resist.

[19] A resist underlayer film which is a cured product of a resist underlayer film forming composition according to any one of [1] to

[18] .

[20] A laminate comprising a semiconductor substrate and the resist underlayer film according to

[19] .

[21] A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of [1] to

[18] ; and forming a resist film on the resist underlayer film.

[22] A method for forming a pattern, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of [1] to

[18] ; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern; and etching the resist underlayer film using the resist pattern as a mask.

[0008] According to the present invention, it is possible to provide a resist underlayer film formation composition capable of forming a resist underlayer film capable of forming a fine resist pattern, as well as a method for manufacturing a resist underlayer film, a laminate, a semiconductor device, and a pattern formation method using the resist underlayer film formation composition.

[0009] (Composition for forming a resist underlayer film) The resist underlayer film composition of the present invention comprises a polymer (A) and a solvent. Here, polymer (A) has repeating units represented by the following formula (1), and at least one of repeating units represented by the following formula (2) and repeating units represented by the following formula (3). (In formula (1), R ａ１ L represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. １ R represents a single bond or a divalent group, and PAG represents a residue of the photoacid generator. In formula (2), R ａ２ X represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. １ is -O- or -NR ２ - (R ２represents a hydrogen atom or a monovalent organic group. ) and R １ X represents a hydrogen atom or a monovalent organic group. １ ga-NR ２ - When R １ and R ２ They may come together to form a ring structure. In formula (3), R ａ３ (where represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms that may be substituted with a halogen atom, and Ar represents a monovalent aromatic group that may have substituents.)

[0010] By using a resist underlayer film formation composition containing such polymer (A), a fine resist pattern can be formed.

[0011] The following describes each component contained in the resist underlayer film formation composition.

[0012] <Polymer (A)> Polymer (A) has repeating units represented by the following formula (1), and at least one of the repeating units represented by the following formula (2) and the following formula (3). (In formula (1), R ａ１ L represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. １ R represents a single bond or a divalent group, and PAG represents a residue of the photoacid generator. In formula (2), R ａ２ X represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. １ is -O- or -NR ２ - (R ２ represents a hydrogen atom or a monovalent organic group. ) and R １ X represents a hydrogen atom or a monovalent organic group. １ ga-NR ２ - When R １ and R ２ They may come together to form a ring structure. In formula (3), R ａ３(where represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms that may be substituted with a halogen atom, and Ar represents a monovalent aromatic group that may have substituents.)

[0013] <<Repeating unit represented by formula (1)>> (In formula (1), R ａ１ L represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. １ (where represents a single bond or a divalent group, and PAG represents a residue of the photoacid generator.)

[0014] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. In this specification, examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group. In this specification, examples of alkyl groups having 1 to 10 carbon atoms substituted with halogen atoms (halogenated alkyl groups) include trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, and 1,1,2,2,3,3,4,4,4-nonafluorobutyl group.

[0015] R in equation (1) ａ１ Hydrogen atoms and methyl groups are preferred as these elements.

[0016] L in equation (1) １represents a single bond or a divalent group. The number of carbon atoms in the divalent group is not particularly limited, and may be, for example, 0 to 100, 0 to 80, 0 to 60, 0 to 50, 0 to 40, 0 to 30, 0 to 20, or 0 to 15. L １ is a divalent group, L １ may have a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom. L １ Examples of the divalent group in include a divalent aromatic group which may have a substituent. Further, examples of the divalent group in L １ include an ester group, an amide group, and the like.

[0017] PAG in formula (1) is a residue of a photoacid generator. In the present invention, a photoacid generator refers to a compound that generates an acid (e.g., carboxylic acid, sulfonic acid, etc.) upon irradiation with radiation. The acid may be a strong acid or a weak acid. A strong acid means an acid having an acid dissociation constant pKa of 1 or less. A weak acid means an acid having an acid dissociation constant pKa of more than 1 and 7 or less

[0018] PAG in formula (1) is preferably represented by the following formula (PAG-1) or the following formula (PAG-2). (In formula (PAG-1), Y １ａ － represents a monovalent group having a monovalent anion structure, and Y １ｃ ＋ represents a monovalent aromatic onium cation. In formula (PAG-2), Y ２ｃ ＋ represents a monovalent group having a monovalent aromatic onium cation structure, and Y ２ａ － represents a monovalent anion.)

[0019] Y in formula (PAG-1) １ｃ ＋ preferably represents a monovalent aromatic sulfonium cation or a monovalent aromatic iodonium cation. Y in formula (PAG-2) ２ｃ ＋preferably represents a monovalent group having a monovalent aromatic sulfonium cation structure, or a monovalent group having a monovalent aromatic iodonium cation structure.

[0020] The aromatic onium cation and the aromatic onium cation structure may have a substituent at any position. The number of substituents is not particularly limited.

[0021] Y １ｃ ＋ includes, for example, a monovalent aromatic sulfonium cation represented by the following formula (C1-1) or a monovalent aromatic iodonium cation represented by the following formula (C1-2). Y ２ｃ ＋ includes, for example, a monovalent group obtained by removing a hydrogen atom from a monovalent aromatic sulfonium cation represented by the following formula (C1-1), or a monovalent group obtained by removing a hydrogen atom from a monovalent aromatic iodonium cation represented by formula (C1-2). (In formula (C1-1), R １０１ , R １０２ , and R １０３ each independently represent any one of the following (i) to (iv), and R １０１ and R １０２ , R １０２ and R １０３ , or R １０１ and R １０３ may be bonded to each other to form a ring; provided that at least one of R １０１ , R １０２ , and R １０３ is any one of the following formulas (ii) to (iv). (i) a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, which may have a substituent and may contain a halogen atom, a carbonyl group, an ester group, an ether group, a thioether group, an amide group, a lactone ring, or an aryl group (ii) an aromatic hydrocarbon group which may have a substituent and may contain -S- (iii) an aralkyl group having 7 to 20 carbon atoms which may have a substituent (iv) a thiophenyl group which may have a substituent In formula (C1-2), R １０４ and R １０５Each independently represents an aryl group having 6 to 20 carbon atoms, which may have substituents, and R １０４ and R １０５ (They may be joined to each other to form a ring.)

[0022] Examples of aromatic hydrocarbon rings in aromatic hydrocarbon groups and aralkyl groups include benzene rings and naphthalene rings. Examples of the number of carbon atoms in the aromatic hydrocarbon group in (ii) above include 6 to 20.

[0023] Examples of substituents (X) in (i) to (iv) above include halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, allyl groups, vinyl groups, alkenyl groups, alkynyl groups, amide groups, alkoxy groups, carboxyl groups, ester groups, acetyl groups, aldehyde groups, epoxy groups, carbonyl groups, thiol groups, thioether groups, sulfonyl groups, sulfide groups, sulfo groups, ether groups, linear, branched, or cyclic alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 20 carbon atoms, monohalogenated methylene groups (-CHX-), dihalogenated methylene groups (-CX-) ２ -), monohalogenated methyl group (-CH ２ X), dihalogenated methyl group (-CHX ２ ), trihalogenated methyl group (-CX ３ Examples include substituents such as halogen atoms (where X represents a halogen atom) or combinations thereof.

[0024] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1) include the monovalent aromatic sulfonium cation represented by the following formula (C1-1-1). (In formula (C1-1-1), each Ar independently represents an optionally substituted aromatic hydrocarbon group.)

[0025] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0026] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1-1) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0027] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1) include the monovalent aromatic sulfonium cation represented by the following formula (C1-1-2). (In formula (C1-1-2), each Ar independently represents an optionally substituted aromatic hydrocarbon group.)

[0028] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0029] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1-2) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0030] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1) include the monovalent aromatic sulfonium cation represented by the following formula (C1-1-3). (In formula (C1-1-3), Ar independently represents an optionally substituted aromatic hydrocarbon group. Z represents -O-, -S-, -SO ２ -, -CR ２ - (R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may have substituents), or -NH-.)

[0031] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include a benzene ring and a naphthalene ring. A hydrocarbon group having 1 to 20 carbon atoms may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include a benzene ring and a naphthalene ring.

[0032] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1-3) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0033] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1) include the monovalent aromatic sulfonium cation represented by the following formula (C1-1-4). (In formula (C1-1-4), Ar represents an aromatic hydrocarbon group which may have substituents. ａ Each of these independently represents a hydrogen atom or a substituent.

[0034] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0035] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1-4) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0036] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1) include the monovalent aromatic sulfonium cation represented by the following formula (C1-1-5). (In formula (C1-1-5), Ar independently represents an aromatic hydrocarbon group which may have substituents. ａ Each of these independently represents a hydrogen atom or a substituent.

[0037] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0038] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1-5) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0039] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1) include the monovalent aromatic sulfonium cation represented by the following formula (C1-1-6). (In formula (C1-1-6), Ar represents an aromatic hydrocarbon group which may have substituents. ｂ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may have substituents. ｂ (It may also form a ring together with -S-.)

[0040] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include a benzene ring and a naphthalene ring. Two R ｂ Examples of rings formed by the combination of -S- include five-membered rings and six-membered rings. The ring may contain atoms such as oxygen atoms and sulfur atoms. The ring may also have the above substituent (X).

[0041] Examples of monovalent aromatic sulfonium cations represented by formula (C1-1-6) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0042] Examples of monovalent aromatic iodonium cations represented by formula (C1-2) include the monovalent aromatic iodonium cation represented by the following formula (C1-2-1). (In formula (C1-2-1), each Ar independently represents an optionally substituted aromatic hydrocarbon group.)

[0043] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0044] Examples of monovalent aromatic iodonium cations represented by formula (C1-2-1) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0045] Examples of monovalent aromatic iodonium cations represented by formula (C1-2) include the monovalent aromatic iodonium cation represented by the following formula (C1-2-2). (In formula (C1-2-2), each Ar independently represents an optionally substituted aromatic hydrocarbon group.)

[0046] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0047] Examples of monovalent aromatic iodonium cations represented by formula (C1-2-2) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0048] Y in equation (PAG-1)１ａ － R １０１ SO ３ － or R １０１ CO ２ － (R １０１ Y in formula (PAG-2) is preferable to represent a divalent organic group having 1 to 40 carbon atoms. ２ａ － R １０２ SO ３ － or R １０２ CO ２ － (R １０２ ) represents a monovalent organic group having 1 to 40 carbon atoms. ) is preferable to represent.

[0049] R １０１ The divalent organic group having 1 to 40 carbon atoms in this compound may or may not have a heteroatom. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc. １０２ The monovalent organic group having 1 to 40 carbon atoms in this compound may or may not have a heteroatom. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms.

[0050] Y １ａ － For example, a monovalent group obtained by removing a hydrogen atom from a monovalent anion represented by the following formula can be cited: Y ２ａ － For example, a monovalent anion represented by the following formula can be cited.

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060] The repeating unit represented by formula (1) is preferably the repeating unit represented by the following formula (1-1), and more preferably the repeating unit represented by the following formula (1-1-1). (In formula (1-1), R ａ１ Ar represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms that may be substituted with a halogen atom. １ represents a divalent aromatic group which may have substituents, and Y １ｃ ＋ (This represents a monovalent aromatic onium cation.) (In formula (1-1-1), R ａ１ Y represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. １ｃ ＋ (This represents a monovalent aromatic onium cation.)

[0061] R in equations (1-1) and (1-1-1) ａ１ Specific examples and preferred examples include R in formula (1). ａ１ Specific examples and preferred examples are given.

[0062] Ar in equation (1-1) １ The number of carbon atoms is not particularly limited; for example, it may be 6 to 40, 6 to 30, or 6 to 20. １ Examples of aromatic rings in the aromatic group include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, and anthracene rings. １ Examples of substituents that may be present include halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, allyl groups, vinyl groups, alkenyl groups, alkynyl groups, amide groups, alkoxy groups, carboxyl groups, ester groups, acetyl groups, aldehyde groups, epoxy groups, carbonyl groups, thiol groups, thioether groups, sulfonyl groups, sulfide groups, sulfo groups, ether groups, linear, branched, or cyclic alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 20 carbon atoms, monohalogenated methylene groups (-CHX-), dihalogenated methylene groups (-CX-) ２ -), monohalogenated methyl group (-CH ２ X), dihalogenated methyl group (-CHX ２ ), trihalogenated methyl group (-CX ３ Examples include substituents such as (where X represents a halogen atom), or combinations thereof. １ The number of substituents on Ar may be one or two or more. １ When has two or more substituents, the two or more substituents may be the same or different.

[0063] Y in equations (1-1) and (1-1-1) １ｃ ＋ Specific examples and preferred examples include Y in formula (PAG-1). １ｃ ＋ Specific examples and preferred examples are given.

[0064] Below are examples of monomers (compounds represented by formula (1A), described later) that can be used to derive the repeating unit represented by formula (1). The following examples also include examples of monomers that can be used as substitutes for the monomers that can derive the repeating unit represented by formula (1), and which can introduce photoacid generators into the polymer.

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105] <<Repeating unit represented by formula (2)>> (In formula (2), R ａ２ X represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom.１ is -O- or -NR ２ - (R ２ represents a hydrogen atom or a monovalent organic group. ) and R １ X represents a hydrogen atom or a monovalent organic group. １ ga-NR ２ - When R １ and R ２ They may be together forming a ring structure.

[0106] R ａ２ Hydrogen atoms and methyl groups are preferred as these elements.

[0107] R １ and R ２ The number of carbon atoms in the monovalent organic group in R is not particularly limited, but may be, for example, 1 to 40, 1 to 30, or 1 to 20. １ and R ２ The monovalent organic group in this compound may or may not have a heteroatom. Examples of heteroatoms include oxygen, sulfur, nitrogen, and halogen atoms.

[0108] R １ and R ２ The monovalent organic group in this expression may or may not have a hydroxyl group. The hydroxyl group may be a phenolic hydroxyl group or a hydroxyl group that is not a phenolic hydroxyl group. The hydroxyl group is, for example, a hydroxyl group bonded to a secondary or tertiary carbon atom. R １ and R ２ For example, it does not contain at least one of a phenolic hydroxyl group or a group that gives a phenolic hydroxyl group through the action of an acid.

[0109] R １ and R ２The monovalent organic group in may or may not have a ring structure. Examples of ring structures include aromatic rings and aliphatic rings. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, and anthracene rings. Examples of aliphatic rings include adamantane derivatives, hydroxyadamantane derivatives, norbornene derivatives, dicyclopentadiene derivatives, tricyclo[5.2.1.02,6]decane derivatives, tricyclo[6.2.1.02,7]undeca-4-ene derivatives, tetrahydrodicyclopentadiene derivatives, camphor derivatives, cyclopropyl rings, cyclobutyl rings, cyclopentyl rings, and cyclohexyl rings.

[0110] R １ and R ２ This is, for example, a hydrocarbon group which may have substituents. Examples of hydrocarbon groups include alkyl groups. Examples of substituents include halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, allyl groups, vinyl groups, alkenyl groups, alkynyl groups, amide groups, alkoxy groups, carboxyl groups, ester groups, acetyl groups, aldehyde groups, epoxy groups, carbonyl groups, thiol groups, thioether groups, sulfonyl groups, sulfide groups, sulfo groups, ether groups, linear, branched, or cyclic alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 20 carbon atoms, monohalogenated methylene groups (-CHX-), dihalogenated methylene groups (-CX-) ２ -), monohalogenated methyl group (-CH ２ X), dihalogenated methyl group (-CHX ２ ), trihalogenated methyl group (-CX ３ Examples include substituents such as halogen atoms (where X represents a halogen atom) or combinations thereof.

[0111] Also, X １ ga-NR ２ - When R １ and R ２ They may also form a ring structure together.

[0112] Examples of monomers used to derive the repeating unit represented by formula (2) include the following compounds. In the following formula, R ０ R represents a hydrogen atom or a methyl group. １ is, =CH ２ It represents.

[0113] <<Repeating unit represented by formula (3)>> (In formula (3), Ra ３ (where represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms that may be substituted with a halogen atom. Ar represents a monovalent aromatic group that may have substituents.)

[0114] R ａ３ Hydrogen atoms and methyl groups are preferred as these elements.

[0115] The number of carbon atoms in Ar is not particularly limited; for example, it may be 6 to 40, 6 to 30, or 6 to 20. The aromatic ring in the aromatic group of Ar may be an aromatic hydrocarbon ring or an aromatic heterocycle. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, and anthracene rings. Substituents that Ar may have include, for example, halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, allyl groups, vinyl groups, alkenyl groups, alkynyl groups, amide groups, alkoxy groups, carboxyl groups, ester groups, acetyl groups, aldehyde groups, epoxy groups, carbonyl groups, thiol groups, thioether groups, sulfonyl groups, sulfide groups, sulfo groups, ether groups, linear, branched, or cyclic alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 20 carbon atoms, monohalogenated methylene groups (-CHX-), and dihalogenated methylene groups (-CX-).２ -), monohalogenomethyl group (-CH ２ X), dihalogenomethyl group (-CHX ２ ), trihalogenomethyl group (-CX ３ ) (X represents a halogen atom), or substituents obtained by combining these groups. Ar may have one or two or more substituents. When Ar has two or more substituents, the two or more substituents may be the same or different. For example, Ar does not contain at least one of a phenolic hydroxy group and a group that provides a phenolic hydroxy group by the action of an acid.

[0116] Examples of monomers used for deriving the repeating unit represented by formula (3) include the following compounds. In the formula below, R ０ represents a hydrogen atom or a methyl group. R １ represents =CH ２ . Me represents a methyl group.

[0117] <<Repeating unit represented by formula (4)>> Polymer (A) may have a repeating unit represented by the following formula (4). (In formula (4), R ２ represents a monovalent organic group.)

[0118] R ２ The number of carbon atoms in the monovalent organic group for is not particularly limited, and may be, for example, 1 to 40, 1 to 30, or 1 to 20. R ２ The monovalent organic group for may or may not have a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom.

[0119] R ２The monovalent organic group in this expression may or may not have a hydroxyl group. The hydroxyl group may be a phenolic hydroxyl group or a hydroxyl group that is not a phenolic hydroxyl group. The hydroxyl group is, for example, a hydroxyl group bonded to a secondary carbon atom or a tertiary carbon atom.

[0120] R ２ The monovalent organic group in may or may not have a ring structure. Examples of ring structures include aromatic rings and aliphatic rings. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, and anthracene rings. Examples of aliphatic rings include adamantane derivatives, hydroxyadamantane derivatives, norbornene derivatives, dicyclopentadiene derivatives, tricyclo[5.2.1.02,6]decane derivatives, tricyclo[6.2.1.02,7]undeca-4-ene derivatives, tetrahydrodicyclopentadiene derivatives, camphor derivatives, cyclopropyl rings, cyclobutyl rings, cyclopentyl rings, and cyclohexyl rings.

[0121] R ２ It may have substituents. Substituents include, for example, halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, allyl groups, vinyl groups, alkenyl groups, alkynyl groups, amide groups, alkoxy groups, carboxyl groups, ester groups, acetyl groups, aldehyde groups, epoxy groups, carbonyl groups, thiol groups, thioether groups, sulfonyl groups, sulfide groups, sulfo groups, ether groups, linear, branched, or cyclic alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 20 carbon atoms, monohalogenated methylene groups (-CHX-), dihalogenated methylene groups (-CX-) ２ -), monohalogenated methyl group (-CH ２ X), dihalogenated methyl group (-CHX ２ ), trihalogenated methyl group (-CX ３ Examples include substituents such as halogen atoms (where X represents a halogen atom) or combinations thereof.

[0122] Examples of monomers used to derive the repeating unit represented by formula (4) include the following compounds:

[0123] Polymer (A) has, for example, a repeating unit represented by formula (1) and a repeating unit represented by formula (2). Polymer (A) has, for example, a repeating unit represented by formula (1), a repeating unit represented by formula (2), and a repeating unit represented by formula (3). Polymer (A) has, for example, a repeating unit represented by formula (1), a repeating unit represented by formula (2), and a repeating unit represented by formula (4).

[0124] Polymer (A) may have repeating units other than those represented by formulas (1) to (4).

[0125] The proportion of repeating units represented by formula (1) in polymer (A) is not particularly limited, but the molar ratio of repeating units represented by formula (1) to the total repeating units of polymer (A) is preferably 0.1 mol% to 60 mol%, and more preferably 0.1 mol% to 50 mol%. If polymer (A) has repeating units represented by formula (2), the proportion of repeating units represented by formula (2) in polymer (A) is not particularly limited, but the molar ratio of repeating units represented by formula (2) to the total repeating units of polymer (A) is preferably 0.1 mol% to 99 mol%, and more preferably 0.1 mol% to 90 mol%. When polymer (A) has repeating units represented by formula (3), the proportion of repeating units represented by formula (3) in polymer (A) is not particularly limited, but the molar ratio of repeating units represented by formula (3) to the total repeating units of polymer (A) is preferably 0.1 mol% to 99 mol%, more preferably 0.1 mol% to 90 mol%, and particularly preferably 0.1 mol% to 60 mol%. When polymer (A) has repeating units represented by formula (4), the proportion of repeating units represented by formula (4) in polymer (A) is not particularly limited, but the molar ratio of repeating units represented by formula (4) to the total repeating units of polymer (A) is preferably 0.1 mol% to 99 mol%, more preferably 0.1 mol% to 90 mol%, and particularly preferably 0.1 mol% to 80 mol%.

[0126] In polymer (A), there may be two or more repeating units represented by formula (2). In that case, polymer (A) is R １ A repeating unit (2-1) represented by formula (2) has a ring structure, and R １ It is preferable that the repeating unit (2-2) represented by formula (2) does not have a ring structure. In the repeating unit (2-2), R １ Preferably, it has a hydroxyl group bonded to a secondary carbon atom.

[0127] The method for synthesizing polymer (A) is not particularly limited, and examples include radical polymerization of monomer raw materials comprising a compound represented by the following formula (1A) and at least one of the compounds represented by the following formula (2A) and the compound represented by the following formula (3A). (In formula (1A), R ａ１ , L １ , and PAG are R in formula (1), respectively. ａ１ , L １ , and is synonymous with PAG. In formula (2A), R ａ２ , X １ , and R １ These are R in equation (2), respectively. ａ２ , X １ , and R １ This is equivalent to: In equation (3A), R ａ３ , and Ar are, respectively, R in equation (3) ａ３ (This is synonymous with Ar.)

[0128] The molecular weight of polymer (A) is not particularly limited. The lower limit of the weight-average molecular weight of polymer (A) is, for example, 1000 to 3000. The upper limit of the weight-average molecular weight of polymer (A) is, for example, 10000 to 40000.

[0129] The content of polymer (A) of the present invention in the resist underlayer film forming composition is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of suitably obtaining the effects of the present invention, for example, 10.1 to 100% by mass is preferred, 10.1 to 90% by mass is more preferred, and 10.1 to 80% by mass is particularly preferred, relative to the film constituent components. Film constituent components refer to components other than the solvent in the resist underlayer film forming composition.

[0130] <Solvent> The solvent is not particularly limited and may be water or an organic solvent. Examples of organic solvents include carboxylic acids having a hydroxyl group, linear or cyclic alkyl ketones, cyclic lactones, alkylene glycol alkyl ethers, alkylene glycol monoalkyl ether carboxylic acid esters (monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers).

[0131] Examples of carboxylic acids having a hydroxyl group include ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, ethyl hydroxyethyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, and methyl 2-hydroxy-3-methylbutyrate.

[0132] Examples of linear or cyclic alkyl ketones include methyl ethyl ketone, cyclopentanone, and cyclohexanone.

[0133] An example of a cyclic lactone is γ-butyrolactone.

[0134] Examples of alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutylcarbinol, and propylene glycol monobutyl ether. Examples of alkylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether.

[0135] Examples of alkylene glycol monoalkyl ether carboxylic acid esters include monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers. Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkylene glycol monoalkyl ether acetates. Examples of alkylene glycol monoalkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate. Examples of alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers include 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methyl carbonate, 2-ethoxyethyl ethyl carbonate, and 2-propoxyethyl methyl carbonate.

[0136] These solvents can be used individually or in combination of two or more.

[0137] The mass percentage of the organic solvent in the solvent is not particularly limited, but 50% to 100% by mass is preferred.

[0138] The solvent content in the resist underlayer film forming composition 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.

[0139] <Crosslinking Agent> The resist underlayer film forming composition may contain a crosslinking agent. The crosslinking agent is not particularly limited. The crosslinking agent has a different structure from polymer (A) of the present invention.

[0140] As crosslinking agents, aminoplast crosslinking agents and phenoplast crosslinking agents are preferred. Aminoplast crosslinking agents are addition condensates of compounds having amino groups, such as melamine and guanamine, with formaldehyde. Phenoplast crosslinking agents are addition condensates of compounds having phenolic hydroxyl groups with formaldehyde.

[0141] Examples of crosslinking agents include compounds having two or more of the following structures. (In the structure, R １０１ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond. The bond is, for example, attached to a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0142] R １０１ Preferably, the group is a hydrogen atom, a methyl group, an ethyl group, or a group represented by the following structure. (In the structure, R １０２ represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bonding bond.

[0143] Preferred crosslinking agents include melamine compounds, guanamine compounds, glycoluryl compounds, urea compounds, and compounds having a phenolic hydroxyl group. These can be used individually or in combination of two or more.

[0144] Examples of melamine compounds include hexamethylmelamine, hexamethoxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are methoxymethylated or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are acyloxymethylated or mixtures thereof.

[0145] Examples of guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, compounds obtained by methoxymethylating 1 to 4 methylol groups of tetramethylolguanamine or mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds obtained by acyloxymethylating 1 to 4 methylol groups of tetramethylolguanamine or mixtures thereof, and the like.

[0146] Examples of glycoluril compounds include tetramethylolglycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, compounds obtained by methoxymethylating 1 to 4 methylol groups of tetramethylolglycoluril or mixtures thereof, compounds obtained by acyloxymethylating 1 to 4 methylol groups of tetramethylolglycoluril or mixtures thereof, and the like.

[0147] Further, the glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E). (In formula (1E), four R １ each independently represent a methyl group or an ethyl group, and R ２ and R ３ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0148] Examples of the glycoluril derivative represented by formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0149] The glycoluril derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0150] (In formula (2E), R ２ and R ３ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R ４ each independently represent an alkyl group having 1 to 4 carbon atoms.)

[0151] (In formula (3d), R １ (This represents a methyl group or an ethyl group.)

[0152] Examples of glycoluryl derivatives represented by formula (2E) include the compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include the compounds represented by formulas (3d-1) and (3d-2) below.

[0153] Examples of urea compounds include tetramethylolurea, tetramethoxymethylurea, compounds in which one to four methylol groups of tetramethylolurea are methoxymethylated or mixtures thereof, and tetramethoxyethylurea.

[0154] Examples of compounds having a phenolic hydroxyl group include compounds represented by the following formulas (G-1) or (G-2). (In equations (G-1) and (G-2), Q １ R indicates a single bond or an m1-valent organic group. １ and R ４ Each of these represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms. ２ and R ５ Each represents either a hydrogen atom or a methyl group. ３ and R ６ Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. １ is 1 ≤ n １ n is an integer ≤ 3. ２ is 2 ≤ n ２ An integer n ≤ 5 ３ is 0 ≤ n ３ n is an integer ≤ 3. ４ is 0 ≤ n ４ integers ≤ 3, 3 ≤ (n １ +n ２ +n ３ +n ４ This shows integers n ≤ 6. ５ is 1 ≤ n５ n is an integer ≤ 3. ６ is 1 ≤ n ６ n is an integer ≤ 4. ７ is 0 ≤ n ７ n is an integer ≤ 3. ８ is 0 ≤ n ８ integers ≤ 3, 2 ≤ (n ５ +n ６ +n ７ +n ８ (This represents an integer between 5 and 2. m1 represents an integer between 2 and 10.)

[0155] Furthermore, examples of compounds having a phenolic hydroxyl group include compounds represented by the following formulas (G-3) or (G-4). Compounds represented by formulas (G-1) or (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. (In equations (G-3) and (G-4), Q ２ R indicates a single bond or an m2 valent organic group. ８ , R ９ , R １１ and R １２ Each represents either a hydrogen atom or a methyl group. ７ and R １０ Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. ９ is 1 ≤ n ９ n is an integer ≤ 3. １０ is 2 ≤ n １０ An integer n ≤ 5 １１ is 0 ≤ n １１ n is an integer ≤ 3. １２ is 0 ≤ n １２ integers ≤ 3, 3 ≤ (n ９ +n １０ +n １１ +n １２ This shows integers n ≤ 6. １３ is 1 ≤ n １３ n is an integer ≤ 3. １４ is 1 ≤ n １４ n is an integer ≤ 4. １５ is 0 ≤ n １５ n is an integer ≤ 3. １６ is 0 ≤ n １６integers ≤ 3, 2 ≤ (n １３ +n １４ +n １５ +n １６ ) indicates an integer ≤ 5. m² indicates an integer between 2 and 10. ) Q ２ Examples of m2 valent organic groups in this context include m2 valent organic groups having 1 to 4 carbon atoms.

[0156] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0157] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds. The above compound can be obtained as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. An example of such a product is TMOM-BP, a product of Asahi Organic Chemicals Co., Ltd.

[0158] Among these, glycoluryl compounds are preferred, specifically tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which one to four methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, compounds in which one to four methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof, and tetramethoxymethyl glycoluryl is more preferred.

[0159] The molecular weight of the crosslinking agent is not particularly limited, but it is preferably 1,000 or less.

[0160] The content of the crosslinking agent in the resist underlayer film forming composition is not particularly limited, but is, for example, 1% to 60% by mass, preferably 10% to 50% by mass, relative to the polymer (A) of the present invention.

[0161] <Curing Catalyst> The curing catalyst included as an optional component in the resist underlayer film formation composition is preferably an acid and / or its salt and / or a thermal acid generator. Examples of acids include p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 4-hydroxybenzenesulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, etc. Salts of the above-mentioned acids can also be used. The salts are not limited to those mentioned above, but ammonia derivative salts such as trimethylamine salt and triethylamine salt, pyridine derivative salts, morpholine derivative salts, etc. can be suitably used. Examples of such salts include pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium-phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium salt of p-phenolsulfonic acid), pyridinium-trifluoromethanesulfonic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid. Examples of thermal acid generators include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE® CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other alkyl organic sulfonates.

[0162] Only one type of curing catalyst may be used, or two or more types may be used in combination.

[0163] When a curing catalyst is used, the content of the curing catalyst is, for example, 0.1% to 50% by mass relative to the crosslinking agent, preferably 1% to 30% by mass.

[0164] <Photoacid Generator, Photodegradable Quencher> The resist underlayer film formation composition may further contain at least one of a photoacid generator and a photodegradable quencher.

[0165] Examples of photoacid generators include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0166] Examples of onium salt compounds include salts of aromatic sulfonium cations or aromatic iodonium cations with sulfonate anions. Examples of aromatic sulfonium cations include the monovalent aromatic sulfonium cation represented by formula (C1-1) mentioned in the description of polymer (A). Specific examples of aromatic sulfonium cations include the specific examples mentioned in the description of the monovalent aromatic sulfonium cation represented by formula (C1-1). Examples of aromatic iodonium cations include the monovalent aromatic iodonium cation represented by formula (C1-2) mentioned in the description of polymer (A). Specific examples of aromatic iodonium cations include the specific examples mentioned in the description of the monovalent aromatic iodonium cation represented by formula (C1-2). Examples of sulfonate anions include the Y in formula (PAG-1) mentioned in the description of polymer (A). １ａ － Sulfonate anions can be cited as examples. Specific examples of sulfonate anions include, for example, Y １ａ － Specific examples of sulfonate anions mentioned in the explanation can be cited.

[0167] Examples of iodonium salt compounds include iodonium salt compounds such as 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.

[0168] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0169] Examples of disulfonyl diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0170] The photodegradable quencher is not particularly limited as long as it is a compound that loses its ability as a quencher upon photodegradation, for example, onium salt compounds. Examples of photodegradable quenchers include salts of aromatic sulfonium cations or aromatic iodonium cations with carboxylic acid anions. An example of an aromatic sulfonium cation is the monovalent aromatic sulfonium cation represented by formula (C1-1) mentioned in the description of polymer (A). Specific examples of aromatic sulfonium cations include the specific examples mentioned in the description of the monovalent aromatic sulfonium cation represented by formula (C1-1). An example of an aromatic iodonium cation is the monovalent aromatic iodonium cation represented by formula (C1-2) mentioned in the description of polymer (A). Specific examples of aromatic iodonium cations include the specific examples mentioned in the description of the monovalent aromatic iodonium cation represented by formula (C1-2). Carboxylic acid anions include, for example, anionic structures containing carboxylic acid derivatives such as benzoic acid and alkyl carboxylic acids, as well as halogen ions and carbonate ions. As an example of a carboxylic acid anion, Y in formula (PAG-1) given in the description of polymer (A) １ａ － Carboxylate anions can be cited as examples. Specific examples of carboxylate anions include, for example, Y １ａ － Specific examples of carboxylic acid anions mentioned in the explanation can be cited.

[0171] Furthermore, anions commonly used as photodegradable quenchers include anionic structures containing carboxylic acid derivatives such as benzoic acid and alkyl carboxylic acids, as well as halogen ions and carbonate ions. For example, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium iodide, triphenylsulfonium nitrate, triphenylsulfonium carbonate, triphenylsulfonium salicylate, triphenylsulfonium 3-hydroxybenzoate, triphenylsulfonium 4-hydroxybenzoate, triphenylsulfonium dihydroxybenzoate, triphenylsulfonium trihydroxybenzoate, triphenylsulfonium nitrobenzoate, triphenylsulfonium cyanobenzoate, triphenylsulfonium methoxybenzoate, triphenylsulfonium methylbenzoate, triphenylsulfonium nitrosalicylate, triphenylsulfonium cyanosalicylate, triphenylsulfonium methoxysalicylate, triphenylsulfonium methylsalicylate, triphenylsulfonium ethylbenzoate, triphenylsulfonium tert-butylbenzoate, triphenylsulfonium biphenylcarboxylic acid, triphenyl pentafluorobenzoate Sulfonium, ethyl salicylate triphenylsulfonium, tert-butyl salicylate triphenylsulfonium, biphenyl carboxylate triphenylsulfonium, tetrafluorosalicylate triphenylsulfonium, cyclopentyl carboxylate triphenylsulfonium, cyclohexyl carboxylate triphenylsulfonium, cyclopentyl salicylate triphenylsulfonium, cyclohexyl salicylate triphenylsulfonium, fluorobenzoate triphenylsulfonium, difluorobenzoate triphenylsulfonium, trifluorobenzoate triphenylsulfonium, chlorobenzoate triphenylsulfonium, dichlorobenzoate triphenylsulfonium, trichlorobenzoate triphenylsulfonium, bromobenzoate triphenylsulfonium, dibromobenzoate triphenylsulfonium, tribromobenzoate triphenylsulfonium, iodobenzoate triphenylsulfonium, diiodobenzoate triphenylsulfonium, triiodobenzoate triphenylsulfoniumTriphenylsulfonium trifluoromethylbenzoate, triphenylsulfonium ditrifluoromethylbenzoate, triphenylsulfonium fluorosalicylate, triphenylsulfonium difluorofluorosalicylate, triphenylsulfonium bromosalicylate, triphenylsulfonium dibromosalicylate, triphenylsulfonium iodosalicylate, triphenylsulfonium diiodosalicylate, triphenylsulfonium trifluoromethylbenzoate, triphenylsulfonium ditrifluoromethylbenzoate, triphenylsulfonium thiolbenzoate, triphenylsulfonium thiolsalicylate, 2,2-dicyclohexyl-2-hydroxycarboxylic acid triphenylsulfonium, 2,2-bis((4-tertbutyl)phenyl)-2-hydroxycarboxylic acid triphenylsulfonium, dicyclohexyl-2-hydroxycarboxylic acid triphenylsulfonium, 9-hydroxy-9H-fluorene-9-carboxylic acid triphenylsulfonium, 1-adamantanecarboxylic acid triphenylsulfonium, naphthalenecarboxylic acid triphenylsulfonium, hydroxynaph Triphenylsulfonium talenecarboxylate, triphenylsulfonium dihydroxynaphthalenecarboxylate, triphenylsulfonium acrylate, triphenylsulfonium methacrylate, triphenylsulfonium acetate, triphenylsulfonium fluoroacetate, triphenylsulfonium trifluoroacetate, triphenylsulfonium bromoacetate, triphenylsulfonium iodoacetate, triphenylsulfonium propionate, triphenylsulfonium butyrate, triphenylsulfonium valerate, triphenylsulfonium caproate, triphenylsulfonium enanthate, triphenylsulfonium caprylate, triphenylsulfonium norbornenecarboxylate, dibenzothiophenium chloride, dibenzothiophenium bromide, dibenzothiophenium iodide, dibenzothiophenium nitrate, dibenzothiophenium carbonate, dibenzothiophenium salicylate, dibenzothiophenium 3-hydroxybenzoate, dibenzothiophenium 4-hydroxybenzoate, dihydroxybenzoate, dibenzothiophenium trihydroxybenzoate,Dibenzothiophenium nitrobenzoate, dibenzothiophenium cyanobenzoate, dibenzothiophenium methoxybenzoate, dibenzothiophenium methylbenzoate, dibenzothiophenium nitrosalicylate, dibenzothiophenium cyanosalicylate, dibenzothiophenium methoxysalicylate, dibenzothiophenium methylsalicylate, dibenzothiophenium ethylbenzoate, dibenzothiophenium tert-butylbenzoate, dibenzothiophenium biphenylcarboxylate, dibenzothiophenium pentafluorobenzoate, Dibenzothiophenium ethyl salicylate, dibenzothiophenium tert-butyl salicylate, dibenzothiophenium biphenyl carboxylate, dibenzothiophenium tetrafluorosalicylate, dibenzothiophenium cyclopentyl carboxylate, dibenzothiophenium cyclohexyl carboxylate, dibenzothiophenium cyclopentyl salicylate, dibenzothiophenium cyclohexyl salicylate, dibenzothiophenium fluorobenzoate, dibenzothiophenium difluorobenzoate, dibenzothiophenium trifluorobenzoate Dibenzothiophenium chlorobenzoate, dibenzothiophenium dichlorobenzoate, dibenzothiophenium trichlorobenzoate, dibenzothiophenium bromobenzoate, dibenzothiophenium dibromobenzoate, dibenzothiophenium tribromobenzoate, dibenzothiophenium iodobenzoate, dibenzothiophenium diiodobenzoate, dibenzothiophenium triiodobenzoate, dibenzothiophenium trifluoromethylbenzoate, dibenzothiophenium ditrifluoromethylbenzoate, diben fluorosalicylate Zothiophenium, dibenzothiophenium difluorofluorosalicylate, dibenzothiophenium bromosalicylate, dibenzothiophenium dibromosalicylate, dibenzothiophenium iodosalicylate, dibenzothiophenium diiodosalicylate, dibenzothiophenium trifluoromethylbenzoate, dibenzothiophenium ditrifluoromethylbenzoate, dibenzothiophenium thiolbenzoate, dibenzothiophenium thiolsalicylate, 2,2-dicyclohexyl-2-hydroxycarboxylate dibenzothiophenium,2,2-Bis((4-tert-butyl)phenyl)-2-hydroxycarboxylate dibenzothiophenium, dicyclohexyl-2-hydroxycarboxylate dibenzothiophenium, 9-hydroxy-9H-fluorene-9-carboxylate dibenzothiophenium, 1-adamantanecarboxylate dibenzothiophenium, naphthalenecarboxylate dibenzothiophenium, hydroxynaphthalenecarboxylate dibenzothiophenium, dihydroxynaphthalenecarboxylate dibenzothiophenium, acrylate dibenzothiophenium, methacrylate dibenzothio Ophenium, dibenzothiophenium acetate, dibenzothiophenium fluoroacetate, dibenzothiophenium trifluoroacetate, dibenzothiophenium bromoacetate, dibenzothiophenium iodoacetate, dibenzothiophenium propionate, dibenzothiophenium butyrate, dibenzothiophenium valerate, dibenzothiophenium caproate, dibenzothiophenium enanthate, dibenzothiophenium caprylate, dibenzothiophenium norbornene carboxylate, diphenyliodonium chloride, diphenyliodonium bromide, di Phenyliodonium iodide, diphenyliodonium nitrate, diphenyliodonium carbonate, diphenyliodonium salicylate, diphenyliodonium 3-hydroxybenzoate, diphenyliodonium 4-hydroxybenzoate, diphenyliodonium dihydroxybenzoate, diphenyliodonium trihydroxybenzoate, diphenyliodonium nitrobenzoate, diphenyliodonium cyanobenzoate, diphenyliodonium methoxybenzoate, diphenyliodonium methylbenzoate, diphenyliodonium nitrosalicylate Nyliodonium, diphenyliodonium cyanosalicylate, diphenyliodonium methoxysalicylate, diphenyliodonium methylsalicylate, diphenyliodonium ethylbenzoate, diphenyliodonium tert-butylbenzoate, diphenyliodonium biphenylcarboxylate, diphenyliodonium pentafluorobenzoate, diphenyliodonium ethylsalicylate, diphenyliodonium tert-butylsalicylate, diphenyliodonium biphenylcarboxylate, diphenyliodonium tetrafluorosalicylate,Diphenyliodonium cyclopentylcarboxylate, diphenyliodonium cyclohexylcarboxylate, diphenyliodonium cyclopentyl salicylate, diphenyliodonium cyclohexyl salicylate, diphenyliodonium fluorobenzoate, diphenyliodonium difluorobenzoate, diphenyliodonium trifluorobenzoate, diphenyliodonium chlorobenzoate, diphenyliodonium dichlorobenzoate, diphenyliodonium trichlorobenzoate, diphenyliodonium bromobenzoate, dibromobenzoate Phenyliodonium, diphenyliodonium tribromobenzoate, diphenyliodonium iodobenzoate, diphenyliodonium diiodobenzoate, diphenyliodonium triiodobenzoate, diphenyliodonium trifluoromethylbenzoate, diphenyliodonium ditrifluoromethylbenzoate, diphenyliodonium fluorosalicylate, diphenyliodonium difluorofluorosalicylate, diphenyliodonium bromosalicylate, diphenyliodonium dibromosalicylate, diphenyliodonium iodo Diphenyliodonium diiodosalicylate, diphenyliodonium trifluoromethylbenzoate, diphenyliodonium ditrifluoromethylbenzoate, diphenyliodonium thiolbenzoate, diphenyliodonium thiolsalicylate, 2,2-dicyclohexyl-2-hydroxycarboxylic acid diphenyliodonium, 2,2-bis((4-tertbutyl)phenyl)-2-hydroxycarboxylic acid diphenyliodonium, dicyclohexyl-2-hydroxycarboxylic acid diphenyliodonium, 9-hydroxy-9H-F Diphenyliodonium ruolene-9-carboxylate, diphenyliodonium 1-adamantanecarboxylate, diphenyliodonium naphthalenecarboxylate, diphenyliodonium hydroxynaphthalenecarboxylate, diphenyliodonium dihydroxynaphthalenecarboxylate, diphenyliodonium acrylate, diphenyliodonium methacrylate, diphenyliodonium acetate, diphenyliodonium fluoroacetate, diphenyliodonium trifluoroacetate, diphenyliodonium bromoacetate, diphenyliodonium iodoacetate,Examples include diphenyliodonium propionate, diphenyliodonium butyrate, diphenyliodonium valerate, diphenyliodonium caproate, diphenyliodonium enanthate, diphenyliodonium caprylate, diphenyliodonium norbornene carboxylate, (2-carboxyphenyl)phenyliodonium hydroxy intramolecular salt, and (2-carboxyphenyl)hydroxyphenyliodonium.

[0172] Only one type of photoacid generator may be used, or two or more types may be used in combination. Only one type of photodegradable quencher may be used, or two or more types may be used in combination.

[0173] When a photoacid generator and a photodegradable quencher are used, the content ratio of the photoacid generator and the photodegradable quencher is, for example, 0.1% to 30% by mass, preferably 1% to 20% by mass, relative to polymer (A).

[0174] <Surfactants> Surfactants are used, for example, to prevent the occurrence of pinholes and striations, and to further improve the applicability to uneven surfaces. Examples of surfactants include linear or branched alkylbenzene sulfonic acid (e.g., dodecylbenzenesulfonic acid), polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and polyoxyethylene sorbitan monolaurate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorinated surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product name), Megafac F171, F173, R-30 (manufactured by DIC Corporation, product name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc., product name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added is usually 2.0% by mass or less, preferably 1.0% by mass or less, relative to the film components of the resist underlayer film forming composition. These surfactants may be added individually or in combination of two or more types.

[0175] The film constituent components contained in the resist underlayer film forming composition of the present invention, i.e., the components excluding the solvent, are, for example, 0.01% to 10% by mass, and preferably 0.01% to 2% by mass.

[0176] The resist underlayer formation composition is preferably used in EB or EUV lithography. The resist underlayer formation composition is preferably used to form an underlayer of a metal-containing resist.

[0177] (Resist Underlayer Film) The resist underlayer film of the present invention is a cured product of the resist underlayer film forming composition described above. The resist underlayer film can be manufactured, for example, by coating the resist underlayer film forming composition described above onto a semiconductor substrate and firing it.

[0178] Examples of semiconductor substrates to which the resist underlayer film formation composition is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0179] When using a semiconductor substrate with an inorganic film formed on its surface, the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on-glass: SOG). Examples of the inorganic film include polysilicon films and silicon oxide films (e.g., SiO2). ２ Examples include substrates, silicon nitride films (e.g., SiN substrates), silicon oxide nitride films (e.g., SiON substrates), BPSG (Boro-Phosphoric Acid Glass) films, titanium nitride films, titanium oxide nitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0180] The resist underlayer film forming composition of the present invention is applied to such a semiconductor substrate by an appropriate coating method such as a spinner or coater. Then, the resist underlayer film is formed by baking using a heating means such as a hot plate. 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. Baking may be performed in an atmospheric environment, or N ２ It's fine to do it in a relaxed atmosphere.

[0181] The thickness of the resist underlayer film can be, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm ( The wavelengths are 5 nm to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.03 μm (30 nm), 0.003 μm (3 nm) to 0.02 μm (20 nm), 0.005 μm (5 nm) to 0.02 μm (20 nm), 0.003 μm (3 nm) to 0.01 μm (10 nm), 0.005 μm (5 nm) to 0.01 μm (10 nm), 0.003 μm (3 nm) to 0.006 μm (6 nm), or 0.005 μm (5 nm).

[0182] The method for measuring the film thickness of the resist underlayer in this specification is as follows: • Measurement device name: Ellipsometer-type film thickness measuring device RE-3100 (SCREEN Corporation) • SWE (single-wavelength ellipsometer) mode • Arithmetic mean of 8 points (for example, 8 points measured at 1 cm intervals in the wafer X direction)

[0183] (Laminate) The laminate of the present invention comprises a semiconductor substrate and a resist underlayer film of the present invention. Examples of the semiconductor substrate include the semiconductor substrate described above. The resist underlayer film is disposed on top of the semiconductor substrate, for example.

[0184] (Method for manufacturing semiconductor devices, method for forming patterns) The method for manufacturing semiconductor devices of the present invention includes at least the following steps: - A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition of the present invention; and - A step of forming a resist film on the resist underlayer film.

[0185] The pattern formation method of the present invention includes at least the following steps: • A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film formation composition of the present invention; • A step of forming a resist film on the resist underlayer film; • A step of irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern; and • A step of etching the resist underlayer film using the resist pattern as a mask.

[0186] Typically, a resist film is formed on top of a resist underlayer. The thickness of the resist film can be, 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.

[0187] The resist film formed on the resist underlayer by a known method (e.g., coating and firing of a resist composition) is not particularly limited as long as it responds to light or electron beam (EB) used for irradiation. Both negative-type and positive-type photoresists can be used. In this specification, resists that respond to EB are also referred to as photoresists. Examples of photoresists include positive-type photoresists consisting of a novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder and a photoacid generator, and chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist and a photoacid generator, and resists containing metal elements. Examples include V146G (manufactured by JSR Corporation), APEX-E (manufactured by Cyprey Corporation), PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), and AR2772 and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Additionally, examples include fluorine-containing polymer photoresists, such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0188] Also, 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, WO201 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 While so-called resist compositions and metal-containing resist compositions such as resist compositions, radiation-sensitive resin compositions, and high-resolution patterning compositions based on organometallic solutions described in JP 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., can be used, they are not limited to these.

[0189] Examples of resist compositions include the following compositions.

[0190] A photosensitive or radiation-sensitive resin composition comprising resin A having repeating units with acid-degradable groups whose polar groups are protected by protecting groups that are removed by the action of an acid, and a compound represented by the following general formula (121).

[0191] In general formula (121), m represents an integer from 1 to 6. １ and R ２ Each of these independently represents either a fluorine atom or a perfluoroalkyl group. １ is -O-, -S-, -COO-, -SO ２ -, or -SO ３ Represents -. L ２ W represents an alkylene group or single bond which may have substituents. １ This represents a cyclic organic group which may have substituents. ＋ This represents a cation.

[0192] A metal-containing film-forming composition for 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 third to seventh period of groups 3 to 15 of the periodic table.

[0193] A radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) that includes an acid-dissociable group, and an acid generator.

[0194] (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. １ R is a hydroxyl group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer from 0 to 11. If n is 2 or greater, multiple R １ They are the same or different. R ２ R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), ３ R is a monovalent group having 1 to 20 carbon atoms and containing the above-mentioned acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. ４(These are a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0195] A resist composition containing a resin (A1) comprising structural units having a cyclic carbonate ester structure, structural units represented by the following formula, and structural units having an acid-unstable group, and an acid generator.

[0196] [In the formula, R ２ X represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom, which may have a halogen atom. １ These are single bonds, -CO-O-* or -CO-NR ４ - represents *, where * represents a bond with -Ar, R ４ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have one or more groups selected from the group consisting of hydroxyl groups and carboxyl groups.

[0197] Examples of resist films include the following:

[0198] A resist film comprising a base resin containing repeating units represented by the following formula (a1) and / or repeating units represented by the following formula (a2), and repeating units that generate acid bonded to the polymer main chain upon exposure.

[0199] (In equations (a1) and (a2), R Ａ Each of these is independently either a hydrogen atom or a methyl group. １ and R ２ These are each independently tertiary alkyl groups having 4 to 6 carbon atoms. ３ Each of these is independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. １ X is a linking group having 1 to 12 carbon atoms, containing a single bond, a phenylene group or a naphthylene group, or at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. ２ (These are single bonds, ester bonds, or amide bonds.)

[0200] Examples of resist materials include the following:

[0201] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0202] (In equations (b1) and (b2), R Ａ X is a hydrogen atom or a methyl group. １ X is a single bond or an ester group. ２ X is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and a portion of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group, or a lactone ring-containing group, and X ２ At least one hydrogen atom in is replaced by a bromine atom. ３ Rf is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. １ ~Rf ４ Each of these is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Also, Rf １ and Rf ２ These may combine to form a carbonyl group. １ ~R ５ Each of these is independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonic acid ester group. １ and R ２These may combine to form a ring with the sulfur atom to which they are bonded.

[0203] A resist material comprising a base resin containing a polymer having repeating units represented by the following formula (a).

[0204] (In formula (a), R Ａ R is a hydrogen atom or a methyl group. １ R is a hydrogen atom or an acid-unstable group. ２ This is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. １ This is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, which may contain a single bond or a phenylene group, or an ester group or a lactone ring. ２ is -O-, -O-CH ２ It is - 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.

[0205] A resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, comprising a base component (A) whose solubility in a developer changes due to the action of the acid and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, wherein the fluorine additive component (F) contains a fluororesin component (F1) having a constituent unit (f1) containing a base-dissociable group and a constituent unit (f2) containing a group represented by the following general formula (f2-r-1), the resist composition.

[0206] [In formula (f2-r-1), Rf ２１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group. n'' is an integer from 0 to 2. * represents a bond.

[0207] The aforementioned constituent unit (f1) includes a constituent unit represented by the following general formula (f1-1) or a constituent unit represented by the following general formula (f1-2).

[0208] [In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group that does not have an acid-dissociable site. A ａｒｙｌ X is a divalent aromatic cyclic group which may have substituents. ０１ R is a single bond or a divalent linking group. ２ These are, independently, organic groups that contain a fluorine atom.

[0209] The resist composition may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MORs), and a typical example is a tin oxide-based resist. Examples of metal oxide resist materials include a coating composition containing a metal oxo-hydroxo network having an organic ligand via a metal-carbon bond and / or metal-carboxylate bond, as described in Japanese Patent Application Publication No. 2019-113855. An example of a metal-containing resist uses a peroxo ligand as a radiosensitizing stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described in the patent document described in paragraph

[0011] of Publication No. 2019-532489, for example. Examples of such patent documents include U.S. Patent No. 9,176,377B2, U.S. Patent Application Publication No. 2013 / 0224652A1, U.S. Patent No. 9,310,684B2, U.S. Patent Application Publication No. 2016 / 0116839A1, and U.S. Patent Application Publication No. 15 / 291738.

[0210] A coating comprising a metal oxo-hydroxo network having organic ligands via metal-carbon bonds and / or metal-carboxylate bonds.

[0211] Inorganic oxo / hydroxo-based compositions.

[0212] A coating solution comprising an organic solvent; a first organometallic composition comprising formula R ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ (Here, 0 < z ≤ 2 and 0 < (z + x) ≤ 4), equation R'ｎ SnX ４－ｎ A first organometallic composition represented by (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 or a combination thereof having a hydrolyzable bond to Sn; and a hydrolyzable metal compound of the formula MX' ｖ A coating solution comprising a hydrolyzable metal compound represented by (where M is a metal selected from groups 2 to 16 of the periodic table, v is a number from 2 to 6, and X' is a ligand or combination thereof having a hydrolyzable M-X bond).

[0213] Organic solvent and formula RSnO （３／２－ｘ／２） (OH) ｘ A coating solution comprising a first organometallic compound represented by the formula (wherein 0 < x < 3), wherein the solution contains about 0.0025 M to about 1.5 M of tin, and R is an alkyl group or cycloalkyl group having 3 to 31 carbon atoms, wherein the alkyl group or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom.

[0214] An aqueous solution of an inorganic pattern-forming precursor comprising a mixture of water, a metal suboxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand containing a peroxide group.

[0215] Other examples of metal-containing resists include the compositions described in Japanese Patent Publication No. 2011-253185, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, Japanese Patent Publication No. 2020-122959, Japanese Patent Publication No. 2020-122960, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367, and WO2021 / 016229. These contents are incorporated into this specification to the same extent as if they were all explicitly stated.

[0216] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and includes a method of applying a coating-type resist material (a composition for forming a metal-containing resist film), which is a metal-containing resist, and firing it.

[0217] Furthermore, the metal-containing resist film may be formed by vapor deposition. An example of a method for forming a metal-containing resist film by vapor deposition is the method described in Japanese Patent Application Publication No. 2017-116923. The contents of Japanese Patent Application Publication No. 2017-116923 are incorporated herein to the same extent as if they were fully disclosed. In Japanese Patent Application Publication No. 2017-116923, the metal-containing resist film in the present invention is referred to as a metal oxide-containing film.

[0218] Irradiation with light or an electron beam is performed, for example, through a mask (reticle) for forming a predetermined pattern. For example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet) or EB (electron beams) are used. The resist underlayer film forming composition of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation, and more preferably for EUV (extreme ultraviolet) exposure. The electron beam irradiation energy and the amount of light exposure are not particularly limited.

[0219] A bake (PEB: Post Exposure Bake) may be performed after irradiation with light or electron beam and before development. The bake temperature is not particularly limited, but is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C. The bake time is not particularly limited, but is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0220] The film can be developed using either a wet process or a dry process.

[0221] For wet development, for example, alkaline developers, acidic developers, and organic solvents are used. The wet development temperature can range from 5°C to 50°C. The wet development time can range from 10 seconds to 300 seconds.

[0222] As alkaline developers, for example, aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous 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; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole and piperidine can be used. Furthermore, appropriate amounts of alcohols such as isopropyl alcohol and nonionic surfactants can be added to the aqueous solutions of the above alkalis. Among these, preferred developers are aqueous solutions of quaternary ammonium salts, and more preferably aqueous solutions of tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers. Instead of an alkaline developer, a method can be used in which development is performed with an organic solvent such as butyl acetate, and the parts of the photoresist whose alkali dissolution rate has not improved are developed.

[0223] Acidic developers and organic solvents can be used as developers for metal-containing resists, and development is performed with the developer after irradiation with light or electron beam. As a result, for example, when a negative-type metal-containing resist film is used, the unexposed areas of the metal-containing resist film are removed, and a pattern of the metal-containing resist film is formed.

[0224] Examples of acidic developers include acidic developers containing halides (e.g., HCl or HBr), organic acids (e.g., formic acid, acetic acid, or citric acid), or organofluorine compounds (e.g., trifluoroacetic acid) (e.g., aqueous acidic developers or acidic developers in organic solvents).

[0225] Examples of developers (organic solvents) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, 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 monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl 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, 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, lactic acid Tyl, butyl lactate, propyl lactate, 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, propyl-3-methoxypropionate, 2-heptanone,Examples include cyclohexanone, acetone, γ-butyrolactone, isopropyl alcohol, propylene glycol methyl ether, and propylene glycol methyl ether acetate. Furthermore, surfactants can be added to these developing solutions.

[0226] Development processes, including dry development, can remove exposed or unexposed regions by any useful development process. In one embodiment using a metal-containing resist, the exposed region may have activated reaction centers, such as metal dangling bonds, M-H groups (where M is a metal atom), or dimerized M-M bonds (where M is a metal atom). In certain embodiments, M-H groups may be selectively removed using one or more dry development processes (e.g., halide chemistry). In other embodiments, M-M bonds may be selectively removed using wet development processes (e.g., using high-temperature ethanol and water to provide soluble M(OH)n groups). In yet another embodiment, the exposed region is removed using wet development (e.g., using a positive-tone developer). In some embodiments, the unexposed region is removed using dry development.

[0227] Dry developing processes may include the use of halides, such as HCl-based or HBr-based processes. While this disclosure is not limited to any particular theory or mechanism of operation, approaches may involve using vapor or plasma to form volatile products with cleaning agents (e.g., HCl, HBr, and BCl). ３ This is understood to utilize the chemical reactivity of the dry-deposited photoresist film with (). The dry-deposited photoresist film can be removed at etching rates of up to 1 nm / second. Rapid removal of the dry-deposited photoresist film by these chemical reactions is applicable to chamber cleaning, back cleaning, bevel cleaning, and PR development. The film can be removed by vapor at various temperatures (e.g., HCl or HBr at temperatures above -10°C, or BCl at temperatures above 80°C). ３ This can be removed using ), but plasma may be used to further accelerate or enhance the reactivity.

[0228] Next, the resist underlayer film is etched using the formed resist pattern as a mask. The etching may be dry etching or wet etching, but dry etching is preferred. If the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed; if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. After that, the semiconductor substrate is processed by a known method (such as dry etching) to manufacture a semiconductor device.

[0229] The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[0230] The weight-average molecular weight (Mw) of the polymers shown in the example below was measured by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC instrument manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows: Column temperature: 40°C Flow rate: 0.35 ml / min Eluent: Tetrahydrofuran (THF) Standard sample: Polystyrene (Tosoh Corporation)

[0231] 〇Polymer Synthesis The polymer used in the composition for forming the resist underlayer film was synthesized using the compound group M, catalyst group C, and solvent group S shown below. Note that B2 was a commercially available product (manufactured by Nippon Soda Co., Ltd., trade name VP-8000).

[0232] ○Compound group M (Boc represents the t-butoxycarbonyl group.)

[0233] ○Catalyst Group C Dimethyl 2,2'-azobisisobutyrate: C1 Tetrabutylphosphonium bromide: C2 2,2'-azobisisobutyronitrile: C3

[0234] ○ Solvent Group S Propylene glycol monomethyl ether (=PGME): S1 N,N-dimethylformamide (=DMF): S2

[0235] [Synthesis Examples 1 to 23, Comparative Synthesis Examples 1 to 2] Compounds shown in Tables 1-1 to 1-3 were placed in a flask, nitrogen purging was performed, and the reaction was carried out at the specified temperature and time shown in Tables 1-1 to 1-3. After the reaction was complete, the polymer solution was cooled, and the polymer was recovered in solid form by reprecipitation treatment as necessary. After drying the recovered polymer, it was dissolved in PGME or PGMEA to make a solution which was used for evaluation. In Comparative Synthesis Examples 1 and 2, since there were no ionic moieties, polymers that underwent ion exchange using cation exchange resin and anion exchange resin were used for evaluation.

[0236]

[0237]

[0238]

[0239] The structures and weight-average molecular weights (Mw) of polymers A1-A23 and B1-B3 are shown below. The numerical values ​​in the structures represent molar ratios (mol%).

[0240] To prepare the resist underlayer film formation compositions, 100 parts by mass of polymers (A1) to (A23) and (B1) to (B3) were mixed with additives (CL1 to CL2, Ad1, PAG1 below) and solvents (PGMEA, PGME) in the mass ratios (parts by mass) shown in Tables 2-1 to 2-3. The mixture was then filtered through a 0.1 μm polytetrafluoroethylene microfilter to prepare the resist underlayer film formation compositions (M1 to M23, N1 to N4).

[0241]

[0242]

[0243]

[0244] ○ Dissolution Test in Resist Solvent The resist underlayer film formation compositions (M1-M23, N1-N4) were each coated onto a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 220°C for 60 seconds to obtain a film with a thickness of 5 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 70 / 30 (mass ratio). A change in film thickness of 5 Å or less was considered "good," and a change greater than 5 Å was considered "poor." The results are shown in Tables 3-1 and 3-2.

[0245]

[0246]

[0247] 〇Lithography Evaluation [Resist Pattern Preparation - 1] Resist underlayer formation compositions (M1-M20, N1-N2) were applied to a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 220°C for 60 seconds to obtain a resist underlayer with a thickness of 5 nm. An EUV positive resist solution was spin-coated onto this and heated at 130°C for 1 minute to form an EUV resist layer. Subsequently, exposure was performed using an ASML EUV exposure apparatus (NXE3400) under the conditions of NA = 0.33 and σ = 0.82 / 0.60 (outer / inner). During exposure, exposure was performed through a mask set so that the line width and the width between lines (space width) of the EUV resist would each be 15 nm after development, i.e., a resist pattern with a line and space (L / S) of 15 nm would be formed. After exposure, post-exposure heating (PEB, 90°C for 1 minute) was performed, and the material was cooled to room temperature (25°C) on a cooling plate. A 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name: NMD-3) was used as the photoresist developer, and paddle development was performed for 30 seconds to form a resist pattern. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG7300) was used to measure the length of the resist pattern.

[0248] [Pattern Collapse Evaluation] The obtained photoresist patterns were evaluated for the feasibility of line-and-space (L / S) formation. A "○" was used if the resist pattern was not collapsed, and a "×" was used if the resist pattern was collapsed. The results are shown in Table 4.

[0249]

[0250] As shown in Table 4, in Comparative Example 1, pattern collapse occurred and the formation of the LS pattern was not confirmed, whereas in Examples 1 to 20, the formation of the LS pattern was confirmed.

[0251] [Roughness Evaluation] For the obtained photoresist patterns, the EUV irradiation dose that formed a 15 nm L / S pattern was set as the optimal irradiation energy, and the roughness at that time was evaluated as LWR (line width roughness), LER (line edge roughness), and SWR (space width roughness). A MetroLER manufactured by Fractilia was used for image analysis. For each roughness, a "○" was used if the roughness was smaller than that of Comparative Example 2, and a "×" was used if it was larger. The results are shown in Table 5.

[0252]

[0253] Table 5 shows that roughness was improved in Examples 1 to 20 compared to Comparative Example 2.

[0254] [Resist Pattern Preparation - 2] Resist underlayer formation compositions (M21-M23, N3-N4) were each coated onto a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 220°C for 60 seconds to obtain a resist underlayer with a thickness of 5 nm. An EUV positive resist solution was spin-coated onto this, and heated at 130°C for 1 minute to form an EUV resist layer. Subsequently, exposure was performed using an ASML EUV lithography apparatus (NXE3400) under the conditions of NA = 0.33 and σ = 0.90 / 0.54 (outer / inner). During exposure, exposure was performed through a mask set to form a resist pattern with a hole size of 22 nm in the EUV resist after development as described below. After exposure, post-exposure heating (PEB, 100°C for 1 minute) was performed, followed by cooling to room temperature (25°C) on a cooling plate. A 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name: NMD-3) was used as the photoresist developer, and paddle development was performed for 30 seconds to form a resist pattern. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG6300) was used to measure the length of the resist pattern.

[0255] [LCDU (Hole Diameter Dimensional Variation) Evaluation] For the obtained photoresist patterns, the EUV irradiation dose that formed a 22 nm hole size pattern was set as the optimal irradiation energy, and the LCDU (Local Critical Dimension Uniformity) at that time was measured. For each sample, if the LCDU was smaller than that of Comparative Example 3 and Comparative Example 4, it was marked with "○", and if it was larger, it was marked with "×". The results are shown in Table 6.

[0256]

Claims

A composition for forming a resist underlayer film, comprising a polymer having a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3), and a solvent. (In formula (1), R ａ１ L represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. １ represents a single bond or a divalent group, and PAG represents a residue of a photoacid generator. In formula (2), R ａ２ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and X １ represents -O- or -NR ２ - (R ２ represents a hydrogen atom or a monovalent organic group.), R １ represents a hydrogen atom or a monovalent organic group. When X １ is -NR ２ -, R １ and R ２ may together form a cyclic structure. In formula (3), R ａ３ (where represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms that may be substituted with a halogen atom, and Ar represents a monovalent aromatic group that may have substituents.) 　 The resist underlayer film forming composition according to claim 1, wherein PAG in formula (1) is represented by the following formula (PAG-1) or the following formula (PAG-2). (In formula (PAG-1), Y １ａ － This represents a monovalent group having a monovalent anionic structure, Y １ｃ ＋ This represents a monovalent aromatic onium cation. In formula (PAG-2), Y ２ｃ ＋ This represents a monovalent group having a monovalent aromatic onium cation structure, Y ２ａ － (This represents a monovalent anion.) In the above formula (PAG-1), Y １ａ － However, R １０１ SO ３ － or R １０１ CO ２ － (R １０１ This represents a divalent organic group with 1 to 40 carbon atoms. In the above formula (PAG-2), Y ２ａ － However, R １０２ SO ３ － or R １０２ CO ２ － (R １０２ This represents a monovalent organic group with 1 to 40 carbon atoms. The resist underlayer film formation composition according to claim 2. 　 In the above formula (PAG-1), the Y １ｃ ＋ However, it represents a monovalent aromatic sulfonium cation or a monovalent aromatic iodonium cation. In the above formula (PAG-2), the Y ２ｃ ＋ However, it represents a monovalent group having a monovalent aromatic sulfonium cation structure, or a monovalent group having a monovalent aromatic iodonium cation structure. The resist underlayer film forming composition according to claim 3. 　 The resist underlayer film forming composition according to claim 1, wherein the repeating unit represented by formula (1) is the repeating unit represented by the following formula (1-1). (In formula (1-1), R ａ１ Ar represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms that may be substituted with a halogen atom. １ represents a divalent aromatic group which may have substituents, and Y １ｃ ＋ (This represents a monovalent aromatic onium cation.) 　 The resist underlayer film forming composition according to claim 1, wherein the repeating unit represented by formula (1) is the repeating unit represented by the following formula (1-1-1). (In formula (1-1-1), R ａ１ Y represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. １ｃ ＋ (This represents a monovalent aromatic onium cation.) 　 The resist underlayer film forming composition according to claim 1, wherein the polymer has repeating units represented by formula (1) and repeating units represented by formula (2). 　 The resist underlayer film forming composition according to claim 1, wherein the Ar in formula (3) does not contain at least one of a phenolic hydroxyl group and a group that gives a phenolic hydroxyl group by the action of an acid. 　 The resist underlayer film forming composition according to claim 1, wherein the molar ratio of the repeating units represented by formula (1) to the total repeating units of the polymer is 0.1 mol% to 60 mol%. 　 The resist underlayer film forming composition according to claim 1, wherein the solvent comprises at least one selected from the group consisting of a carboxylic acid having a hydroxyl group, a linear or cyclic alkyl ketone, a cyclic lactone, an alkylene glycol monoalkyl ether, a monocarboxylic acid ester of an alkylene glycol monoalkyl ether, and an alkoxycarboxylic acid ester of an alkylene glycol monoalkyl ether. 　 The resist underlayer film forming composition according to claim 1, further comprising a crosslinking agent. 　 The resist underlayer film forming composition according to claim 11, wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents. 　 The resist underlayer film forming composition according to claim 11, wherein the content of the crosslinking agent is 1% by mass to 60% by mass relative to the polymer. 　 The resist underlayer film forming composition according to claim 1, further comprising a curing catalyst. 　 The resist underlayer film forming composition according to claim 1, further comprising at least one of a photoacid generator and a photodegradable quencher. 　 The resist underlayer film forming composition according to claim 1, further comprising a surfactant. 　 A resist underlayer film forming composition according to claim 1, used in EB or EUV lithography. 　 The resist underlayer film forming composition according to claim 1, used for forming an underlayer film of a metal-containing resist. 　 A resist underlayer film, which is a cured product of a resist underlayer film forming composition according to any one of claims 1 to 18. Semiconductor substrate and The resist underlayer film according to claim 19, A laminate comprising the following features. 　 A step of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of claims 1 to 18, The steps include forming a resist film on the aforementioned resist underlayer film, A method for manufacturing semiconductor devices, including 　 A step of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of claims 1 to 18, The steps include forming a resist film on the aforementioned resist underlayer film, The steps include irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern, A step of etching the resist underlayer film using the resist pattern as a mask, A pattern formation method, including the following.

Images