Composition for forming resist underlayer film

Abstract

Provided is, inter alia, a composition for forming a resist underlayer film, which is resistant to solvents and has excellent sensitivity in resist patterning.　This composition for forming a resist underlayer film contains a polymer (A) and a solvent (B), the polymer (A) having a sulfonic acid group.

Description

Composition for forming 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 producing a semiconductor element, and a method for forming a pattern.

[0002] In the manufacture of semiconductor devices, microfabrication by lithography using a resist composition has traditionally been performed. This microfabrication process involves forming a thin film of a photoresist composition on a semiconductor substrate, such as a silicon wafer, irradiating the substrate with actinic rays such as ultraviolet light through a mask pattern bearing a device pattern, developing the thin film, and 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, the integration density of semiconductor devices has increased, 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 use of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. As a result, poor resist pattern formation due to influences from the semiconductor substrate, etc., has become a major problem. To address this issue, methods of providing a resist underlayer film between the resist and the semiconductor substrate have been widely investigated.

[0003] A resist underlayer film-forming composition has been proposed, which comprises a reaction product of a compound (A) represented by formula (1) (in formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocycle) dissolved in a solvent, a compound (B) having two functional groups reactive with an epoxy group, and a compound (C) having one functional group reactive with an epoxy group (see Patent Document 1).

[0004] International Publication No. 2022 / 075339

[0005] Properties required for a resist underlayer film include, for example, insolubility in a resist solvent to prevent intermixing with a resist film formed on top (resistance to the solvent), and the ability to form a good resist pattern by improving the reduction in the exposure dose required for pattern formation of the resist pattern (excellent sensitivity of the 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 that is resistant to solvents and produces a good sensitivity of the resist pattern, as well as methods for producing a resist underlayer film, a laminate, and a semiconductor device, and a pattern formation method that use the composition for forming a resist underlayer film.

[0006] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have 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 (A) and a solvent (B), wherein the polymer (A) is a polymer having a sulfonic acid group. [2] The composition for forming a resist underlayer film according to [1], wherein the polymer (A) has a structure represented by the following formula (X): (In formula (X), A represents a hydrogen atom, a methyl group, or an ethyl group. Ta represents the following formula (X1). * represents a bond.) (In formula (X1), Ra represents an aromatic hydrocarbon group which may have a substituent, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms. The substituent is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. * represents a bond. n represents 0 or 1.) [3] The composition for forming a resist underlayer film according to [1], wherein the polymer (A) has a structure represented by the following formula (X2): (In formula (X2), Ra represents an aromatic hydrocarbon group which may have a substituent, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms. The substituent is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. * represents a bond. n represents 0 or 1.) [4] The composition for forming a resist underlayer film according to [2], wherein the group represented by formula (X1) is any group selected from groups represented by the following formulas (X1-1) to (X1-5): (In formulas (X1-1) to (X1-5), Rx is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. nx represents an integer of 0 to 4. * represents a bond.) [5] The composition for forming a resist underlayer film according to [1], wherein the polymer (A) is a polymer (Y) having a repeating unit represented by the following formula (Y): In formula (Y), A represents a hydrogen atom, a methyl group, or an ethyl group. Qa and Qb represent the following formula (Y5) or the following formula (Y6), respectively. １ , and T ２ and each represent a hydrogen atom or the following formula (X1): １ and T ２ has a repeating unit represented by the following formula (X1): (In formula (Y5) and formula (Y6), Q １ represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, an anthrylene group, or the following formula (M1), and the alkylene group, the phenylene group, the naphthylene group, and the anthrylene group may each be substituted with an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxy group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxy group, or a group consisting of a combination thereof. １ and n ２ Each of Z represents 0 or 1. １ and Z２ represents a single bond or a group represented by the following formula (Y6-1): １ represents the following formula (Y2), (Y3), (Y4), or (Y0). * represents a bond. (In formula (M1), Y １０１ represents an alkylene group having 1 to 10 carbon atoms, at least one hydrogen atom of which may be substituted with a fluorine atom; R １０１ , and R １０２ represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and n １０ and n １１ Each represents an integer of 0 to 4. * represents a bond. (In formula (Y6-1), m represents an integer of 1 to 4. n represents an integer of 0 to 4. p1 and p2 each independently represent 0 or 1. *3 represents a bond bonding to the nitrogen atom in formula (Y6). *4 represents a bond.) (In formula (Y2), formula (Y3), formula (Y4) and formula (Y0), R １ and R ２ each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the alkynyl group having 2 to 6 carbon atoms, the benzyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, a carboxy group, and an alkylthio group having 1 to 6 carbon atoms. １ and R ２ may be bonded to each other to form a ring having 3 to 6 carbon atoms. ３represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the alkynyl group having 2 to 6 carbon atoms, the benzyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. * represents a bond. *1 represents a bond bonding to a carbon atom. *2 represents a bond bonding to a nitrogen atom. (In formula (X1), Ra represents an aromatic hydrocarbon group which may have a substituent, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms. The substituent is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. * represents a bond. n represents 0 or 1.) [6] The composition for forming a resist underlayer film according to [5], wherein formula (X1) is the following formula (X2): (In formula (X2), Ra represents an aromatic hydrocarbon group which may have a substituent, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms. The substituent is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. * represents a bond. n represents 0 or 1.) [7] The composition for forming a resist underlayer film according to any one of [1] to [6], further comprising a crosslinking agent (C). [8] The composition for forming a resist underlayer film according to [7], wherein the crosslinking agent (C) is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents. [9] A resist underlayer film which is a cured product of the composition for forming a resist underlayer film according to any one of [1] to [8].

[10] A laminate comprising: a semiconductor substrate; and the resist underlayer film according to [9].

[11] A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [8], and forming a resist film on the resist underlayer film.

[12] A method for forming a pattern, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [8], forming a resist film on the resist underlayer film, irradiating the resist film with light or an electron beam and 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 composition for forming a resist underlayer film that is resistant to solvents and provides good sensitivity of a resist pattern, as well as methods for producing a resist underlayer film, a laminate, and a semiconductor element, and a pattern forming method, all of which use the composition for forming a resist underlayer film.

[0009] (Composition for forming a resist underlayer film) The composition for forming a resist underlayer film of the present invention contains a polymer (A) and a solvent (B). The polymer (A) is a polymer having a sulfonic acid group. The composition for forming a resist underlayer film of the present invention may contain a crosslinking agent (C). The composition for forming a resist underlayer film of the present invention may or may not contain an acid catalyst (D) which is a crosslinker catalyst. In the composition for forming a resist underlayer film containing the polymer (A) and the solvent (B), by using a polymer having a sulfonic acid group as the polymer (A), the resist underlayer film formed from the composition for forming a resist underlayer film exhibits good resistance to the solvent, and a resist pattern can be formed on the resist underlayer film with a low exposure dose (i.e., a resist pattern with good sensitivity can be formed).

[0010] <Polymer (A)> The polymer (A) is not particularly limited as long as it is a polymer having a sulfonic acid group, but a preferred embodiment of the polymer (A) is, for example, a polymer that is a reaction product of a hydroxyl group in the polymer reacting with a sulfonic acid anhydride. Note that the hydroxyl group reacted with the sulfonic acid anhydride does not include the hydroxyl group of a carboxylic acid. The polymer (A) is an organic polymer.

[0011] Preferred embodiments of the polymer (A) include, for example, the polymers of the following first and second embodiments. The polymer of the first embodiment is a polymer having a structure represented by the following formula (X). The polymer of the second embodiment is a polymer having a structure represented by the following formula (X2).

[0012] <<First Embodiment>> A preferred embodiment of the polymer (A) is, for example, a polymer having a structure represented by the following formula (X).

[0013] (In formula (X), A represents a hydrogen atom, a methyl group, or an ethyl group. Ta represents the following formula (X1). * represents a bond.)

[0014] (In formula (X1), Ra represents an aromatic hydrocarbon group which may have a substituent, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms. The substituent is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. * represents a bond. n represents 0 or 1.)

[0015] The aromatic hydrocarbon group for Ra may be a monocyclic aromatic hydrocarbon group or a condensed ring aromatic hydrocarbon group.

[0016] Examples of (X1) include monovalent groups represented by the following formulae (X1-1) to (X1-5).

[0017]

[0018] (In formulas (X1-1) to (X1-5), Rx represents a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. nx represents an integer of 0 to 4. * represents a bond.)

[0019] <<Second Embodiment>> A preferred embodiment of the polymer (A) is, for example, a polymer having a structure represented by the following formula (X2).

[0020] (In formula (X2), Ra represents an aromatic hydrocarbon group, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms, which may have a substituent. The substituent is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. * represents a bond.)

[0021] Ra in formula (X2) has the same meaning as Ra in formula (X1).

[0022] Examples of (X2) include the monovalent groups represented by (X1-1) above.

[0023] A preferred embodiment of the polymer (A) is, for example, a polymer (Y) having a repeating unit represented by the following formula (Y).

[0024] In formula (Y), A represents a hydrogen atom, a methyl group, or an ethyl group. Qa and Qb represent the following formula (Y5) or the following formula (Y6), respectively. １ , and T ２ and each represent a hydrogen atom or the above formula (X1), provided that the polymer (Y) is １ and T ２ has a repeating unit represented by the above formula (X1).

[0025] (In formula (Y5) and formula (Y6), Q １ represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, an anthrylene group, or the following formula (M1), and the alkylene group, the phenylene group, the naphthylene group, and the anthrylene group may each be substituted with an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxy group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxy group, or a group consisting of a combination thereof. １ and n ２ Each of Z represents 0 or 1. １ and Z ２ represents a single bond or a group represented by the following formula (Y6-1): １ represents the following formula (Y2), (Y3), (Y4), or (Y0). * represents a bond.

[0026] (In formula (M1), Y １０１ represents an alkylene group having 1 to 10 carbon atoms, at least one hydrogen atom of which may be substituted with a fluorine atom; R １０１ , and R １０２ represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and n １０ and n １１ Each represents an integer of 0 to 4. * represents a bond.

[0027] (In formula (Y6-1), m represents an integer of 1 to 4. n represents an integer of 0 to 4. p1 and p2 each independently represent 0 or 1. *3 represents a bond bonding to the nitrogen atom in formula (Y6). *4 represents a bond.)

[0028] (In formula (Y2), formula (Y3), formula (Y4) and formula (Y0), R １ and R ２ each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the alkynyl group having 2 to 6 carbon atoms, the benzyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, a carboxy group, and an alkylthio group having 1 to 6 carbon atoms. １ and R ２ may be bonded to each other to form a ring having 3 to 6 carbon atoms. ３ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the alkynyl group having 2 to 6 carbon atoms, the benzyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. * represents a bond. *1 represents a bond bonding to a carbon atom. *2 represents a bond bonding to a nitrogen atom.

[0029] In the repeating unit represented by the formula (Y), the formula (X1) is preferably the formula (X2).

[0030] Examples of the group represented by formula (Y5) include the following groups.

[0031]

[0032] (* represents a bond.)

[0033] Examples of the group represented by formula (Y6) include the following groups.

[0034]

[0035]

[0036]

[0037]

[0038]

[0039] (* represents a bond.)

[0040] Examples of the group represented by the above formula (M1) include the following groups.

[0041] (* represents a bond.)

[0042] Examples of the repeating unit represented by formula (Y) include repeating units represented by the following formulae (Y-1) to (Y-21).

[0043]

[0044]

[0045]

[0046]

[0047] (In formulas (Y-1) to (Y-20), T １ and T ２ is T in formula (Y) １ and T ２ It is synonymous with

[0048] T in polymer (Y) １ , and T２ and are each a hydrogen atom, examples of the polymer (Y′) include the polymers described in WO 2013 / 018802, the contents of which are incorporated herein by reference in their entirety.

[0049] The polymer (Y) according to the present invention is １ , and T ２ can be obtained by reacting a polymer (Y') containing hydrogen atoms with a sulfonic acid anhydride. In other words, the polymer (Y) is a reaction product obtained by reacting a sulfonic acid anhydride with the hydroxyl groups contained in the polymer (Y'). Here, the sulfonic acid anhydride is preferably a cyclic sulfonic acid anhydride, and examples thereof include cyclic sulfonic acid anhydrides represented by the following formulas (t-1) to (t-7):

[0050]

[0051] When polymer (Y') is reacted with cyclic sulfonic acid anhydride, sulfonic acid groups are introduced into hydroxyl groups of polymer (Y'), as shown in the following formula (IL-1), and polymer (Y) according to the present invention can be obtained. １ and T ２ is a hydrogen atom, the above (t-1) is given as an example of a cyclic sulfonic acid anhydride. In this way, the polymer (Y) according to the present invention can be obtained by fixing a sulfonic acid group in a polymer by utilizing the ring-opening reaction of a sulfonic acid anhydride.

[0052]

[0053] Polymer (Y') is produced, for example, by the reaction described below. For example, the case where Qa in polymer (Y') is a group represented by formula (Y6) will be described below as an example. Polymer (Y') is produced, for example, by the reaction of a compound represented by formula (Y7) below with a compound represented by formula (Y8) below. (In formula (Y7), X １represents the formula (Y2), the formula (Y3), the formula (Y4), or the formula (Y0). In formula (8), Qb represents the formula (Y5) or the formula (Y6). A represents a hydrogen atom, a methyl group, or an ethyl group.

[0054] The reaction between the compound represented by formula (Y7) and the compound represented by formula (Y8) is preferably carried out in a solution state in an organic solvent such as benzene, toluene, xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or N-methylpyrrolidone. In this reaction, a quaternary ammonium salt such as benzyltriethylammonium chloride, tetrabutylammonium chloride, or tetraethylammonium bromide can also be used as a catalyst. The reaction temperature and reaction time of this reaction are not limited and may be changed depending on the compound used, its concentration, etc. The reaction time may be selected from the range of 0.1 to 100 hours, and the reaction temperature may be selected from the range of 20°C to 200°C, as appropriate. When a catalyst is used, it can be used in the range of 0.001 to 30% by mass based on the total mass of the compounds used.

[0055] The ratio of the compounds represented by formula (Y7) and formula (Y8) used in the reaction may be any ratio, and the molar ratio of the two compounds [compound represented by formula (Y7) : compound represented by formula (Y8)] is preferably 3:1 to 1:3, and more preferably 3:2 to 2:3.

[0056] The weight average molecular weight of the polymer (A) is not particularly limited, but is preferably from 1,000 to 30,000, more preferably from 2,000 to 20,000, and particularly preferably from 3,000 to 15,000.

[0057] The content of polymer (A) in the composition for forming a resist underlayer film is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 40% by mass to 90% by mass, more preferably 45% by mass to 85% by mass, and particularly preferably 50% by mass to 80% by mass, based on the film-constituting components. In the present invention, the film-constituting components refer to components other than the solvent contained in the composition.

[0058] <Solvent (B)> The solvent (B) is not particularly limited and may be water or an organic solvent. Examples of the organic solvent include alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

[0059] Examples of the alkylene group of the alkylene glycol monoalkyl ether include alkylene groups having 2 to 4 carbon atoms. Examples of the alkyl group of the alkylene glycol monoalkyl ether include alkyl groups having 1 to 4 carbon atoms. Examples of the number of carbon atoms of the alkylene glycol monoalkyl ether include 3 to 8. Examples of the alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0060] Examples of the alkylene group of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include alkylene groups having 2 to 4 carbon atoms. Examples of the alkyl group of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include alkyl groups having 1 to 4 carbon atoms. Examples of the monocarboxylic acid of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include saturated monocarboxylic acids having 2 to 4 carbon atoms. Examples of saturated monocarboxylic acids having 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid. Examples of the number of carbon atoms of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include those having 5 to 10 carbon atoms. Examples of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.

[0061] Other organic solvents include, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0062] Among these solvents (B), alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.

[0063] These solvents (B) may be used alone or in combination of two or more.

[0064] The mass proportion of the organic solvent in the solvent (B) is not particularly limited, but is preferably 50 mass % to 100 mass %.

[0065] The content of the solvent (B) in the composition for forming a resist underlayer film is not particularly limited, but is preferably 50% by mass to 99.99% by mass, more preferably 75% by mass to 99.95% by mass, and particularly preferably 90% by mass to 99.9% by mass.

[0066] <Crosslinking Agent (C)> The crosslinking agent (C) is not particularly limited. The crosslinking agent (C) has a structure different from that of the polymer (A).

[0067] The crosslinking agent (C) is preferably an aminoplast crosslinking agent or a phenoplast crosslinking agent. The aminoplast crosslinking agent is an addition condensation product of a compound having an amino group, such as melamine or guanamine, with formaldehyde. The phenoplast crosslinking agent is an addition condensation product of a compound having a phenolic hydroxy group with formaldehyde.

[0068] Examples of the crosslinking agent (C) 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 bonded to, for example, a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0069] R １０１ is preferably 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 bond.

[0070] The crosslinking agent (C) is preferably a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, or a compound having a phenolic hydroxy group, which may be used alone or in combination of two or more.

[0071] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been acyloxymethylated, or a mixture thereof.

[0072] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof; and the like.

[0073] Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof.

[0074] The glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E). (In formula (1E), four R １ each independently represents a methyl group or an ethyl group, R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0075] Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0076] 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).

[0077] (In formula (2E), R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; R ４ each independently represents an alkyl group having 1 to 4 carbon atoms.

[0078] (In formula (3d), R １ represents a methyl group or an ethyl group.)

[0079] Examples of glycoluril derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2) below.

[0080]

[0081]

[0082] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds in which one to four methylol groups are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea.

[0083] Examples of the compound having a phenolic hydroxy group include compounds represented by the following formula (G-1) or (G-2).

[0084] (In formula (G-1) and formula (G-2), Q １ represents a single bond or a monovalent organic group. １ and R ４ R represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. ２ and R ５ R represents a hydrogen atom or a methyl group. ３ and R ６ n 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 an integer ≦3, n ２ is 2≦n ２ n is an integer ≦5 ３ is 0≦n ３ an integer ≦3, n ４ is 0≦n ４ an integer ≦3, 3≦(n １ +n２ +n ３ +n ４ ) represents an integer ≦6. ５ is 1≦n ５ an integer ≦3, n ６ is 1≦n ６ an integer ≦4, n ７ is 0≦n ７ an integer ≦3, n ８ is 0≦n ８ an integer ≦3, 2≦(n ５ +n ６ +n ７ +n ８ ) represents an integer of ≦5. m1 represents an integer of 2 to 10.

[0085] Examples of compounds having a phenolic hydroxy group include compounds represented by the following formula (G-3) or formula (G-4): The compound represented by formula (G-1) or formula (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms.

[0086] (In formula (G-3) and formula (G-4), Q ２ represents a single bond or a divalent organic group. ８ , R ９ , R １１ and R １２ R represents a hydrogen atom or a methyl group. ７ and R １０ n 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 an integer ≦3, n １０ is 2≦n １０ n is an integer ≦5 １１ is 0≦n １１ an integer ≦3, n １２ is 0≦n １２ an integer ≦3, 3≦(n ９ +n １０ +n １１ +n １２ ) represents an integer ≦6. １３ is 1≦n １３ an integer ≦3, n１４ is 1≦n １４ an integer ≦4, n １５ is 0≦n １５ an integer ≦3, n １６ is 0≦n １６ an integer ≦3, 2≦(n １３ +n １４ +n １５ +n １６ ) represents an integer of ≦5. m2 represents an integer of 2 to 10. ２ In the above, the m2-valent organic group includes, for example, an m2-valent organic group having 1 to 4 carbon atoms.

[0087] Examples of the compound represented by formula (G-1) or formula (G-2) include the following compounds:

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] Examples of the compound represented by formula (G-3) or formula (G-4) include the following compounds:

[0094]

[0095] The above compound is available as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. An example of the product is TMOM-BP, a product name of Asahi Organic Chemicals Co., Ltd.

[0096] Among these, glycoluril compounds are preferred, specifically tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds in which one to four methylol groups have been methoxymethylated or mixtures thereof, and tetramethylol glycoluril compounds in which one to four methylol groups have been acyloxymethylated or mixtures thereof, with tetramethoxymethyl glycoluril being more preferred.

[0097] The molecular weight of the crosslinking agent (C) is not particularly limited, but is preferably 1,000 or less.

[0098] The content of the crosslinking agent (C) in the composition for forming a resist underlayer film is not particularly limited, but is, for example, 1% by mass to 70% by mass, and preferably 5% by mass to 60% by mass, relative to the polymer (A).

[0099] <Acid catalyst (D)> The composition for forming a resist underlayer film of the present invention may or may not contain an acid catalyst (D) which is a crosslinker catalyst. The acid catalyst (D) contained as an optional component in the composition for forming a resist underlayer film may be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0100] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0101] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal 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 nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0102] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0103] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0104] The acid catalyst (D) may be used alone or in combination of two or more.

[0105] When the acid catalyst (D) is used, the content of the acid catalyst (D) relative to the crosslinking agent (C) is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass.

[0106] <Other Components> A surfactant may be further added to the composition for forming a resist underlayer film in order to prevent pinholes, striations, and the like from occurring and to further improve the coatability against surface irregularities.

[0107] Examples of surfactants include linear or branched alkylbenzenesulfonic acids (e.g., dodecylbenzenesulfonic acid, etc.), 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. nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as Eftop EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, and R-30 (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by AGC Inc.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants to be added is usually 2.0 mass % or less, and preferably 1.0 mass % or less, based on the total solid content of the composition for forming a resist underlayer film. These surfactants may be added alone or in combination of two or more.

[0108] The composition for forming a resist underlayer film may contain a polymerization inhibitor (radical trapping agent) as necessary. Examples of the polymerization inhibitor include 2,6-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-tert-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and 4-methoxy-1-naphthol. The content of the polymerization inhibitor in the composition for forming a resist underlayer film is not particularly limited, but is preferably 1 mass % or less based on the solid content.

[0109] The solid content of the composition for forming a resist underlayer film of the present invention, that is, the content of components excluding the solvent, is, for example, 0.01% by mass to 10% by mass.

[0110] The composition for forming a resist underlayer film is preferably used for EUV lithography.The composition for forming a resist underlayer film is preferably used for forming an underlayer film of a metal-containing resist.

[0111] (Resist Underlayer Film) The resist underlayer of the present invention is a cured product of the composition for forming a resist underlayer film described above. The resist underlayer film can be produced, for example, by applying the composition for forming a resist underlayer film described above onto a semiconductor substrate and baking it.

[0112] Examples of semiconductor substrates onto which the resist underlayer film-forming composition can be applied include silicon wafers, germanium wafers, and wafers of compound semiconductors such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0113] When a semiconductor substrate having an inorganic film formed on its surface is used, the inorganic film can be 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 a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium nitride oxide film, a tungsten film, a gallium nitride film, and a gallium arsenide film.

[0114] The resist underlayer film-forming composition of the present invention is applied to such a semiconductor substrate by a suitable application method such as a spinner or coater. The composition is then baked using a heating means such as a hot plate to form a resist underlayer film. The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 to 60 minutes. A baking temperature of 120°C to 350°C and a baking time of 0.5 to 30 minutes are preferred, and a baking temperature of 150°C to 300°C and a baking time of 0.8 to 10 minutes are more preferred.

[0115] The thickness of the resist underlayer film may 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 (5 nm) to 0.05 μm (5 0 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), 0.005 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).

[0116] The method for measuring the film thickness of the resist underlayer film in this specification is as follows: Name of measuring device: Ellipso film thickness measuring device RE-3100 (SCREEN Corporation) SWE (single wavelength ellipsometer) mode Arithmetic mean of 8 points (for example, measuring 8 points at 1 cm intervals in the X direction of the wafer)

[0117] (Laminate) The laminate of the present invention includes a semiconductor substrate and the resist underlayer film of the present invention. Examples of the semiconductor substrate include the semiconductor substrates described above. The resist underlayer film is disposed on the semiconductor substrate, for example.

[0118] (Method for manufacturing a semiconductor element, method for forming a pattern) The method for manufacturing a semiconductor element of the present invention includes at least the following steps: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, and forming a resist film on the resist underlayer film.

[0119] The pattern forming method of the present invention includes at least the following steps: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, forming a resist film on the resist underlayer film, irradiating the resist film with light or an electron beam and then developing the resist film to obtain a resist pattern, and etching the resist underlayer film using the resist pattern as a mask.

[0120] Typically, a resist layer is formed on the resist underlayer film. The film thickness of the resist layer is, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, or 1,000 nm or less. The lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, or 10 nm.

[0121] The resist film formed on the resist underlayer film by a known method (e.g., coating and baking a resist composition) is not particularly limited as long as it is responsive to light or electron beam (EB) irradiation. Both negative and positive photoresists can be used. In this specification, resists responsive to EB are also referred to as photoresists. Examples of photoresists include positive photoresists composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; chemically amplified photoresists composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; chemically amplified photoresists composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate, a low-molecular-weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator; and resists containing metal elements. Examples of such photoresists include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley Co., Ltd., PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. Further 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).

[0122] 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 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., radiation-sensitive resin compositions, so-called resist compositions such as high-resolution patterning compositions based on organometallic solutions, and metal-containing resist compositions can be used, but are not limited to these.

[0123] Examples of the resist composition include the following compositions.

[0124] An actinic ray-sensitive or radiation-sensitive resin composition comprising: Resin A having a repeating unit having an acid-decomposable group in which a polar group is protected with a protecting group that is cleaved by the action of an acid; and a compound represented by the following general formula (121):

[0125] In the general formula (121), m represents an integer of 1 to 6. １ and R ２ each independently represents a fluorine atom or a perfluoroalkyl group. １ is -O-, -S-, -COO-, -SO ２ - or -SO ３ - represents. ２ represents an alkylene group which may have a substituent or a single bond. １ represents a cyclic organic group which may have a substituent. ＋ represents a cation.

[0126] 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 Periods 3 to 7 of Groups 3 to 15 of the periodic table.

[0127] 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) containing an acid-dissociable group; and an acid generator.

[0128] In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. １ is a hydroxy group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 11. When n is 2 or more, multiple R １ are the same or different. ２ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. ３ is a monovalent group having 1 to 20 carbon atoms containing the above acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R ４is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0129] A resist composition comprising: a resin (A1) containing a structural unit having a cyclic carbonate structure, a structural unit represented by the following formula, and a structural unit having an acid labile group; and an acid generator.

[0130] [In the formula, R ２ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom; X １ represents a single bond, —CO—O—*, or —CO—NR ４ -*, * represents a bond to -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 a hydroxy group and a carboxy group.]

[0131] Examples of the resist film include the following.

[0132] A resist film comprising a base resin comprising a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to a polymer main chain upon exposure:

[0133] (In formula (a1) and formula (a2), R Ａ are each independently a hydrogen atom or a methyl group. １ and R ２ are each independently a tertiary alkyl group having 4 to 6 carbon atoms. ３ are each independently a fluorine atom or a methyl group, and m is an integer of 0 to 4. １ X is a single bond, a phenylene group, or a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. ２ is a single bond, an ester bond, or an amide bond.

[0134] Examples of resist materials include the following:

[0135] A resist material comprising a polymer having a repeating unit represented by the following formula (b1) or (b2):

[0136] (In formula (b1) and formula (b2), R Ａ is a hydrogen atom or a methyl group. １ is a single bond or an ester group. ２ 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 some 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 contained in X is substituted with 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 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. １ and Rf ２ may combine to form a carbonyl group. １ ~R ５ are each 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, in which some or all of the hydrogen atoms may be substituted with a hydroxy group, a carboxy 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 in which 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 sulfonate ester group. １ and R ２may be bonded to form a ring together with the sulfur atom to which they are attached.

[0137] A resist material comprising a base resin containing a polymer containing a repeating unit represented by the following formula (a):

[0138] (In formula (a), R Ａ is a hydrogen atom or a methyl group. １ is a hydrogen atom or an acid labile group. ２ is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. １ X is a single bond, a phenylene group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which may contain an ester group or a lactone ring. ２ is -O-, -O-CH ２ - or -NH-. m is an integer of 1 to 4. u is an integer of 0 to 3. However, m+u is an integer of 1 to 4.

[0139] A resist composition that generates an 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) comprises a fluororesin component (F1) that has a structural unit (f1) that includes a base dissociable group, and a structural unit (f2) that includes a group represented by the following general formula (f2-r-1):

[0140] [In formula (f2-r-1), Rf ２１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkyl group, or a cyano group. n" is an integer of 0 to 2. * is a bond.

[0141] The structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0142] [In formulas (f1-1) and (f1-2), each 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 represents a divalent aromatic cyclic group which may have a substituent. ０１ is a single bond or a divalent linking group. ２ are each independently an organic group having a fluorine atom.

[0143] The resist composition may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist. Examples of metal oxide resist materials include coating compositions containing metal oxo-hydroxo networks having organic ligands via metal-carbon bonds and / or metal carboxylate bonds, as described in JP-A-2019-113855. One example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described, for example, in the patent document described in paragraph

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

[0144] A coating comprising a metal oxo-hydroxo network having organic ligands with metal carbon and / or metal carboxylate bonds.

[0145] Inorganic oxo / hydroxo-based compositions.

[0146] a coating solution comprising an organic solvent; a first organometallic composition having the formula R ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ (where 0<z≦2 and 0<(z+x)≦4), formula R′ｎ SnX ４－ｎ wherein n=1 or 2, or mixtures thereof, where R and R′ are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn, or a combination thereof; and a hydrolyzable metal compound having the formula MX′ ｖ wherein M is a metal selected from groups 2 to 16 of the periodic table of the elements, v is a number from 2 to 6, and X' is a ligand having a hydrolyzable M-X bond or a combination thereof.

[0147] an organic solvent and a solution of the formula RSnO （３／２－ｘ／２） (OH) ｘ and a first organometallic compound of the formula: wherein 0<x<3, wherein the solution contains from about 0.0025M to about 1.5M tin, and R is an alkyl or cycloalkyl group having from 3 to 31 carbon atoms, the alkyl or cycloalkyl group being bonded to the tin at a secondary or tertiary carbon atom.

[0148] An aqueous inorganic patterning precursor solution comprising a mixture of water, metal suboxide cations, polyatomic inorganic anions, and radiation-sensitive ligands comprising peroxide groups.

[0149] Other examples of metal-containing resists include those described in JP 2011-253185 A, WO 2015 / 026482, WO 2016 / 065120, WO 2017 / 066319, WO 2017 / 156388, WO 2018 / 031896, JP 2020-122959 A, JP 2020-122960 A, WO 2019 / 099981, WO 2019 / 199467, WO 2019 / 195522, WO 2019 / 195522, WO 2020 / 210660, WO 2021 / 011367, and WO 2021 / 016229. The contents of these are incorporated herein in their entirety to the same extent as if set forth in full.

[0150] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and examples include a method in which a coating-type resist material (a composition for forming a metal-containing resist film) that is a metal-containing resist is coated and baked.

[0151] The metal-containing resist film may also be formed by vapor deposition. Examples of methods for forming a metal-containing resist film by vapor deposition include the method described in JP 2017-116923 A. The contents of JP 2017-116923 A are incorporated herein by reference to the same extent as if fully set forth herein. In JP 2017-116923 A, the metal-containing resist film of the present invention is referred to as a metal oxide-containing film.

[0152] Irradiation with light or electron beams is carried out, for example, through a mask (reticle) for forming a predetermined pattern. For example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) can be used. The composition for forming a resist underlayer film of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation, more preferably for EUV (extreme ultraviolet) exposure. The irradiation energy of the electron beam and the exposure dose of light are not particularly limited.

[0153] After irradiation with light or electron beams and before development, baking (PEB: Post Exposure Bake) may be performed. The baking 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 baking 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.

[0154] For example, an alkaline developer or an organic solvent is used for development. The development temperature is, for example, 5°C to 50°C. The development time is, for example, 10 seconds to 300 seconds. Examples of alkaline developers that can be used include aqueous solutions of alkalis such as inorganic alkalis (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia); primary amines (e.g., ethylamine and n-propylamine); secondary amines (e.g., diethylamine and di-n-butylamine); tertiary amines (e.g., triethylamine and methyldiethylamine); alcohol amines (e.g., dimethylethanolamine and triethanolamine); quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline); and cyclic amines (e.g., pyrrole and piperidine). Furthermore, the aqueous solutions of the alkalis may be used by adding an appropriate amount of alcohols (e.g., isopropyl alcohol) or a nonionic surfactant. Among these, preferred developers are aqueous solutions of quaternary ammonium salts, more preferably aqueous solutions of tetramethylammonium hydroxide and choline. Furthermore, surfactants and the like may also be added to these developers. Alternatively, development may be carried out with an organic solvent such as butyl acetate instead of an alkaline developer, and the portions of the photoresist where the alkaline dissolution rate is not improved may be developed.

[0155] An organic solvent can be used as a developer for the metal-containing resist, and development is carried out with the developer (solvent) after irradiation with light or electron beams. As a result, for example, when a negative metal-containing resist film is used, the metal-containing resist film in the unexposed areas is removed, and a pattern of the metal-containing resist film is formed. Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol 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-methyl ... -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, ethyl lactate, 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,Examples of the developer include propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate. Furthermore, surfactants and the like can also be added to these developers.

[0156] 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. Thereafter, the semiconductor substrate is processed by a known method (e.g., dry etching), thereby manufacturing a semiconductor device.

[0157] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0158] The weight-average molecular weights of the polymers shown in the following synthesis examples are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows: GPC column: Shodex KF803L, Shodex KF802, Shodex KF801 (registered trademark) (Showa Denko K.K.) Column temperature: 40°C Solvent: N,N-dimethylformamide (DMF) Flow rate: 0.6 ml / min Standard sample: polystyrene (manufactured by Tosoh Corporation)

[0159] Synthesis Example 1-1 100 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were dissolved in 682 g of propylene glycol monomethyl ether, and the mixture was allowed to react at 130°C for 24 hours to obtain a solution containing a polymer. GPC analysis of the obtained polymer revealed that it had a weight average molecular weight of 6,800 in terms of standard polystyrene. The obtained polymer has a repeating unit structure represented by the following formula (1a):

[0160]

[0161] Synthesis Example 1-2 The polymer solution obtained in Synthesis Example 1-1 was evaporated to dryness to precipitate a powder, which was then dried under reduced pressure. 2.0 g of the obtained polymer powder and 0.05 g of 2-sulfobenzoic anhydride (Tokyo Chemical Industry Co., Ltd.) were dissolved in 10.25 g of PGMEA (propylene glycol monomethyl ether acetate) and refluxed at 130°C for 24 hours. GPC analysis of the obtained polymer revealed that the weight-average molecular weight, calculated as standard polystyrene, was 10,000. The obtained polymer had a repeating unit structure represented by the following formula (1b):

[0162]

[0163] Synthesis Example 2-1 9.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 12.93 g of bisphenol AF (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.30 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 58.08 g of propylene glycol monomethyl ether, and the mixture was allowed to react at 105°C for 24 hours to obtain a solution containing a polymer. GPC analysis of the obtained polymer revealed that the weight average molecular weight, calculated as standard polystyrene, was 8,500. The obtained polymer was a polymer having the structure of formula (2a) as a repeating unit structure.

[0164]

[0165] Synthesis Example 2-2 The polymer solution obtained in Synthesis Example 2-1 was evaporated to dryness to precipitate a powder, which was then dried under reduced pressure. 2.0 g of the obtained polymer powder and 0.05 g of 2-sulfobenzoic anhydride (Tokyo Chemical Industry Co., Ltd.) were dissolved in 10.25 g of PGMEA and refluxed at 130°C for 24 hours. GPC analysis of the obtained polymer revealed that the weight-average molecular weight, calculated as standard polystyrene, was 8900. The obtained polymer had a repeating unit structure of formula (2b).

[0166]

[0167] Synthesis Example 3-1 10.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 7.44 g of phenobarbital (manufactured by Shikoku Chemical Industry Co., Ltd.), 0.9834 g of 4-hydroxybenzoic acid, and 1.45 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 29.81 g of propylene glycol monomethyl ether, and the mixture was allowed to react at 105°C for 24 hours to obtain a solution containing a polymer. GPC analysis of the obtained polymer revealed that the weight average molecular weight, calculated as standard polystyrene, was 9,000. The obtained polymer had a repeating unit structure of formula (3a).

[0168]

[0169] Synthesis Example 3-2 The polymer solution obtained in Synthesis Example 3-1 was evaporated to dryness to precipitate a powder, which was then dried under reduced pressure. 2.0 g of the obtained polymer powder and 0.2 g of 2-sulfobenzoic anhydride (Tokyo Chemical Industry Co., Ltd.) were dissolved in 10.25 g of PGMEA and refluxed at 130°C for 24 hours. GPC analysis of the obtained polymer revealed that the weight-average molecular weight, calculated as standard polystyrene, was 9,300. The obtained polymer had a repeating unit structure of formula (3b).

[0170]

[0171] Example 1 To 0.580 g of the polymer solution (solid content 13.88% by mass) obtained in Synthesis Example 1-2, 0.40 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.), 34.05 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter having a pore size of 0.05 μm, to obtain a composition for forming a resist underlayer film for lithography.

[0172] Example 2 0.400 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.), 34.05 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added to and dissolved in 0.580 g of the polymer solution (solid content 13.80% by mass) obtained in Synthesis Example 2-2. The mixture was then filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a composition for forming a resist underlayer film for lithography.

[0173] Example 3 0.40 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.), 34.13 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added to and dissolved in 0.498 g of the polymer solution (solid content 16.05% by mass) obtained in Synthesis Example 3-2. The mixture was then filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a composition for forming a resist underlayer film for lithography.

[0174] Comparative Example 1 To 0.580 g of the polymer solution (solid content 4.86% by mass) obtained in Synthesis Example 1-1, 0.362 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.), 0.165 g of a 1% by mass propylene glycol monomethyl ether solution of pyridinium toluenesulfonic acid, 32.98 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a composition for forming a resist underlayer film for lithography.

[0175] Comparative Example 2 To 0.415 g of the polymer solution (solid content 18.88% by mass) obtained in Synthesis Example 2-1, 0.391 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.), 0.178 g of a 1% by mass propylene glycol monomethyl ether solution of pyridinium toluenesulfonic acid, 33.85 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a composition for forming a resist underlayer film for lithography.

[0176] Comparative Example 3 To 0.443 g of the polymer solution (solid content 17.65% by mass) obtained in Synthesis Example 3-1, 0.391 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.), 0.178 g of a 1% by mass propylene glycol monomethyl ether solution of pyridinium toluenesulfonate, 34.05 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a composition for forming a resist underlayer film for lithography.

[0177] Comparative Example 4 To 0.580 g of the polymer solution (solid content 4.86% by mass) obtained in Synthesis Example 1-1, 0.362 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.), 32.98 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter having a pore size of 0.05 μm, yielding a composition for forming a resist underlayer film for lithography.

[0178] Comparative Example 5 To 0.415 g of the polymer solution (solid content 18.88% by mass) obtained in Synthesis Example 2-1, 0.391 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.), 33.85 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter having a pore size of 0.05 μm, to obtain a composition for forming a resist underlayer film for lithography.

[0179] Comparative Example 6 To 0.443 g of the polymer solution (solid content 17.65% by mass) obtained in Synthesis Example 3-1, 0.391 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.), 34.05 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter having a pore size of 0.05 μm, yielding a composition for forming a resist underlayer film for lithography.

[0180] (Elution Test in Photoresist Solvent) Each of the resist underlayer film-forming compositions of Examples 1 to 3 and Comparative Examples 1 to 6 was applied to a silicon wafer, which was a semiconductor substrate, using a spinner. The silicon wafer was placed on a hot plate and baked at 215°C for 1 minute to form a resist underlayer film (film thickness 5 nm). These resist underlayer films were immersed in a solvent used in photoresists, propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 7 / 3 (mass ratio), and solvent resistance was evaluated based on the change in film thickness before and after immersion. Film loss of 2 Å or less was considered pass, and film loss of more than 2 Å was considered fail.

[0181] For the resist underlayer films of Examples 1 to 3 and Comparative Examples 1 to 6, whether or not an acid was immobilized in the polymer contained in the resist underlayer film-forming composition from which the resist underlayer film was formed is shown in Table 1 below as "Whether or Not an Acid Was Immobilized in the Polymer." Furthermore, whether or not an acid catalyst was added to the resist underlayer film-forming composition from which the resist underlayer film was formed is shown in Table 1 below as "Whether or Not an Acid Catalyst Was Added to the Underlayer Film-forming Composition." Furthermore, the solvent resistance test results for the resist underlayer films are shown in Table 1 below as "Solvent Resistance Test Results."

[0182]

[0183] The results in Table 1 show that in Examples 1 to 3, resist underlayer films exhibiting solvent resistance could be formed without adding an acid catalyst.

[0184] (Formation of Positive Resist Pattern Using Electron Beam Lithography Apparatus) The resist underlayer film-forming compositions of Example 1 and Comparative Example 1 were each applied to a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 215°C for 60 seconds to obtain a 5 nm-thick resist underlayer film. A positive EUV resist solution (containing a methacrylic polymer) was spin-coated onto the resist underlayer film and heated at 110°C for 60 seconds to form an EUV resist film. The resist film was exposed under specified conditions using an electron beam lithography apparatus (ELS-G130). After exposure, the resist was baked at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and developed with an alkaline developer (2.38%) to form a line-and-space pattern with a CD size of 20 nm and a pitch of 40 nm. A scanning electron microscope (CG4100, manufactured by Hitachi High-Technologies Corporation) was used to measure the resist pattern. In the formation of the resist pattern, the exposure dose required to form a line pattern with a CD size of 20 nm was defined as sensitivity and compared. The results of the exposure dose required to form a line pattern with a CD size of 20 nm in Example 1 and Comparative Example 1 are shown in Table 2 below.

[0185]

[0186] The results in Table 2 show that Example 1 has a lower exposure dose required for pattern formation and is superior in sensitivity compared to Comparative Example 1. These results demonstrate that a resist underlayer film having pattern-forming ability with good sensitivity can be formed in Example 1. Therefore, according to the present invention, it is possible to provide a composition for forming a resist underlayer film that is resistant to solvents and produces a resist pattern with good sensitivity.

Claims

1. A composition for forming a resist underlayer film, comprising a polymer (A) and a solvent (B), wherein the polymer (A) is a polymer having a sulfonic acid group.

2. The composition for forming a resist underlayer film according to claim 1, wherein the polymer (A) has a structure represented by the following formula (X): (In formula (X), A represents a hydrogen atom, a methyl group, or an ethyl group. Ta represents the following formula (X1). * represents a bond.) (In formula (X1), Ra represents an aromatic hydrocarbon group which may have a substituent, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms. The substituent is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. * represents a bond. n represents 0 or 1.) 3. The composition for forming a resist underlayer film according to claim 1, wherein the polymer (A) has a structure represented by the following formula (X2): (In formula (X2), Ra represents an aromatic hydrocarbon group, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms, which may have a substituent. The substituent is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. * represents a bond.) 4. The composition for forming a resist underlayer film according to claim 2, wherein the group represented by formula (X1) is any group selected from groups represented by the following formulas (X1-1) to (X1-5): (In formulas (X1-1) to (X1-5), Rx represents a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. nx represents an integer of 0 to 4. * represents a bond.) 5. The composition for forming a resist underlayer film according to claim 1, wherein the polymer (A) is a polymer (Y) having a repeating unit represented by the following formula (Y): In formula (Y), A represents a hydrogen atom, a methyl group, or an ethyl group. Qa and Qb represent the following formula (Y5) or the following formula (Y6), respectively. １ , and T ２ and each represent a hydrogen atom or the following formula (X1): １ and T ２ has a repeating unit represented by the following formula (X1): (In formula (Y5) and formula (Y6), Q １ represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, an anthrylene group, or the following formula (M1), and the alkylene group, the phenylene group, the naphthylene group, and the anthrylene group may each be substituted with an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxy group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxy group, or a group consisting of a combination thereof. １ and n ２ Each of Z represents 0 or 1. １ and Z ２ represents a single bond or a group represented by the following formula (Y6-1): １ represents the following formula (Y2), the following formula (Y3), the following formula (Y4), or the following formula (Y0). * represents a bond. (In formula (M1), Y １０１ represents an alkylene group having 1 to 10 carbon atoms, at least one hydrogen atom of which may be substituted with a fluorine atom; R １０１ , and R １０２ represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and n １０ and n １１ Each represents an integer of 0 to 4. * represents a bond. (In formula (Y6-1), m represents an integer of 1 to 4. n represents an integer of 0 to 4. p1 and p2 each independently represent 0 or 1. *3 represents a bond bonding to the nitrogen atom in formula (Y6). *4 represents a bond.) (In formula (Y2), formula (Y3), formula (Y4) and formula (Y0), R １ and R ２ each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the alkynyl group having 2 to 6 carbon atoms, the benzyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, a carboxy group, and an alkylthio group having 1 to 6 carbon atoms. １ and R ２ may be bonded to each other to form a ring having 3 to 6 carbon atoms. ３ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the alkynyl group having 2 to 6 carbon atoms, the benzyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. * represents a bond. *1 represents a bond bonding to a carbon atom. *2 represents a bond bonding to a nitrogen atom. (In formula (X1), Ra represents an aromatic hydrocarbon group which may have a substituent, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms. The substituent is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. * represents a bond. n represents 0 or 1.) 6. The composition for forming a resist underlayer film according to claim 5, wherein the formula (X1) is the following formula (X2): (In formula (X2), Ra represents an aromatic hydrocarbon group which may have a substituent, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms. The substituent is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. * represents a bond. n represents 0 or 1.) 7. The composition for forming a resist underlayer film according to claim 1, further comprising a crosslinking agent (C).

8. The composition for forming a resist underlayer film according to claim 7, wherein the crosslinking agent (C) is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

9. A resist underlayer film, which is a cured product of the composition for forming a resist underlayer film according to any one of claims 1 to 8.

10. A laminate comprising: a semiconductor substrate; and the resist underlayer film according to claim 9.

11. A method for manufacturing a semiconductor device, comprising: a step of forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of claims 1 to 8; and a step of forming a resist film on the resist underlayer film.

12. A pattern formation method comprising: a step of forming a resist underlayer film on a semiconductor substrate using a composition for forming a resist underlayer film according to any one of claims 1 to 8; 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 and 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.

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